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Atmospheric Pressure Plasma Synthesized Gold Nanoparticle/Carbon Nanotube Hybrids for Photo-thermal ConversionDaye Sun,? James McLaughlan,?,§ Li Zhang,∥ Brian G. Falzon,? Davide Mariotti,⊥? Paul Maguire,⊥ Dan Sun,* ??Advanced Composites Research Group (ACRG), School of Mechanical and Aerospace Engineering, Queen’s University, Belfast, UK?School of Electronic and Electrical Engineering, University of Leeds, UK§Leeds Institute of Cancer and Pathology, University of Leeds, UK∥Research Center for Nano-Biomaterials, Analytical & Testing Center, Sichuan University, Chengdu, China⊥Nanotechnology and Integrated Bioengineering Centre, Ulster University, UKKEYWORDS: Gold Nanoparticles, Carbon Nanotubes, Plasma Synthesis, Surface Enhanced Raman Scattering, Photothermal Conversion ABSTRACT: In this work, a room temperature atmospheric pressure direct-current plasma has been deployed for the one-step synthesis of gold nanoparticle/carboxyl group functionalized carbon nanotube (AuNP/CNT-COOH) nanohybrids in aqueous solution for the first time. Uniformly distributed AuNPs are formed on the surface of CNT-COOH, without the use of reducing agents or surfactants. The size of the AuNP can be tuned by changing the gold salt precursor concertation. UV-Vis, ζ-potential and X-ray photoelectron spectroscopy suggest that carboxyl surface functional groups on CNTs served as nucleation and growth sites for AuNPs and the multiple potential reaction pathways induced by the plasma-chemistry have been elucidated in detail. The nanohybrids exhibit significantly enhanced Raman scattering and photothermal conversion efficiency, properties that are essential for potential multi-modal cancer treatment applications.1. INTRODUCTIONAuNPs are currently approved by the Food and Drug Administration (FDA)ADDIN CSL_CITATION {"citationItems":[{"id":"ITEM-1","itemData":{"DOI":"10.1002/btm2.10003","ISBN":"0039022643407","ISSN":"23806761","PMID":"25319803","abstract":"Nature continues to be the ultimate in nanotechnology, where polymeric nanometer-scale architectures play a central role in biological systems. Inspired by the way nature forms functional supramolecular assemblies, researchers are trying to make nanostructures and to incorporate these into macrostructures as nature does. Recent advances and progress in nanoscience have demonstrated the great potential that nanomaterials have for applications in healthcare. In the realm of drug delivery, nanomaterials have been used in vivo to protect the drug entity in the systemic circulation, ensuring reproducible absorption of bioactive molecules that do not naturally penetrate biological barriers, restricting drug access to specific target sites. Several building blocks have been used in the formulation of nanoparticles. Thus, stability, drug release, and targeting can be tailored by surface modification. Herein the state of the art of stimuli-responsive polymeric nanoparticles are reviewed. Such systems are able to control drug release by reacting to naturally occurring or external applied stimuli. Special attention is paid to the design and nanoparticle formulation of these so-called smart drug-delivery systems. Future strategies for further developments of a promising controlled drug delivery responsive system are also outlined.","author":[{"dropping-particle":"","family":"Anselmo","given":"Aaron C.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Mitragotri","given":"Samir","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Bioengineering & Translational Medicine","id":"ITEM-1","issue":"1","issued":{"date-parts":[["2016"]]},"page":"10-29","title":"Nanoparticles in the clinic","type":"article-journal","volume":"1"},"uris":[""]}],"mendeley":{"formattedCitation":"¹","plainTextFormattedCitation":"1","previouslyFormattedCitation":"¹"},"properties":{"noteIndex":0},"schema":""}1 for non-invasive biomedical applications and have been widely explored in cancer treatment for drug delivery, bio-imaging, diagnose and photothermal therapy (PTT) due to their unique physical/chemical properties and high biocompatibility.ADDIN CSL_CITATION {"citationItems":[{"id":"ITEM-1","itemData":{"DOI":"10.1021/am3012752","ISBN":"1944-8252 (Electronic)\\r1944-8244 (Linking)","ISSN":"19448244","PMID":"23106388","abstract":"Five-nanometer sized gold nanoparticles (Au NPs) stabilized with citrate ions have been reacted with various amounts of dihydrolipoic acid (DHLA) (×28, ×56, ×140, ×222, relative to Au NPs). Ligand exchange between citrate and the dithiol resulted in DHLA-capped Au NPs, whose degree of inertia was found to be related to the density of capping. The results revealed the importance of DHLA coating density to enhance the colloidal stability and modulate the reactivity toward free radicals and proteins of biological relevance. Thus, Au NPs capped with the highest amount of DHLA were found to be the ones that were, first, the most resistant to environmental changes, then characterized by the lowest residual catalytic reactivity of their metallic core, and finally the lowest interacting with proteins through nonspecific adsorption. The physicochemical properties conferred to Au NPs prepared with the ×222 excess should be valuable for further pharmaceutical development of nanoparticle platforms.","author":[{"dropping-particle":"","family":"Tournebize","given":"Juliana","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Boudier","given":"Ariane","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Sapin-Minet","given":"Anne","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Maincent","given":"Philippe","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Leroy","given":"Pierre","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Schneider","given":"Rapha?l","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"ACS Applied Materials and Interfaces","id":"ITEM-1","issue":"11","issued":{"date-parts":[["2012"]]},"page":"5790-5799","title":"Role of gold nanoparticles capping density on stability and surface reactivity to design drug delivery platforms","type":"article-journal","volume":"4"},"uris":["",""]},{"id":"ITEM-2","itemData":{"DOI":"10.1021/nl8029114","ISBN":"1530-6984","ISSN":"1530-6984","PMID":"18983199","abstract":"X-ray based computed tomography (CT) is among the most convenient imaging/diagnostic tools in hospitals today in terms of availability, efficiency, and cost. However, in contrast to magnetic resonance imaging (MRI) and various nuclear medicine imaging modalities, CT is not considered a molecular imaging modality since targeted and molecularly specific contrast agents have not yet been developed. Here we describe a targeted molecular imaging platform that enables, for the first time, cancer detection at the cellular and molecular level with standard clinical CT. The method is based on gold nanoprobes that selectively and sensitively target tumor selective antigens while inducing distinct contrast in CT imaging (increased X-ray attenuation). We present an in vitro proof of principle demonstration for head and neck cancer, showing that the attenuation coefficient for the molecularly targeted cells is over 5 times higher than for identical but untargeted cancer cells or for normal cells. We expect this novel imaging tool to lead to significant improvements in cancer therapy due to earlier detection, accurate staging, and microtumor identification.","author":[{"dropping-particle":"","family":"Popovtzer","given":"Rachela","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Popovtzer","given":"Rachela","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Agrawal","given":"Ashish","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Agrawal","given":"Ashish","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Kotov","given":"Nicholas A","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Kotov","given":"Nicholas A","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Popovtzer","given":"Aron","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Popovtzer","given":"Aron","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Balter","given":"James","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Balter","given":"James","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Carey","given":"Thomas E","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Carey","given":"Thomas E","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Kopelman","given":"Raoul","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Kopelman","given":"Raoul","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Nano letters","id":"ITEM-2","issue":"12","issued":{"date-parts":[["2008"]]},"page":"4593-4596","title":"Targeted Gold Nanoparticles Enable Molecular CT Imaging of Cancer.","type":"article","volume":"8"},"uris":[""]},{"id":"ITEM-3","itemData":{"DOI":"10.1021/acsami.5b11192","ISSN":"1944-8244","PMID":"26883478","abstract":"Timely and accurate diagnosis of cancer is crucial to cancer treatment. However, serological diagnosis of cancer still faces great challenge because the conventional methodology based on the enzyme-linked immune sorbent assay (ELISA) is costly, time-consuming, and complicated, involving multiple steps. Herein, lactose-functionalized gold nanorods (Lac-GNRs) are fabricated as efficient biosensors to detect cancerous conditions based on the unique surface plasmon resonance properties of GNRs and high specificity of lactose to the galectin-1 cancer biomarker. A trace concentration of galectin-1 as small as 10 ?13 M can be detected by Lac-GNRs. The comparative study among BSA, galectin-3, and galectin-1 demonstrates the good specificity of Lac-GNRs to galectin-1 either in aqueous solutions or in the complex and heterogeneous serum specimens. Clinical tests show that the Lac-GNRs biosensors can readily distinguish the serums of cancer patients from those of healthy persons simply by using a microplate reader or even direct visual observation. The Lac-GNRs biosensing platform is highly efficient and easy to use and have great potential in rapid screening of cancer patients.","author":[{"dropping-particle":"","family":"Zhao","given":"Yuetao","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Tong","given":"Liping","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Li","given":"Yong","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Pan","given":"Haobo","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Zhang","given":"Wei","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Guan","given":"Min","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Li","given":"Weihao","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Chen","given":"Yixin","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Li","given":"Qing","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Li","given":"Zhongjun","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Wang","given":"Huaiyu","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Yu","given":"Xue-Feng","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Chu","given":"Paul K.","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"ACS Applied Materials & Interfaces","id":"ITEM-3","issue":"9","issued":{"date-parts":[["2016"]]},"page":"5813-5820","title":"Lactose-Functionalized Gold Nanorods for Sensitive and Rapid Serological Diagnosis of Cancer","type":"article-journal","volume":"8"},"uris":["",""]},{"id":"ITEM-4","itemData":{"DOI":"10.1021/am500302t","ISBN":"1944-8244","ISSN":"1944-8252","PMID":"24842534","abstract":"Nanoparticles of varying composition, size, shape, and architecture have been explored for use as photothermal agents in the field of cancer nanomedicine. Among them, gold nanoparticles provide a simple platform for thermal ablation owing to its biocompatibility in vivo. However, the synthesis of such gold nanoparticles exhibiting suitable properties for photothermal activity involves cumbersome routes using toxic chemicals as capping agents, which can cause concerns in vivo. Herein, gold nanoparticles, synthesized using green chemistry routes possessing near-infrared (NIR) absorbance facilitating photothermal therapy, would be a viable alternative. In this study, anisotropic gold nanoparticles were synthesized using an aqueous route with cocoa extract which served both as a reducing and stabilizing agent. The as-prepared gold nanoparticles were subjected to density gradient centrifugation to maximize its NIR absorption in the wavelength range of 800-1000 nm. The particles also showed good biocompatibility when tested in vitro using A431, MDA-MB231, L929, and NIH-3T3 cell lines up to concentrations of 200 μg/mL. Cell death induced in epidermoid carcinoma A431 cells upon irradiation with a femtosecond laser at 800 nm at a low power density of 6 W/cm(2) proved the suitability of green synthesized NIR absorbing anisotropic gold nanoparticles for photothermal ablation of cancer cells. These gold nanoparticles also showed good X-ray contrast when tested using computed tomography (CT), proving their feasibility for use as a contrast agent as well. This is the first report on green synthesized anisotropic and cytocompatible gold nanoparticles without any capping agents and their suitability for photothermal therapy.","author":[{"dropping-particle":"","family":"Fazal","given":"Sajid","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Jayasree","given":"Aswathy","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Sasidharan","given":"Sisini","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Koyakutty","given":"Manzoor","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"V","family":"Nair","given":"Shantikumar","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Menon","given":"Deepthy","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"ACS applied materials & interfaces","id":"ITEM-4","issued":{"date-parts":[["2014"]]},"page":"8080-8089","title":"Green Synthesis of Anisotropic Gold Nanoparticles for Photothermal Therapy of Cancer.","type":"article-journal","volume":"6"},"uris":[""]}],"mendeley":{"formattedCitation":"^2–5","plainTextFormattedCitation":"2–5","previouslyFormattedCitation":"^2–5"},"properties":{"noteIndex":0},"schema":""}2–5 Nanocarbon based materials, such as graphene, graphene oxide and carbon nanotubes (CNTs), on the other hand, have also been explored for a wide range of healthcare applications including cancer diagnostics, treatment, and sensing.ADDIN CSL_CITATION {"citationItems":[{"id":"ITEM-1","itemData":{"DOI":"10.1016/j.jcis.2018.10.050","ISSN":"10957103","abstract":"For personalized cancer treatment, developing smart biomaterials with multiple biological functions is indispensable in nanomedicine fields. In this work, we developed a highly efficient near-infrared- (NIR-) and pH-responsive carboxymethyl chitosan-functionalized reduced graphene oxide/aldehyde functionalized poly (ethylene glycol) (CMC-rGO/CHO-PEG) hydrogel, which exhibits outstanding delivery performance of antitumor drug, doxorubicin hydrochloride (DOX). CMC was functionalized on the GO nanosheets via a controllable approach in order to achieve strong NIR absorption property and good distribution of rGO. The intercalation effect of CMC-rGO complex improved rGO distribution in the 3D hydrogel, contributing to the enhanced photothermal performance of CMC-rGO/CHO-PEG hydrogel. Furthermore, potential utilization of these CMC-rGO/CHO-PEG hydrogel for drug loading was studied, which provided pH-sensitive release of DOX payload. Particularly, DOX could be released in a more efficient way under acidic environment (pH = 6.5) than that under physiological environment (pH = 7.4). Therefore, this rGO hybridized PEG hydrogel holds strategic potential as a novel drug release platform for combined chem-photothermal therapy.","author":[{"dropping-particle":"","family":"Liu","given":"Wei","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Zhang","given":"Xiaoyuan","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Zhou","given":"Lin","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Shang","given":"Li","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Su","given":"Zhiqiang","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Journal of Colloid and Interface Science","id":"ITEM-1","issued":{"date-parts":[["2019"]]},"title":"Reduced graphene oxide (rGO) hybridized hydrogel as a near-infrared (NIR)/pH dual-responsive platform for combined chemo-photothermal therapy","type":"article-journal"},"uris":[""]},{"id":"ITEM-2","itemData":{"DOI":"10.1016/j.bios.2016.01.081","ISBN":"0956-5663","ISSN":"18734235","PMID":"26856633","abstract":"Graphene (G)-based composite materials have been widely explored for the sensing applications ascribing to their atom-thick two-dimensional conjugated structures, high conductivity, large specific surface areas and controlled modification. With the enormous advantages of film structure, G-based composite films (GCFs), prepared by combining G with different functional nanomaterials (noble metals, metal compounds, carbon materials, polymer materials, etc.), show unique optical, mechanical, electrical, chemical, and catalytic properties. Therefore, great quantities of sensors with high sensitivity, selectivity, and stability have been created in recent years. In this review, we focus on the recent advances in the fabrication technologies of GCFs and their specific sensing applications. In addition, the relationship between the properties of GCFs and sensing performance is concentrated on. Finally, the personal perspectives and key challenges of GCFs are mentioned in the hope to shed a light on their potential future research directions.","author":[{"dropping-particle":"","family":"Yu","given":"Xiaoqing","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Zhang","given":"Wensi","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Zhang","given":"Panpan","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Su","given":"Zhiqiang","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Biosensors and Bioelectronics","id":"ITEM-2","issued":{"date-parts":[["2017"]]},"title":"Fabrication technologies and sensing applications of graphene-based composite films: Advances and challenges","type":"article"},"uris":[""]},{"id":"ITEM-3","itemData":{"DOI":"10.1039/c5nr00084j","ISSN":"20403372","PMID":"25735233","abstract":"The preparation and applications of graphene (G)-based materials are attracting increasing interests due to their unique electronic, optical, magnetic, thermal, and mechanical properties. Compared to G-based hybrid and composite materials, G-based inorganic hybrid membrane (GIHM) offers enormous advantages ascribed to their facile synthesis, planar two-dimensional multilayer structure, high specific surface area, and mechanical stability, as well as their unique optical and mechanical properties. In this review, we report the recent advances in the technical fabrication and structure-specific applications of GIHMs with desirable thickness and compositions. In addition, the advantages and disadvantages of the methods utilized for creating GIHMs are discussed in detail. Finally, the potential applications and key challenges of GIHMs for future technical applications are mentioned.","author":[{"dropping-particle":"","family":"Zhao","given":"Xinne","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Zhang","given":"Panpan","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Chen","given":"Yuting","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Su","given":"Zhiqiang","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Wei","given":"Gang","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Nanoscale","id":"ITEM-3","issued":{"date-parts":[["2015"]]},"title":"Recent advances in the fabrication and structure-specific applications of graphene-based inorganic hybrid membranes","type":"article-journal"},"uris":["",""]}],"mendeley":{"formattedCitation":"^6–8","plainTextFormattedCitation":"6–8","previouslyFormattedCitation":"^6–9"},"properties":{"noteIndex":0},"schema":""}6–8 CNTs, in particular, have gained increasing attention in cancer therapies for the delivery of anti-cancer drugs, hyperthermia, and bio-imaging in virtue of their unique structural, thermal, and chemical properties.ADDIN CSL_CITATION {"citationItems":[{"id":"ITEM-1","itemData":{"DOI":"10.1021/acsami.5b03739","ISSN":"19448252","PMID":"26107995","abstract":"Multidrug resistance and radioresistance are major obstacles for successful cancer therapy. Due to the unique characteristics of high surface area, improved cellular uptake, and the possibility to be easily bound with therapeutics, carbon nanotubes (CNTs) have attracted increasing attention as potential nanodrug delivery systems. In this study, a CNT-based radiosensitive nanodrug delivery system was rationally designed to antagonize the multidrug resistance in hepatocellular carcinoma. The nanosystem was loaded with a potent anticancer ruthenium polypyridyl complex (RuPOP) via π-π interaction and formation of a hydrogen bond. The functionalized nanosystem (RuPOP@MWCNTs) enhanced the cellular uptake of RuPOP in liver cancer cells, especially drug-resistant R-HepG2 cells, through endocytosis. Consistently, the selective cellular uptake endowed the nanosystem amplified anticancer efficacy against R-HepG2 cells but not in normal cells. Interestingly, RuPOP@MWCNTs significantly enhanced the anticancer efficacy of clinically used X-ray against R-HepG2 cells through induction of apoptosis and G0/G1 cell cycle arrest, with the involvement of ROS overproduction, which activated several downstream signaling pathways, including DNA damage-mediated p53 phosphorylation, activation of p38, and inactivation of AKT and ERK. Moreover, the nanosystem also effectively reduces the toxic side effects of loaded drugs and prolongs the blood circulation in vivo. Taken together, the results demonstrate the rational design of functionalized carbon nanotubes and their application as effective nanomedicine to overcome cancer multidrug resistance.","author":[{"dropping-particle":"","family":"Wang","given":"Ni","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Feng","given":"Yanxian","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Zeng","given":"Lilan","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Zhao","given":"Zhennan","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Chen","given":"Tianfeng","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"ACS Applied Materials and Interfaces","id":"ITEM-1","issue":"27","issued":{"date-parts":[["2015"]]},"page":"14933-14945","title":"Functionalized multiwalled carbon nanotubes as carriers of ruthenium complexes to antagonize cancer multidrug resistance and radioresistance","type":"article-journal","volume":"7"},"uris":["",""]},{"id":"ITEM-2","itemData":{"DOI":"10.1021/acsami.5b08087","ISBN":"1944-8252 (Electronic)\\r1944-8244 (Linking)","ISSN":"19448252","PMID":"26653008","abstract":"Lymph node (LN) status is a major indicator of stage and survival of lung cancer patients. LN dissection is a primary option for lung cancer LN metastasis; however, this strategy elicits adverse effects and great trauma. Therefore, developing a minimally invasive technique to cure LN metastasis of lung cancer is desired. In this study, multiwalled carbon nanotubes (MWNTs) coated with manganese oxide (MnO) and polyethylene glycol (PEG) (namely MWNTs-MnO-PEG) was employed as a lymphatic theranostic agent to diagnose and treat metastatic LNs. After single local injection and lymph drainage were performed, regional LNs were clearly mapped by T1-weighted magnetic resonance (MR) of MnO and dark dye imaging of MWNTs. Meanwhile, metastatic LNs could be simultaneously ablated by near-infrared (NIR) irradiation under the guidance of dual-modality mapping. The excellent result was obtained in mice bearing LNs metastasis models, showing that MWNTs-MnO-PEG as a multifunctional theranostic agent was competent for dual-modality mapping guided photothermal therapy of metastatic LNs.","author":[{"dropping-particle":"","family":"Wang","given":"Sheng","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Zhang","given":"Qin","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Yang","given":"Peng","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Yu","given":"Xiangrong","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Huang","given":"Li Yong","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Shen","given":"Shun","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Cai","given":"Sanjun","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"ACS Applied Materials and Interfaces","id":"ITEM-2","issue":"6","issued":{"date-parts":[["2016"]]},"page":"3736-3743","title":"Manganese Oxide-Coated Carbon Nanotubes As Dual-Modality Lymph Mapping Agents for Photothermal Therapy of Tumor Metastasis","type":"article-journal","volume":"8"},"uris":["",""]},{"id":"ITEM-3","itemData":{"DOI":"10.1038/nnano.2008.231","ISBN":"1748-3395 (Electronic)\\r1748-3387 (Linking)","ISSN":"1748-3387","PMID":"18772918","abstract":"Photoacoustic imaging of living subjects offers higher spatial resolution and allows deeper tissues to be imaged compared with most optical imaging techniques. As many diseases do not exhibit a natural photoacoustic contrast, especially in their early stages, it is necessary to administer a photoacoustic contrast agent. A number of contrast agents for photoacoustic imaging have been suggested previously, but most were not shown to target a diseased site in living subjects. Here we show that single-walled carbon nanotubes conjugated with cyclic Arg-Gly-Asp (RGD) peptides can be used as a contrast agent for photoacoustic imaging of tumours. Intravenous administration of these targeted nanotubes to mice bearing tumours showed eight times greater photoacoustic signal in the tumour than mice injected with non-targeted nanotubes. These results were verified ex vivo using Raman microscopy. Photoacoustic imaging of targeted single-walled carbon nanotubes may contribute to non-invasive cancer imaging and monitoring of nanotherapeutics in living subjects.","author":[{"dropping-particle":"","family":"la Zerda","given":"A","non-dropping-particle":"De","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Zavaleta","given":"C","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Keren","given":"S","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Vaithilingam","given":"S","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Bodapati","given":"S","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Liu","given":"Z","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Levi","given":"J","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Smith","given":"B R","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Ma","given":"T J","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Oralkan","given":"O","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Cheng","given":"Z","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Chen","given":"X","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Dai","given":"H","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Khuri-Yakub","given":"B T","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Gambhir","given":"S S","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Nat Nanotechnol","id":"ITEM-3","issue":"9","issued":{"date-parts":[["2008"]]},"page":"557-562","title":"Carbon nanotubes as photoacoustic molecular imaging agents in living mice","type":"article-journal","volume":"3"},"uris":["",""]}],"mendeley":{"formattedCitation":"^9–11","plainTextFormattedCitation":"9–11","previouslyFormattedCitation":"^10–12"},"properties":{"noteIndex":0},"schema":""}9–11 For instance, CNTs can effectively accumulate in tumour cells/tissues due to their enhanced permeability and retention effects induced by the defectiveness, leakage and abnormalities in tumour cells/tissues.ADDIN CSL_CITATION {"citationItems":[{"id":"ITEM-1","itemData":{"DOI":"10.1016/j.drudis.2006.07.005","ISBN":"1359-6446 (Print)\\n1359-6446 (Linking)","ISSN":"13596446","PMID":"16935749","abstract":"Of the tumor targeting strategies, the enhanced permeability and retention (EPR) effect of macromolecules is a key mechanism for solid tumor targeting, and considered a gold standard for novel drug design. In this review, we discuss various endogenous factors that can positively impact the EPR effect in tumor tissues. Further, we discuss ways to augment the EPR effect by use of exogenous agents, as well as practical methods available in the clinical setting. Some innovative examples developed by researchers to combat cancer by the EPR mechanism are also discussed. ? 2006 Elsevier Ltd. All rights reserved.","author":[{"dropping-particle":"","family":"Iyer","given":"Arun K.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Khaled","given":"Greish","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Fang","given":"Jun","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Maeda","given":"Hiroshi","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Drug Discovery Today","id":"ITEM-1","issue":"17-18","issued":{"date-parts":[["2006"]]},"page":"812-818","title":"Exploiting the enhanced permeability and retention effect for tumor targeting","type":"article","volume":"11"},"uris":["",""]},{"id":"ITEM-2","itemData":{"DOI":"10.1038/nnano.2009.231","ISBN":"1748-3387","ISSN":"17483395","PMID":"19809462","abstract":"Carbon nanotubes have shown promise as contrast agents for photoacoustic and photothermal imaging of tumours and infections because they offer high resolution and allow deep tissue imaging. However, in vivo applications have been limited by the relatively low absorption displayed by nanotubes at near-infrared wavelengths and concerns over toxicity. Here, we show that gold-plated carbon nanotubes-termed golden carbon nanotubes-can be used as photoacoustic and photothermal contrast agents with enhanced near-infrared contrast ( approximately 10(2)-fold) for targeting lymphatic vessels in mice using extremely low laser fluence levels of a few mJ cm(-2). Antibody-conjugated golden carbon nanotubes were used to map the lymphatic endothelial receptor, and preliminary in vitro viability tests show golden carbon nanotubes have minimal toxicity. This new nanomaterial could be an effective alternative to existing nanoparticles and fluorescent labels for non-invasive targeted imaging of molecular structures in vivo.","author":[{"dropping-particle":"","family":"Kim","given":"Jin Woo","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Galanzha","given":"Ekaterina I.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"V.","family":"Shashkov","given":"Evgeny","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Moon","given":"Hyung Mo","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Zharov","given":"Vladimir P.","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Nature Nanotechnology","id":"ITEM-2","issue":"10","issued":{"date-parts":[["2009"]]},"page":"688-694","publisher":"Nature Publishing Group","title":"Golden carbon nanotubes as multimodal photoacoustic and photothermal high-contrast molecular agents","type":"article-journal","volume":"4"},"uris":[""]},{"id":"ITEM-3","itemData":{"DOI":"10.1021/ja303737a","ISBN":"0002-7863","ISSN":"00027863","PMID":"22667448","abstract":"Cancer imaging requires selective high accumulation of contrast agents in the tumor region and correspondingly low uptake in healthy tissues. Here, by making use of a novel synthetic polymer to solubilize single-walled carbon nanotubes (SWNTs), we prepared a well-functionalized SWNT formulation with long blood circulation (half-life of ～30 h) in vivo to achieve ultrahigh accumulation of ～30% injected dose (ID)/g in 4T1 murine breast tumors in Balb/c mice. Functionalization dependent blood circulation and tumor uptake were investigated through comparisons with phospholipid-PEG solubilized SWNTs. For the first time, we performed video-rate imaging of tumors based on the intrinsic fluorescence of SWNTs in the second near-infrared (NIR-II, 1.1-1.4 μm) window. We carried out dynamic contrast imaging through principal component analysis (PCA) to immediately pinpoint the tumor within ～20 s after injection. Imaging over time revealed increasing tumor contrast up to 72 h after injection, allowing for its unambiguous identification. The 3D reconstruction of the SWNTs distribution based on their stable photoluminescence inside the tumor revealed a high degree of colocalization of SWNTs and blood vessels, suggesting enhanced permeability and retention (EPR) effect as the main cause of high passive tumor uptake of the nanotubes.","author":[{"dropping-particle":"","family":"Robinson","given":"Joshua T.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Hong","given":"Guosong","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Liang","given":"Yongye","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Zhang","given":"Bo","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Yaghi","given":"Omar K.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Dai","given":"Hongjie","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Journal of the American Chemical Society","id":"ITEM-3","issue":"25","issued":{"date-parts":[["2012"]]},"page":"10664-10669","title":"In vivo fluorescence imaging in the second near-infrared window with long circulating carbon nanotubes capable of ultrahigh tumor uptake","type":"article-journal","volume":"134"},"uris":["",""]}],"mendeley":{"formattedCitation":"^12–14","plainTextFormattedCitation":"12–14","previouslyFormattedCitation":"^13–15"},"properties":{"noteIndex":0},"schema":""}12–14 Although the toxicity issue of CNTs remains controversial, it is believed to be closely related to the dosage used as well as the structure/properties of the CNTs (such as length, diameter, alignment, degree of entanglement surface functionalities.ADDIN CSL_CITATION {"citationItems":[{"id":"ITEM-1","itemData":{"DOI":"10.1038/nbt0708-774","ISBN":"1087-0156","ISSN":"10870156","PMID":"18612299","abstract":"Toxicological and pharmacological studies suggest guidelines for the safe use of carbon nanotubes in medicine.","author":[{"dropping-particle":"","family":"Kostarelos","given":"Kostas","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Nature Biotechnology","id":"ITEM-1","issued":{"date-parts":[["2008"]]},"title":"The long and short of carbon nanotube toxicity","type":"article"},"uris":["",""]},{"id":"ITEM-2","itemData":{"DOI":"10.1021/ar300028m","ISBN":"1520-4898 (Electronic)\\n0001-4842 (Linking)","ISSN":"00014842","PMID":"22999420","abstract":"Because of their unique physical, chemical, electrical, and mechanical properties, carbon nanotubes (CNTs) have attracted a great deal of research interest and have many potential applications. As large-scale production and application of CNTs increases, the general population is more likely to be exposed to CNTs either directly or indirectly, which has prompted considerable attention about human health and safety issues related to CNTs. Although considerable experimental data related to CNT toxicity at the molecular, cellular, and whole animal levels have been published, the results are often conflicting. Therefore, a systematic understanding of CNT toxicity is needed but has not yet been developed. In this Account, we highlight recent investigations into the basis of CNT toxicity carried out by our team and by other laboratories. We focus on several important factors that explain the disparities in the experimental results of nanotoxicity, such as impurities, amorphous carbon, surface charge, shape, length, agglomeration, and layer numbers. The exposure routes, including inhalation, intravenous injection, or dermal or oral exposure, can also influence the in vivo behavior and fate of CNTs. The underlying mechanisms of CNT toxicity include oxidative stress, inflammatory responses, malignant transformation, DNA damage and mutation (errors in chromosome number as well as disruption of the mitotic spindle), the formation of granulomas, and interstitial fibrosis. These findings provide useful insights for de novo design and safe application of carbon nanotubes and their risk assessment to human health. To obtain reproducible and accurate results, researchers must establish standards and reliable detection methods, use standard CNT samples as a reference control, and study the impact of various factors systematically. In addition, researchers need to examine multiple types of CNTs, different cell lines and animal species, multidimensional evaluation methods, and exposure conditions. To make results comparable among different institutions and countries, researchers need to standardize choices in toxicity testing such as that of cell line, animal species, and exposure conditions. The knowledge presented here should lead to a better understanding of the key factors that can influence CNT toxicity so that their unwanted toxicity might be avoided.","author":[{"dropping-particle":"","family":"Liu","given":"Ying","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Zhao","given":"Yuliang","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Sun","given":"Baoyun","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Chen","given":"Chunying","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Accounts of Chemical Research","id":"ITEM-2","issued":{"date-parts":[["2013"]]},"title":"Understanding the toxicity of carbon nanotubes","type":"article-journal"},"uris":["",""]}],"mendeley":{"formattedCitation":"^15,16","plainTextFormattedCitation":"15,16","previouslyFormattedCitation":"^16,17"},"properties":{"noteIndex":0},"schema":""}15,16) and therefore cannot be generalized.ADDIN CSL_CITATION {"citationItems":[{"id":"ITEM-1","itemData":{"DOI":"10.1016/j.carbon.2007.03.035","ISBN":"0008-6223","ISSN":"00086223","abstract":"Carbon nanotube (CNT) mediated delivery system of drugs etc. has currently aroused a large interest. Because the delivery system will be ultimately introduced into the human body, the information about the in vivo biological behavior and consequences of CNTs becomes very important. Here, using [14C-taurine]-multi-walled CNTs (MWCNTs) as tracers, we show the biodistribution and translocation pathways of MWCNTs in mice by three different routes. After mice were exposed by intravenous injection, MWCNTs predominately accumulated in liver and retained for long time. Transmission electron micrographs clearly show the remarkable entrapment of MWCNTs in hepatic macrophages (Kupffer cells). The biological index examinations indicate low liver acute toxicity of MWCNTs. Some favorable aspects of MWCNTs being used as a drug nanovehicle are also discussed. ? 2007 Elsevier Ltd. All rights reserved.","author":[{"dropping-particle":"","family":"Deng","given":"X.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Jia","given":"G.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Wang","given":"H.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Sun","given":"H.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Wang","given":"X.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Yang","given":"S.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Wang","given":"T.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Liu","given":"Y.","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Carbon","id":"ITEM-1","issued":{"date-parts":[["2007"]]},"title":"Translocation and fate of multi-walled carbon nanotubes in vivo","type":"article-journal"},"uris":["",""]},{"id":"ITEM-2","itemData":{"DOI":"10.3109/17435390.2010.509519","ISBN":"1743-5404 (Electronic)\\r1743-5390 (Linking)","ISSN":"17435390","PMID":"20858045","abstract":"Nanotoxicology studies require investigations of several physico-chemical aspects of the particle/body fluid interaction, here described by reviewing recent literature in the light of new experimental data. Current characterization mostly covers morphology and metric-related characteristics (form, chemical composition, specific surface area, primary particle size and size distribution), and is mandatory in any experimental study. To unveil toxicity mechanisms, several other physico-chemical properties relevant to (geno) toxicity need to be assessed, typically the release or quenching of radical/ROS (Reactive Oxygen Species), the presence of active metal ions, evidence of structural defects. Major tasks for physical chemists working on nanoparticles-induced genotoxicity are described with some examples: (i), Tailored preparation of the same material in different sizes; (ii) particle modification changing a single property at a time; and (iii) identification of appropriate reference materials. Phenomena occurring during the contact between nanoparticles and cellular media or biological fluids (dispersion, agglomeration/aggregation, protein adsorption) are discussed in relation to the surface properties of the nanoparticles considered.","author":[{"dropping-particle":"","family":"Fubini","given":"Bice","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Ghiazza","given":"Mara","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Fenoglio","given":"Ivana","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Nanotoxicology","id":"ITEM-2","issued":{"date-parts":[["2010"]]},"title":"Physico-chemical features of engineered nanoparticles relevant to their toxicity","type":"article"},"uris":["",""]},{"id":"ITEM-3","itemData":{"DOI":"10.1038/nnano.2008.111","ISBN":"1748-3387","ISSN":"17483395","PMID":"18654567","abstract":"Carbon nanotubes have distinctive characteristics, but their needle-like fibre shape has been compared to asbestos, raising concerns that widespread use of carbon nanotubes may lead to mesothelioma, cancer of the lining of the lungs caused by exposure to asbestos. Here we show that exposing the mesothelial lining of the body cavity of mice, as a surrogate for the mesothelial lining of the chest cavity, to long multiwalled carbon nanotubes results in asbestos-like, length-dependent, pathogenic behaviour. This includes inflammation and the formation of lesions known as granulomas. This is of considerable importance, because research and business communities continue to invest heavily in carbon nanotubes for a wide range of products under the assumption that they are no more hazardous than graphite. Our results suggest the need for further research and great caution before introducing such products into the market if long-term harm is to be avoided.","author":[{"dropping-particle":"","family":"Poland","given":"Craig A.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Duffin","given":"Rodger","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Kinloch","given":"Ian","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Maynard","given":"Andrew","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Wallace","given":"William A.H.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Seaton","given":"Anthony","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Stone","given":"Vicki","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Brown","given":"Simon","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"MacNee","given":"William","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Donaldson","given":"Ken","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Nature Nanotechnology","id":"ITEM-3","issued":{"date-parts":[["2008"]]},"title":"Carbon nanotubes introduced into the abdominal cavity of mice show asbestos-like pathogenicity in a pilot study","type":"article-journal"},"uris":["",""]},{"id":"ITEM-4","itemData":{"DOI":"10.1039/b502429c","ISBN":"1742-206X","ISSN":"1742-206X","PMID":"16880981","abstract":"Carbon nanotubes (CNTs) are single-or multi-cylindrical graphene structures that possess diameters of a few nanometers, while the length can be up to a few micrometers. These could have unusual toxicological properties, in that they share intermediate morphological characteristics of both fibers and nanoparticles. To date, no detailed study has been carried out to determine the effect of length on CNT cytotoxicity. In this paper, we investigated the activation of the human acute monocytic leukemia cell line THP-1 in vitro and the response in subcutaneous tissue in vivo to CNTs of different lengths. We used 220 nm and 825 nm-long CNT samples for testing, referred to as ''220-CNTs'' and ''825-CNTs'', respectively. 220-CNTs and 825-CNTs induced human monocytes in vitro, although the activity was significantly lower than that of microbial lipopeptide and lipopolysaccharide, and no activity appeared following variation in the length of CNTs. On the other hand, the degree of inflammatory response in subcutaneous tissue in rats around the 220-CNTs was slight in comparison with that around the 825-CNTs. These results indicated that the degree of inflammation around 825-CNTs was stronger than that around 220-CNTs since macrophages could envelop 220-CNTs more readily than 825-CNTs. However, no severe inflammatory response such as necrosis, degeneration or neutrophil infiltration in vivo was observed around both CNTs examined throughout the experimental period.","author":[{"dropping-particle":"","family":"Sato","given":"Yoshinori","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Yokoyama","given":"Atsuro","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Shibata","given":"Ken-ichiro","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Akimoto","given":"Yuki","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Ogino","given":"Shin-ichi","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Nodasaka","given":"Yoshinobu","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Kohgo","given":"Takao","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Tamura","given":"Kazuchika","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Akasaka","given":"Tsukasa","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Uo","given":"Motohiro","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Motomiya","given":"Kenichi","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Jeyadevan","given":"Balachandran","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Ishiguro","given":"Mikio","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Hatakeyama","given":"Rikizo","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Watari","given":"Fumio","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Tohji","given":"Kazuyuki","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Molecular BioSystems","id":"ITEM-4","issued":{"date-parts":[["2005"]]},"title":"Influence of length on cytotoxicity of multi-walled carbon nanotubes against human acute monocytic leukemia cell line THP-1 in vitro and subcutaneous tissue of rats in vivo","type":"article-journal"},"uris":["",""]}],"mendeley":{"formattedCitation":"^17–20","plainTextFormattedCitation":"17–20","previouslyFormattedCitation":"^18–21"},"properties":{"noteIndex":0},"schema":""}17–20 For these reasons, further efforts are still required to control the dosage-related toxicity of CNTs and to improve the tumour-targeting efficiency of AuNPs in cancer applications.ADDIN CSL_CITATION {"citationItems":[{"id":"ITEM-1","itemData":{"DOI":"10.1038/nnano.2009.231","ISBN":"1748-3387","ISSN":"17483395","PMID":"19809462","abstract":"Carbon nanotubes have shown promise as contrast agents for photoacoustic and photothermal imaging of tumours and infections because they offer high resolution and allow deep tissue imaging. However, in vivo applications have been limited by the relatively low absorption displayed by nanotubes at near-infrared wavelengths and concerns over toxicity. Here, we show that gold-plated carbon nanotubes-termed golden carbon nanotubes-can be used as photoacoustic and photothermal contrast agents with enhanced near-infrared contrast ( approximately 10(2)-fold) for targeting lymphatic vessels in mice using extremely low laser fluence levels of a few mJ cm(-2). Antibody-conjugated golden carbon nanotubes were used to map the lymphatic endothelial receptor, and preliminary in vitro viability tests show golden carbon nanotubes have minimal toxicity. This new nanomaterial could be an effective alternative to existing nanoparticles and fluorescent labels for non-invasive targeted imaging of molecular structures in vivo.","author":[{"dropping-particle":"","family":"Kim","given":"Jin Woo","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Galanzha","given":"Ekaterina I.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"V.","family":"Shashkov","given":"Evgeny","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Moon","given":"Hyung Mo","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Zharov","given":"Vladimir P.","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Nature Nanotechnology","id":"ITEM-1","issue":"10","issued":{"date-parts":[["2009"]]},"page":"688-694","publisher":"Nature Publishing Group","title":"Golden carbon nanotubes as multimodal photoacoustic and photothermal high-contrast molecular agents","type":"article-journal","volume":"4"},"uris":[""]},{"id":"ITEM-2","itemData":{"DOI":"10.1021/acs.chemmater.6b05164","ISSN":"15205002","abstract":"Cell-mediated nanoparticle delivery has been proposed for an effective cancer therapy. However, there are limitations in loading nanoparticles within cells as the internalized nanoparticles cause cytotoxicity and leak out of the cells via exocytosis. Here, we introduce hybrid sheets composed of gold nanoparticles (AuNPs) and graphene oxide (GO), which stably adhere to the cell surface and exhibit a remarkable photothermal effect. To form AuNP/GO sheets in which GO is sandwiched between two AuNP monolayers, AuNPs are coated with α-synuclein protein and subsequently adsorbed onto GO sheets. Attaching AuNP/GO sheets to the tumor-tropic mesenchymal stem cell (MSC) surface enhances the loading efficiency of AuNPs in MSCs by avoiding the cytotoxicity and exocytosis issues. Furthermore, the tight packing of AuNPs on microscaled GO sheets enhances the photothermal effect via strong plasmon coupling between AuNPs. The injection of AuNP/GO sheet-attached MSCs into tumor-bearing mice significantly improves the photo...","author":[{"dropping-particle":"","family":"Kang","given":"Seokyung","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Lee","given":"Junghee","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Ryu","given":"Seungmi","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Kwon","given":"Yeji","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Kim","given":"Kyung Hun","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Jeong","given":"Dae Hong","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Paik","given":"Seung R.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Kim","given":"Byung Soo","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Chemistry of Materials","id":"ITEM-2","issue":"8","issued":{"date-parts":[["2017"]]},"page":"3461-3476","title":"Gold Nanoparticle/Graphene Oxide Hybrid Sheets Attached on Mesenchymal Stem Cells for Effective Photothermal Cancer Therapy","type":"article-journal","volume":"29"},"uris":[""]}],"mendeley":{"formattedCitation":"^13,21","plainTextFormattedCitation":"13,21","previouslyFormattedCitation":"^14,22"},"properties":{"noteIndex":0},"schema":""}13,21 The creation of AuNP/CNT hybrid nano-systems with enhanced opto-thermic properties may offer the opportunity to address these specific challenges, for instance by reducing the dosage. In this sense, fundamental opto-thermic properties of AuNP/CNT hybrids are very important and can be used to optimize the nano-systems and assess initial viability. This approach avoids carrying out full and extensive toxicity studies on a very large range of morphologies, chemical compositions, configurations etc. Such hybrid may also potentially serve as a new nanomedicine platform providing multi-theranostic functions including cellular imaging/detection, photothermal therapy, and cancer drug delivery.ADDIN CSL_CITATION {"citationItems":[{"id":"ITEM-1","itemData":{"DOI":"10.1021/ja300140c","ISBN":"0002-7863","ISSN":"1520-5126","PMID":"22486413","abstract":"Single-walled carbon nanotubes (SWNTs) with various unique optical properties are interesting nanoprobes widely explored in biomedical imaging and phototherapies. Herein, DNA-functionalized SWNTs are modified with noble metal (Ag or Au) nanoparticles via an in situ solution phase synthesis method comprised of seed attachment, seeded growth, and surface modification with polyethylene glycol (PEG), yielding SWNT-Ag-PEG and SWNT-Au-PEG nanocomposites stable in physiological environments. With gold or silver nanoparticles decorated on the surface, the SWNT-metal nanocomposites gain an excellent concentration and excitation-source dependent surface-enhanced Raman scattering (SERS) effect. Using a near-infrared (NIR) laser as the excitation source, targeted Raman imaging of cancer cells labeled with folic acid (FA) conjugated SWNT-Au nanocomposite (SWNT-Au-PEG-FA) is realized, with images acquired in significantly shortened periods of time as compared to that of using nonenhanced SWNT Raman probes. Owing to the strong surface plasmon resonance absorption contributed by the gold shell, the SWNTs-Au-PEG-FA nanocomposite also offers remarkably improved photothermal cancer cell killing efficacy. This work presents a facile approach to synthesize water-soluble noble metal coated SWNTs with a strong SERS effect suitable for labeling and fast Raman spectroscopic imaging of biological samples, which has been rarely realized before. The SWNT-Au-PEG nanocomposite developed here may thus be an interesting optical theranostic probe for cancer imaging and therapy.","author":[{"dropping-particle":"","family":"Wang","given":"Xiaojing","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Wang","given":"Chao","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Cheng","given":"Liang","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Lee","given":"Shuit-Tong","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Liu","given":"Zhuang","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Journal of the American Chemical Society","id":"ITEM-1","issue":"17","issued":{"date-parts":[["2012"]]},"page":"7414-22","title":"Noble metal coated single-walled carbon nanotubes for applications in surface enhanced Raman scattering imaging and photothermal therapy.","type":"article-journal","volume":"134"},"uris":[""]},{"id":"ITEM-2","itemData":{"DOI":"10.1021/am406031n","ISSN":"1944-8244","PMID":"24606763","abstract":"Golden single-walled carbon nanotubes (SWNTs) were prepared by growing gold nanoparticles onto the bilayer polysaccharide functionalized SWNTs. The layer-by-layer self-assembly of sodium alginate and chitosan on SWNTs provided an ideal surface with high density of active metal-binding groups such as amino and carboxylic acid groups, and then an approach of seed growth was adopted to facilitate the formation of gold nanoparticles coated SWNTs. The resulting golden SWNT hybrids have good water dispersibility and biocompatibility and tend to enter cancer cells. Interestingly, they have an enhanced NIR absorption and effectively transfer NIR laser into heat. The material can quickly cause localized hyperthermia, resulting in rapid cell death, and therefore appears to act as a highly effective photothermal converter for cancer ablation.","author":[{"dropping-particle":"","family":"Meng","given":"Lingjie","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Xia","given":"Wenjian","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Liu","given":"Li","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Niu","given":"Lvye","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Lu","given":"Qinghua","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"ACS Applied Materials & Interfaces","id":"ITEM-2","issue":"7","issued":{"date-parts":[["2014"]]},"page":"4989-4996","title":"Golden Single-Walled Carbon Nanotubes Prepared Using Double Layer Polysaccharides Bridge for Photothermal Therapy","type":"article-journal","volume":"6"},"uris":[""]},{"id":"ITEM-3","itemData":{"DOI":"10.1039/C6TB02755E","ISBN":"2050-750X\\r2050-7518","ISSN":"2050-750X","abstract":"Combining doxorubicin with thermal therapy in the clinic has led to startling results in the treatment of problematic cancers. Here, we describe a multimodal multi-walled carbon nanotube material that combines tumor targeting, doxorubicin delivery, and photothermal therapy for localized cancer treatment. The agent was constructed layer-by-layer from polypyrrole and gold nanoparticles on multi-walled carbon nanotubes. The gold surface was modified with tumor targeting folic acid terminated PEGylated chains, which also provide water-dispersibility, biocompatibility and should extend the half-life in blood. The material has a high loading/unloading capacity for the cytotoxic agent doxorubicin. Release of the doxorubicin, combined with the photothermal properties of the material that induces localized hyperthermia, leads to efficient cancer cell death.","author":[{"dropping-particle":"","family":"Wang","given":"Daquan","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Hou","given":"Chen","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Meng","given":"Lingjie","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Long","given":"Jiangang","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Jing","given":"Jiange","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Dang","given":"Dongfeng","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Fei","given":"Zhaofu","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Dyson","given":"Paul J.","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"J. Mater. Chem. B","id":"ITEM-3","issue":"7","issued":{"date-parts":[["2017"]]},"page":"1380-1387","publisher":"Royal Society of Chemistry","title":"Stepwise growth of gold coated cancer targeting carbon nanotubes for the precise delivery of doxorubicin combined with photothermal therapy","type":"article-journal","volume":"5"},"uris":[""]},{"id":"ITEM-4","itemData":{"DOI":"10.1039/c2cc32313c","ISBN":"1364-548X (Electronic)\\r1359-7345 (Linking)","ISSN":"1359-7345","PMID":"22627619","abstract":"This communication reports the design of a novel aptamer conjugated gold nanocage decorated SWCNTs hybrid nanomaterial for targeted imaging and selective photothermal destruction of the prostate cancer cells.","author":[{"dropping-particle":"","family":"Khan","given":"Sadia Afrin","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Kanchanapally","given":"Rajashekhar","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Fan","given":"Zhen","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Beqa","given":"Lule","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Singh","given":"Anant Kumar","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Senapati","given":"Dulal","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Ray","given":"Paresh Chandra","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Chemical Communications","id":"ITEM-4","issue":"53","issued":{"date-parts":[["2012"]]},"page":"6711","title":"A gold nanocage–CNT hybrid for targeted imaging and photothermal destruction of cancer cells","type":"article-journal","volume":"48"},"uris":[""]},{"id":"ITEM-5","itemData":{"DOI":"10.1021/jacs.5b13475","ISBN":"1520-5126 (Electronic) 0002-7863 (Linking)","ISSN":"15205126","PMID":"27193381","abstract":"We report a new type of carbon nanotube ring (CNTR) coated with gold nanoparticles (CNTR@AuNPs) using CNTR as a template and surface attached redox-active polymer as a reducing agent. This nanostructure of CNTR bundle embedded in the gap of closely attached AuNPs can play multiple roles as a Raman probe to detect cancer cells and a photoacoustic (PA) contrast agent for imaging-guided cancer therapy. The CNTR@AuNP exhibits substantially higher Raman and optical signals than CNTR coated with a complete Au shell (CNTR@ AuNS) and straight CNT@AuNP. The extinction intensity of CNTR@AuNP is about 120-fold higher than that of CNTR at 808 nm, and the surface enhanced Raman scattering (SERS) signal of CNTR@AuNP is about 110 times stronger than that of CNTR, presumably due to the combined effects of enhanced coupling between the embedded CNTR and the plasmon mode of the closely attached AuNPs, and the strong electromagnetic field in the cavity of the AuNP shell originated from the intercoupling of AuNPs. The greatly enhanced PA signal and photothermal conversion property of CNTR@AuNP were successfully employed for imaging and imaging-guided cancer therapy in two tumor xenograft models. Experimental observations were further supported by numerical simulations and perturbation theory analysis.","author":[{"dropping-particle":"","family":"Song","given":"Jibin","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Wang","given":"Feng","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Yang","given":"Xiangyu","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Ning","given":"Bo","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Harp","given":"Mary G.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Culp","given":"Stephen H.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Hu","given":"Song","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Huang","given":"Peng","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Nie","given":"Liming","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Chen","given":"Jingyi","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Chen","given":"Xiaoyuan","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Journal of the American Chemical Society","id":"ITEM-5","issue":"22","issued":{"date-parts":[["2016"]]},"page":"7005-7015","title":"Gold Nanoparticle Coated Carbon Nanotube Ring with Enhanced Raman Scattering and Photothermal Conversion Property for Theranostic Applications","type":"article-journal","volume":"138"},"uris":[""]}],"mendeley":{"formattedCitation":"^22–26","plainTextFormattedCitation":"22–26","previouslyFormattedCitation":"^23–27"},"properties":{"noteIndex":0},"schema":""}22–26 Several strategies have been attempted for the synthesis of AuNP/CNT nanohybrids. Wet chemistry based synthesis is one of the most common approaches, where harsh/hazardous reducing chemicals (such as sodium borohydride) are normally required.ADDIN CSL_CITATION {"citationItems":[{"id":"ITEM-1","itemData":{"DOI":"10.1016/j.snb.2016.11.096","ISSN":"09254005","abstract":"The present work describes the synthesis of a nanocomposite between carbon nanotubes and gold nanoparticles through modified Brust-Schiffin route. Observations by XRD, TEM and TGA techniques showed an uniform, well-distributed and non-agglomerated dispersion of gold nanoparticles (7 ± 4 nm of average size) completely loaded onto MWCNTs surface. After further structural characterizations, the nanocomposite was casted onto a glassy carbon electrode and characterized by cyclic voltammetry. A seven-fold density current enhancement was observed, provided by the high superficial electroactive area of the active material. Sensing properties of so-synthesized nanocomposite were tested for dopamine detection in presence of ascorbic and uric acid by square wave voltammetry. After analytical parameters optimization, the dopamine-sensor presented linear range of 4.8 × 10?7–5.7 × 10?6 mol L?1 with detection and quantification limits of 7.1 × 10?8 and 2.4 × 10?7 mol L?1 respectively and high sensitivity. The proposed method was applied in synthetic cerebrospinal fluids samples and the detection of DA in presence of potentially interferences in real samples was performed with satisfactory results.","author":[{"dropping-particle":"","family":"Caetano","given":"Fabio R.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Felippe","given":"Leticia B.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Zarbin","given":"Aldo J.G.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Bergamini","given":"Márcio F.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Marcolino-Junior","given":"Luiz H.","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Sensors and Actuators, B: Chemical","id":"ITEM-1","issued":{"date-parts":[["2017"]]},"page":"43-50","title":"Gold nanoparticles supported on multi-walled carbon nanotubes produced by biphasic modified method and dopamine sensing application","type":"article-journal","volume":"243"},"uris":["",""]}],"mendeley":{"formattedCitation":"²⁷","plainTextFormattedCitation":"27","previouslyFormattedCitation":"²⁸"},"properties":{"noteIndex":0},"schema":""}27 Although greener reducing agents (such as gallic acid) has been proposed, wet chemistry based synthesis still remain laborious and mostly require elevated temperature, long processing time, and cumbersome cleansing processes.ADDIN CSL_CITATION {"citationItems":[{"id":"ITEM-1","itemData":{"DOI":"10.1016/j.bios.2014.09.021","ISBN":"1873-4235 (Electronic)\\r0956-5663 (Linking)","ISSN":"18734235","PMID":"25240957","abstract":"A plasmon-assisted fluoro-immunoassay (PAFI) was developed for the detection of the influenza virus by using Au nanoparticle (Au NP)-decorated carbon nanotubes (AuCNTs) that were synthesized using phytochemical composites at room temperature in deionized water. Specific antibodies (Abs) against the influenza virus were conjugated onto the surface of AuCNTs and cadmium telluride quantum dots (QDs), which had a photoluminescence intensity that varied as a function of virus concentration and a detection limit of 0.1. pg/mL for all three types of influenza viruses examined. The clinically isolated influenza viruses (A/Yokohama/110/2009 (H3N2)) were detected in the range of 50-10,000. PFU/mL, with a detection limit of 50. PFU/mL. From a series of proof-of-concept and clinical experiments, the developed PAFI biosensing system provided robust signal production and enhancement, as well as an excellent selectivity and sensitivity for influenza viruses. This nanoparticle-based technique could be potentially developed as an efficient detection platform for the influenza virus.","author":[{"dropping-particle":"","family":"Lee","given":"Jaewook","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Ahmed","given":"Syed Rahin","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Oh","given":"Sangjin","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Kim","given":"Jeonghyo","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Suzuki","given":"Tetsuro","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Parmar","given":"Kaushik","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Park","given":"Simon S.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Lee","given":"Jaebeom","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Park","given":"Enoch Y.","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Biosensors and Bioelectronics","id":"ITEM-1","issued":{"date-parts":[["2014"]]},"page":"311-317","title":"A plasmon-assisted fluoro-immunoassay using gold nanoparticle-decorated carbon nanotubes for monitoring the influenza virus","type":"article-journal","volume":"64"},"uris":["",""]}],"mendeley":{"formattedCitation":"²⁸","plainTextFormattedCitation":"28","previouslyFormattedCitation":"²⁹"},"properties":{"noteIndex":0},"schema":""}28 Raghuveer et al. proposed microwave assisted chemical reduction routines which could markedly reduce the reaction time, however, harsh reducing agents and potentially hazardous radiation source are inevitable.ADDIN CSL_CITATION {"citationItems":[{"id":"ITEM-1","itemData":{"DOI":"10.1021/cm051911g","ISBN":"0897-4756","ISSN":"08974756","author":[{"dropping-particle":"","family":"Raghuveer","given":"Makala S.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Agrawal","given":"Saurabh","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Bishop","given":"Nikki","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Ramanath","given":"Ganapathiraman","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Chemistry of Materials","id":"ITEM-1","issue":"6","issued":{"date-parts":[["2006"]]},"page":"1390-1393","title":"Microwave-assisted single-step functionalization and in situ derivatization of carbon nanotubes with gold nanoparticles","type":"article-journal","volume":"18"},"uris":[""]}],"mendeley":{"formattedCitation":"²⁹","plainTextFormattedCitation":"29","previouslyFormattedCitation":"³⁰"},"properties":{"noteIndex":0},"schema":""}29 Alternative methods, such as solid-state thermal evaporation or sputtering require more sophisticated facilities and AuNPs that formed randomly on the CNT surfaces are often aggregated.ADDIN CSL_CITATION {"citationItems":[{"id":"ITEM-1","itemData":{"DOI":"10.1016/j.carbon.2010.05.045","ISSN":"00086223","abstract":"Hybrid materials consisting of oxygen plasma-treated multiwalled carbon nanotubes decorated with metal nanoparticles (e.g., Rh, Pd, Au or Ni) can be tailored for the recognition of benzene vapors with high sensitivity and selectivity. Metal nanoparticles donate or accept a significant amount of charge upon adsorption of a target molecule, so as to affect electron transport in the nanotube. The plasma treatment enables the cleaning, activation, functionalization and metal decoration of carbon nanotubes in a single step, which offers enormous flexibility for tuning the interfacial properties of the resulting hybrid materials. When combined in a microsensor array operating at room temperature, the use of benzene-sensitive and benzene-insensitive metal-decorated multiwalled carbon nanotubes can provide selective detection of benzene at trace levels with a detection limit below 50 ppb. ?? 2010 Elsevier Ltd. All rights reserved.","author":[{"dropping-particle":"","family":"Leghrib","given":"Radouane","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Felten","given":"Alexandre","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Demoisson","given":"Fréderic","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Reniers","given":"Fran?ois","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Pireaux","given":"Jean Jacques","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Llobet","given":"Eduard","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Carbon","id":"ITEM-1","issue":"12","issued":{"date-parts":[["2010"]]},"page":"3477-3484","title":"Room-temperature, selective detection of benzene at trace levels using plasma-treated metal-decorated multiwalled carbon nanotubes","type":"article-journal","volume":"48"},"uris":[""]}],"mendeley":{"formattedCitation":"³⁰","plainTextFormattedCitation":"30","previouslyFormattedCitation":"³¹"},"properties":{"noteIndex":0},"schema":""}30 The hybridising of CNTs with AuNPs can also be achieved via electrochemical or electroless deposition, however, in both cases CNTs need to be immobilized on a substrate.ADDIN CSL_CITATION {"citationItems":[{"id":"ITEM-1","itemData":{"DOI":"10.1021/ja0508828","ISBN":"0002-7863","ISSN":"00027863","PMID":"15853300","abstract":"Noble metal nanoparticles can be electrodeposited on carbon nanotubes under potential control. The nanotube sidewalls serve both as the electrodeposition template and as the wire electrically connecting the deposited nanoparticles.","author":[{"dropping-particle":"","family":"Quinn","given":"Bernadette M.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Dekker","given":"Cees","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Lemay","given":"Serge G.","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Journal of the American Chemical Society","id":"ITEM-1","issue":"17","issued":{"date-parts":[["2005"]]},"page":"6146-6147","title":"Electrodeposition of noble metal nanoparticles on carbon nanotubes","type":"article-journal","volume":"127"},"uris":[""]},{"id":"ITEM-2","itemData":{"DOI":"10.1021/ja053479+","ISBN":"0002-7863","ISSN":"00027863","PMID":"16076167","abstract":"By simply supporting carbon nanotubes with a metal substrate of a redox potential lower than that of the metal ions to be reduced into nanoparticles, we have developed a facile yet versatile and effective substrate-enhanced electroless deposition (SEED) method for functionalizing nanotubes with a large variety of metal nanoparticles, including those otherwise impossible by more conventional electroless deposition methods, in the absence of any additional reducing agent. The nanotube-supported metal nanoparticles thus produced are electrochemically active, and the newly developed SEED process represents a significant advance in functionalization of carbon nanotubes with metal nanoparticles for a wide range of potential applications, including in advanced sensing and catalytic systems.","author":[{"dropping-particle":"","family":"Qu","given":"Liangti","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Dai","given":"Liming","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Journal of the American Chemical Society","id":"ITEM-2","issue":"31","issued":{"date-parts":[["2005"]]},"page":"10806-10807","title":"Substrate-enhanced electroless deposition of metal nanoparticles on carbon nanotubes","type":"article-journal","volume":"127"},"uris":[""]}],"mendeley":{"formattedCitation":"^31,32","plainTextFormattedCitation":"31,32","previouslyFormattedCitation":"^32,33"},"properties":{"noteIndex":0},"schema":""}31,32The application of AuNP/CNT hybrids specifically for cancer treatments has favoured other and more recent synthesis techniques. Layer-by-layer (LbL) assembly has been the main technique deployed to date.ADDIN CSL_CITATION {"citationItems":[{"id":"ITEM-1","itemData":{"DOI":"10.1021/ja300140c","ISBN":"0002-7863","ISSN":"1520-5126","PMID":"22486413","abstract":"Single-walled carbon nanotubes (SWNTs) with various unique optical properties are interesting nanoprobes widely explored in biomedical imaging and phototherapies. Herein, DNA-functionalized SWNTs are modified with noble metal (Ag or Au) nanoparticles via an in situ solution phase synthesis method comprised of seed attachment, seeded growth, and surface modification with polyethylene glycol (PEG), yielding SWNT-Ag-PEG and SWNT-Au-PEG nanocomposites stable in physiological environments. With gold or silver nanoparticles decorated on the surface, the SWNT-metal nanocomposites gain an excellent concentration and excitation-source dependent surface-enhanced Raman scattering (SERS) effect. Using a near-infrared (NIR) laser as the excitation source, targeted Raman imaging of cancer cells labeled with folic acid (FA) conjugated SWNT-Au nanocomposite (SWNT-Au-PEG-FA) is realized, with images acquired in significantly shortened periods of time as compared to that of using nonenhanced SWNT Raman probes. Owing to the strong surface plasmon resonance absorption contributed by the gold shell, the SWNTs-Au-PEG-FA nanocomposite also offers remarkably improved photothermal cancer cell killing efficacy. This work presents a facile approach to synthesize water-soluble noble metal coated SWNTs with a strong SERS effect suitable for labeling and fast Raman spectroscopic imaging of biological samples, which has been rarely realized before. The SWNT-Au-PEG nanocomposite developed here may thus be an interesting optical theranostic probe for cancer imaging and therapy.","author":[{"dropping-particle":"","family":"Wang","given":"Xiaojing","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Wang","given":"Chao","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Cheng","given":"Liang","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Lee","given":"Shuit-Tong","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Liu","given":"Zhuang","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Journal of the American Chemical Society","id":"ITEM-1","issue":"17","issued":{"date-parts":[["2012"]]},"page":"7414-22","title":"Noble metal coated single-walled carbon nanotubes for applications in surface enhanced Raman scattering imaging and photothermal therapy.","type":"article-journal","volume":"134"},"uris":[""]},{"id":"ITEM-2","itemData":{"DOI":"10.1021/am406031n","ISSN":"1944-8244","PMID":"24606763","abstract":"Golden single-walled carbon nanotubes (SWNTs) were prepared by growing gold nanoparticles onto the bilayer polysaccharide functionalized SWNTs. The layer-by-layer self-assembly of sodium alginate and chitosan on SWNTs provided an ideal surface with high density of active metal-binding groups such as amino and carboxylic acid groups, and then an approach of seed growth was adopted to facilitate the formation of gold nanoparticles coated SWNTs. The resulting golden SWNT hybrids have good water dispersibility and biocompatibility and tend to enter cancer cells. Interestingly, they have an enhanced NIR absorption and effectively transfer NIR laser into heat. The material can quickly cause localized hyperthermia, resulting in rapid cell death, and therefore appears to act as a highly effective photothermal converter for cancer ablation.","author":[{"dropping-particle":"","family":"Meng","given":"Lingjie","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Xia","given":"Wenjian","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Liu","given":"Li","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Niu","given":"Lvye","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Lu","given":"Qinghua","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"ACS Applied Materials & Interfaces","id":"ITEM-2","issue":"7","issued":{"date-parts":[["2014"]]},"page":"4989-4996","title":"Golden Single-Walled Carbon Nanotubes Prepared Using Double Layer Polysaccharides Bridge for Photothermal Therapy","type":"article-journal","volume":"6"},"uris":[""]},{"id":"ITEM-3","itemData":{"DOI":"10.1039/C6TB02755E","ISBN":"2050-750X\\r2050-7518","ISSN":"2050-750X","abstract":"Combining doxorubicin with thermal therapy in the clinic has led to startling results in the treatment of problematic cancers. Here, we describe a multimodal multi-walled carbon nanotube material that combines tumor targeting, doxorubicin delivery, and photothermal therapy for localized cancer treatment. The agent was constructed layer-by-layer from polypyrrole and gold nanoparticles on multi-walled carbon nanotubes. The gold surface was modified with tumor targeting folic acid terminated PEGylated chains, which also provide water-dispersibility, biocompatibility and should extend the half-life in blood. The material has a high loading/unloading capacity for the cytotoxic agent doxorubicin. Release of the doxorubicin, combined with the photothermal properties of the material that induces localized hyperthermia, leads to efficient cancer cell death.","author":[{"dropping-particle":"","family":"Wang","given":"Daquan","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Hou","given":"Chen","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Meng","given":"Lingjie","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Long","given":"Jiangang","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Jing","given":"Jiange","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Dang","given":"Dongfeng","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Fei","given":"Zhaofu","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Dyson","given":"Paul J.","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"J. Mater. Chem. B","id":"ITEM-3","issue":"7","issued":{"date-parts":[["2017"]]},"page":"1380-1387","publisher":"Royal Society of Chemistry","title":"Stepwise growth of gold coated cancer targeting carbon nanotubes for the precise delivery of doxorubicin combined with photothermal therapy","type":"article-journal","volume":"5"},"uris":[""]},{"id":"ITEM-4","itemData":{"DOI":"10.1039/c2cc32313c","ISBN":"1364-548X (Electronic)\\r1359-7345 (Linking)","ISSN":"1359-7345","PMID":"22627619","abstract":"This communication reports the design of a novel aptamer conjugated gold nanocage decorated SWCNTs hybrid nanomaterial for targeted imaging and selective photothermal destruction of the prostate cancer cells.","author":[{"dropping-particle":"","family":"Khan","given":"Sadia Afrin","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Kanchanapally","given":"Rajashekhar","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Fan","given":"Zhen","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Beqa","given":"Lule","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Singh","given":"Anant Kumar","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Senapati","given":"Dulal","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Ray","given":"Paresh Chandra","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Chemical Communications","id":"ITEM-4","issue":"53","issued":{"date-parts":[["2012"]]},"page":"6711","title":"A gold nanocage–CNT hybrid for targeted imaging and photothermal destruction of cancer cells","type":"article-journal","volume":"48"},"uris":[""]},{"id":"ITEM-5","itemData":{"DOI":"10.1021/jacs.5b13475","ISBN":"1520-5126 (Electronic) 0002-7863 (Linking)","ISSN":"15205126","PMID":"27193381","abstract":"We report a new type of carbon nanotube ring (CNTR) coated with gold nanoparticles (CNTR@AuNPs) using CNTR as a template and surface attached redox-active polymer as a reducing agent. This nanostructure of CNTR bundle embedded in the gap of closely attached AuNPs can play multiple roles as a Raman probe to detect cancer cells and a photoacoustic (PA) contrast agent for imaging-guided cancer therapy. The CNTR@AuNP exhibits substantially higher Raman and optical signals than CNTR coated with a complete Au shell (CNTR@ AuNS) and straight CNT@AuNP. The extinction intensity of CNTR@AuNP is about 120-fold higher than that of CNTR at 808 nm, and the surface enhanced Raman scattering (SERS) signal of CNTR@AuNP is about 110 times stronger than that of CNTR, presumably due to the combined effects of enhanced coupling between the embedded CNTR and the plasmon mode of the closely attached AuNPs, and the strong electromagnetic field in the cavity of the AuNP shell originated from the intercoupling of AuNPs. The greatly enhanced PA signal and photothermal conversion property of CNTR@AuNP were successfully employed for imaging and imaging-guided cancer therapy in two tumor xenograft models. Experimental observations were further supported by numerical simulations and perturbation theory analysis.","author":[{"dropping-particle":"","family":"Song","given":"Jibin","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Wang","given":"Feng","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Yang","given":"Xiangyu","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Ning","given":"Bo","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Harp","given":"Mary G.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Culp","given":"Stephen H.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Hu","given":"Song","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Huang","given":"Peng","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Nie","given":"Liming","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Chen","given":"Jingyi","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Chen","given":"Xiaoyuan","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Journal of the American Chemical Society","id":"ITEM-5","issue":"22","issued":{"date-parts":[["2016"]]},"page":"7005-7015","title":"Gold Nanoparticle Coated Carbon Nanotube Ring with Enhanced Raman Scattering and Photothermal Conversion Property for Theranostic Applications","type":"article-journal","volume":"138"},"uris":[""]}],"mendeley":{"formattedCitation":"^22–26","plainTextFormattedCitation":"22–26","previouslyFormattedCitation":"^23–27"},"properties":{"noteIndex":0},"schema":""}22–26 The LbL technique involves multiple steps which normally starts with functionalization of CNTs surfaces with polymers, biomacromolecule, or thiols to form an intermediated layer. The surface modified CNTs are then either hybridized with pre-synthesized AuNPs through electrostatic interactionADDIN CSL_CITATION {"citationItems":[{"id":"ITEM-1","itemData":{"DOI":"10.1021/ja300140c","ISBN":"0002-7863","ISSN":"1520-5126","PMID":"22486413","abstract":"Single-walled carbon nanotubes (SWNTs) with various unique optical properties are interesting nanoprobes widely explored in biomedical imaging and phototherapies. Herein, DNA-functionalized SWNTs are modified with noble metal (Ag or Au) nanoparticles via an in situ solution phase synthesis method comprised of seed attachment, seeded growth, and surface modification with polyethylene glycol (PEG), yielding SWNT-Ag-PEG and SWNT-Au-PEG nanocomposites stable in physiological environments. With gold or silver nanoparticles decorated on the surface, the SWNT-metal nanocomposites gain an excellent concentration and excitation-source dependent surface-enhanced Raman scattering (SERS) effect. Using a near-infrared (NIR) laser as the excitation source, targeted Raman imaging of cancer cells labeled with folic acid (FA) conjugated SWNT-Au nanocomposite (SWNT-Au-PEG-FA) is realized, with images acquired in significantly shortened periods of time as compared to that of using nonenhanced SWNT Raman probes. Owing to the strong surface plasmon resonance absorption contributed by the gold shell, the SWNTs-Au-PEG-FA nanocomposite also offers remarkably improved photothermal cancer cell killing efficacy. This work presents a facile approach to synthesize water-soluble noble metal coated SWNTs with a strong SERS effect suitable for labeling and fast Raman spectroscopic imaging of biological samples, which has been rarely realized before. The SWNT-Au-PEG nanocomposite developed here may thus be an interesting optical theranostic probe for cancer imaging and therapy.","author":[{"dropping-particle":"","family":"Wang","given":"Xiaojing","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Wang","given":"Chao","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Cheng","given":"Liang","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Lee","given":"Shuit-Tong","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Liu","given":"Zhuang","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Journal of the American Chemical Society","id":"ITEM-1","issue":"17","issued":{"date-parts":[["2012"]]},"page":"7414-22","title":"Noble metal coated single-walled carbon nanotubes for applications in surface enhanced Raman scattering imaging and photothermal therapy.","type":"article-journal","volume":"134"},"uris":[""]},{"id":"ITEM-2","itemData":{"DOI":"10.1039/C6TB02755E","ISBN":"2050-750X\\r2050-7518","ISSN":"2050-750X","abstract":"Combining doxorubicin with thermal therapy in the clinic has led to startling results in the treatment of problematic cancers. Here, we describe a multimodal multi-walled carbon nanotube material that combines tumor targeting, doxorubicin delivery, and photothermal therapy for localized cancer treatment. The agent was constructed layer-by-layer from polypyrrole and gold nanoparticles on multi-walled carbon nanotubes. The gold surface was modified with tumor targeting folic acid terminated PEGylated chains, which also provide water-dispersibility, biocompatibility and should extend the half-life in blood. The material has a high loading/unloading capacity for the cytotoxic agent doxorubicin. Release of the doxorubicin, combined with the photothermal properties of the material that induces localized hyperthermia, leads to efficient cancer cell death.","author":[{"dropping-particle":"","family":"Wang","given":"Daquan","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Hou","given":"Chen","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Meng","given":"Lingjie","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Long","given":"Jiangang","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Jing","given":"Jiange","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Dang","given":"Dongfeng","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Fei","given":"Zhaofu","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Dyson","given":"Paul J.","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"J. Mater. Chem. B","id":"ITEM-2","issue":"7","issued":{"date-parts":[["2017"]]},"page":"1380-1387","publisher":"Royal Society of Chemistry","title":"Stepwise growth of gold coated cancer targeting carbon nanotubes for the precise delivery of doxorubicin combined with photothermal therapy","type":"article-journal","volume":"5"},"uris":[""]},{"id":"ITEM-3","itemData":{"DOI":"10.1039/c2cc32313c","ISBN":"1364-548X (Electronic)\\r1359-7345 (Linking)","ISSN":"1359-7345","PMID":"22627619","abstract":"This communication reports the design of a novel aptamer conjugated gold nanocage decorated SWCNTs hybrid nanomaterial for targeted imaging and selective photothermal destruction of the prostate cancer cells.","author":[{"dropping-particle":"","family":"Khan","given":"Sadia Afrin","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Kanchanapally","given":"Rajashekhar","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Fan","given":"Zhen","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Beqa","given":"Lule","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Singh","given":"Anant Kumar","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Senapati","given":"Dulal","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Ray","given":"Paresh Chandra","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Chemical Communications","id":"ITEM-3","issue":"53","issued":{"date-parts":[["2012"]]},"page":"6711","title":"A gold nanocage–CNT hybrid for targeted imaging and photothermal destruction of cancer cells","type":"article-journal","volume":"48"},"uris":[""]}],"mendeley":{"formattedCitation":"^22,24,25","plainTextFormattedCitation":"22,24,25","previouslyFormattedCitation":"^23,25,26"},"properties":{"noteIndex":0},"schema":""}22,24,25 or AuNPs formed in situ via conventional chemical reduction methodADDIN CSL_CITATION {"citationItems":[{"id":"ITEM-1","itemData":{"DOI":"10.1021/am406031n","ISSN":"1944-8244","PMID":"24606763","abstract":"Golden single-walled carbon nanotubes (SWNTs) were prepared by growing gold nanoparticles onto the bilayer polysaccharide functionalized SWNTs. The layer-by-layer self-assembly of sodium alginate and chitosan on SWNTs provided an ideal surface with high density of active metal-binding groups such as amino and carboxylic acid groups, and then an approach of seed growth was adopted to facilitate the formation of gold nanoparticles coated SWNTs. The resulting golden SWNT hybrids have good water dispersibility and biocompatibility and tend to enter cancer cells. Interestingly, they have an enhanced NIR absorption and effectively transfer NIR laser into heat. The material can quickly cause localized hyperthermia, resulting in rapid cell death, and therefore appears to act as a highly effective photothermal converter for cancer ablation.","author":[{"dropping-particle":"","family":"Meng","given":"Lingjie","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Xia","given":"Wenjian","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Liu","given":"Li","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Niu","given":"Lvye","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Lu","given":"Qinghua","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"ACS Applied Materials & Interfaces","id":"ITEM-1","issue":"7","issued":{"date-parts":[["2014"]]},"page":"4989-4996","title":"Golden Single-Walled Carbon Nanotubes Prepared Using Double Layer Polysaccharides Bridge for Photothermal Therapy","type":"article-journal","volume":"6"},"uris":[""]},{"id":"ITEM-2","itemData":{"DOI":"10.1021/jacs.5b13475","ISBN":"1520-5126 (Electronic) 0002-7863 (Linking)","ISSN":"15205126","PMID":"27193381","abstract":"We report a new type of carbon nanotube ring (CNTR) coated with gold nanoparticles (CNTR@AuNPs) using CNTR as a template and surface attached redox-active polymer as a reducing agent. This nanostructure of CNTR bundle embedded in the gap of closely attached AuNPs can play multiple roles as a Raman probe to detect cancer cells and a photoacoustic (PA) contrast agent for imaging-guided cancer therapy. The CNTR@AuNP exhibits substantially higher Raman and optical signals than CNTR coated with a complete Au shell (CNTR@ AuNS) and straight CNT@AuNP. The extinction intensity of CNTR@AuNP is about 120-fold higher than that of CNTR at 808 nm, and the surface enhanced Raman scattering (SERS) signal of CNTR@AuNP is about 110 times stronger than that of CNTR, presumably due to the combined effects of enhanced coupling between the embedded CNTR and the plasmon mode of the closely attached AuNPs, and the strong electromagnetic field in the cavity of the AuNP shell originated from the intercoupling of AuNPs. The greatly enhanced PA signal and photothermal conversion property of CNTR@AuNP were successfully employed for imaging and imaging-guided cancer therapy in two tumor xenograft models. Experimental observations were further supported by numerical simulations and perturbation theory analysis.","author":[{"dropping-particle":"","family":"Song","given":"Jibin","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Wang","given":"Feng","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Yang","given":"Xiangyu","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Ning","given":"Bo","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Harp","given":"Mary G.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Culp","given":"Stephen H.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Hu","given":"Song","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Huang","given":"Peng","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Nie","given":"Liming","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Chen","given":"Jingyi","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Chen","given":"Xiaoyuan","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Journal of the American Chemical Society","id":"ITEM-2","issue":"22","issued":{"date-parts":[["2016"]]},"page":"7005-7015","title":"Gold Nanoparticle Coated Carbon Nanotube Ring with Enhanced Raman Scattering and Photothermal Conversion Property for Theranostic Applications","type":"article-journal","volume":"138"},"uris":[""]}],"mendeley":{"formattedCitation":"^23,26","plainTextFormattedCitation":"23,26","previouslyFormattedCitation":"^24,27"},"properties":{"noteIndex":0},"schema":""}23,26. Many of these hybrid structures feature heavily aggregated AuNP (with varying size and morphology) coated on the CNT surface. The effects of AuNP size and the process-structure-property relationship with respect to the synthesis of such hybrid structures have not been well established in the context of cancer treatment. left0Scheme SEQ Figure \* ARABIC 1. Diagram of the APP set-up 00Scheme SEQ Figure \* ARABIC 1. Diagram of the APP set-up Non-equilibrium atmospheric pressure plasma (APP) and in particular APP-liquid interactions, have demonstrated exceptional versatility in the synthesis and surface engineering of nanomaterials.ADDIN CSL_CITATION {"citationItems":[{"id":"ITEM-1","itemData":{"DOI":"10.1088/0022-3727/43/32/323001","ISBN":"0022-3727","ISSN":"0022-3727","abstract":"Microplasmas have attracted a tremendous amount of interest from the plasma community because of their small physical size, stable operation at atmospheric pressure, non-thermal characteristics, high electron densities and non-Maxwellian electron energy distributions. These properties make microplasmas suitable for a wide range of materials applications, including the synthesis of nanomaterials. Research has shown that vapour-phase precursors can be injected into a microplasma to homogeneously nucleate nanoparticles in the gas phase. Alternatively, microplasmas have been used to evaporate solid electrodes and form metal or metal-oxide nanostructures of various composition and morphology. Microplasmas have also been coupled with liquids to directly reduce aqueous metal salts and produce colloidal dispersions of nanoparticles. This topical review discusses the unique features of microplasmas that make them advantageous for nanomaterials synthesis, gives an overview of the diverse approaches previously reported in the literature and looks ahead to the potential for scale-up of current microplasma-based processes.","author":[{"dropping-particle":"","family":"Mariotti","given":"Davide","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Sankaran","given":"R Mohan","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Journal of Physics D: Applied Physics","id":"ITEM-1","issue":"32","issued":{"date-parts":[["2010","8","18"]]},"page":"323001","title":"Microplasmas for nanomaterials synthesis","type":"article-journal","volume":"43"},"uris":[""]},{"id":"ITEM-2","itemData":{"DOI":"10.1002/ppap.201500187","ISSN":"16128869","abstract":"? 2016 The Authors.Atmospheric pressure plasmas (APPs) have achieved great scientific and technological advances for a wide range of applications. The synthesis and treatment of materials by APPs have always attracted great attention due to potential economic benefits if compared to low-pressure plasma processes. Nonetheless, APPs present very distinctive features that suggest atmospheric pressure operation could bring other benefits for emerging new technologies. In particular, materials synthesized by APPs which are suitable candidates for third generation photovoltaics are reviewed here. Atmospheric pressure plasmas offer unique capabilities for new emerging advanced materials, which are required for next generation technologies. Here advances and opportunities are reviewed in the context of materials processing for third generation photovoltaic devices.","author":[{"dropping-particle":"","family":"Mariotti","given":"Davide","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Belmonte","given":"Thierry","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Benedikt","given":"Jan","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Velusamy","given":"Tamilselvan","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Jain","given":"Gunisha","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"?vr?ek","given":"Vladimir","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Plasma Processes and Polymers","id":"ITEM-2","issue":"1","issued":{"date-parts":[["2016"]]},"page":"70-90","title":"Low-Temperature Atmospheric Pressure Plasma Processes for \"Green\" Third Generation Photovoltaics","type":"article","volume":"13"},"uris":["",""]},{"id":"ITEM-3","itemData":{"DOI":"10.1051/epjap/2011110203","ISBN":"2011110203","ISSN":"1286-0042","abstract":"Two different atmospheric pressure microplasma systems are discussed and used for the synthesis and surface engineering of a range of nanomaterials. Specifically a gas-phase approach from vaporized tetramethylsilane has been used to synthesize silicon carbide nanoparticles with diameters below 10 nm. A different microplasma system that interfaces with a liquid solution has then been used for the synthesis of surfactant-free electrically stabilized gold nanoparticles with varying size. A similar microplasma-liquid system has been finally successfully used to tailor surface properties of silicon nanoparticles and to reduce graphene oxide into graphene. The synthesis and surface engineering mechanisms are also discussed.","author":[{"dropping-particle":"","family":"McKenna","given":"J.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Patel","given":"J.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Mitra","given":"S.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Soin","given":"N.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"?vr?ek","given":"V.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Maguire","given":"P.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Mariotti","given":"D.","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"The European Physical Journal Applied Physics","id":"ITEM-3","issue":"2","issued":{"date-parts":[["2011"]]},"page":"24020","title":"Synthesis and surface engineering of nanomaterials by atmospheric-pressure microplasmas","type":"article-journal","volume":"56"},"uris":[""]},{"id":"ITEM-4","itemData":{"DOI":"10.1002/adfm.201301468","ISBN":"1616-301X","ISSN":"1616301X","abstract":"Substantial improvements of the absolute photoluminescence quantum yield (QY) for surfactant-free silicon nanocrystals (Si-ncs) by atmospheric pressure microplasma 3-dimensional surface engineering are reported. The effect of surface characteristics on carrier multiplication mechanisms is explored using transient induced absorption and photoluminescence QY. Surface engineering of Si-ncs is demonstrated to lead to more than 120 times increase in the absolute QY (from 0.1% up to 12%) within an important spectral range of the solar emission (2.3-3 eV). The Si-ncs QY is shown to be stable when Si-ncs are stored in ethanol at ambient conditions for three months.","author":[{"dropping-particle":"","family":"Svrcek","given":"Vladimir","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Dohnalova","given":"Katerina","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Mariotti","given":"Davide","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Trinh","given":"Minh Tuan","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Limpens","given":"Rens","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Mitra","given":"Somak","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Gregorkiewicz","given":"Tom","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Matsubara","given":"Koiji","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Kondo","given":"Michio","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Advanced Functional Materials","id":"ITEM-4","issue":"48","issued":{"date-parts":[["2013"]]},"page":"6051-6058","title":"Dramatic enhancement of photoluminescence quantum yields for surface-engineered Si nanocrystals within the solar spectrum","type":"article-journal","volume":"23"},"uris":["",""]},{"id":"ITEM-5","itemData":{"DOI":"10.1021/jp400938x","ISSN":"19327447","abstract":"We have demonstrated that three-dimensional (3D) surface engineering of silicon nanocrystals (SiNCs) by direct current microplasma processing in water with poly(3,4-ethylenedioxythiophene) doped by poly(styrenesulfonate) (PEDOT:PSS) can lead to nanocomposites with enhanced optoelectronic performance. Specifically, we have successfully shown improved photoluminescence properties of SiNCs inside water-based solution. The results also confirm that SiNCs become stable in water with potential application impact for biorelated applications. We have also shown that the microplasma processing in the presence of the polymer helps prevent the fast oxidation process over a longer period of time in comparison to the unprocessed sample. Furthermore, the assessment of transport properties confirmed the improvement of exciton dissociation after microplasma surface engineering; this can have direct implications for higher performance optoelectronic devices including solar cells.\\nWe have demonstrated that three-dimensional (3D) surface engineering of silicon nanocrystals (SiNCs) by direct current microplasma processing in water with poly(3,4-ethylenedioxythiophene) doped by poly(styrenesulfonate) (PEDOT:PSS) can lead to nanocomposites with enhanced optoelectronic performance. Specifically, we have successfully shown improved photoluminescence properties of SiNCs inside water-based solution. The results also confirm that SiNCs become stable in water with potential application impact for biorelated applications. We have also shown that the microplasma processing in the presence of the polymer helps prevent the fast oxidation process over a longer period of time in comparison to the unprocessed sample. Furthermore, the assessment of transport properties confirmed the improvement of exciton dissociation after microplasma surface engineering; this can have direct implications for higher performance optoelectronic devices including solar cells.","author":[{"dropping-particle":"","family":"Mitra","given":"Somak","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Cook","given":"Steffan","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"?vr?ek","given":"Vladimir","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Blackley","given":"Ross A.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Zhou","given":"Wuzong","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Kova?","given":"Janez","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Cvelbar","given":"Uros","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Mariotti","given":"Davide","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Journal of Physical Chemistry C","id":"ITEM-5","issue":"44","issued":{"date-parts":[["2013"]]},"page":"23198-23207","title":"Improved optoelectronic properties of silicon nanocrystals/polymer nanocomposites by microplasma-induced liquid chemistry","type":"article-journal","volume":"117"},"uris":["",""]},{"id":"ITEM-6","itemData":{"DOI":"10.1002/ppap.201600224","ISSN":"16128869","abstract":"? 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.CuO is a versatile p-type material for energy applications capable of imparting diverse functionalities by manipulating its band-energy diagram. We present ultra-small quantum confined cupric oxide nanoparticles (CuO NPs) synthesized via a simple one-step environmentally friendly atmospheric pressure microplasma synthesis process. The proposed method, based on the use of a hybrid plasma-liquid cell, enables the synthesis of CuO NPs directly from solid metal copper in ethanol with neither surfactants nor reducing agents. CuO NPs films are then used for the first time in all-inorganic third generation solar cell devices demonstrating highly effective functionalities as blocking layer.","author":[{"dropping-particle":"","family":"Velusamy","given":"Tamilselvan","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Liguori","given":"Anna","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Macias-Montero","given":"Manuel","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Padmanaban","given":"Dilli Babu","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Carolan","given":"Darragh","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Gherardi","given":"Matteo","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Colombo","given":"Vittorio","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Maguire","given":"Paul","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Svrcek","given":"Vladimir","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Mariotti","given":"Davide","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Plasma Processes and Polymers","id":"ITEM-6","issue":"7","issued":{"date-parts":[["2017"]]},"title":"Ultra-small CuO nanoparticles with tailored energy-band diagram synthesized by a hybrid plasma-liquid process","type":"article-journal","volume":"14"},"uris":["",""]}],"mendeley":{"formattedCitation":"^33–38","plainTextFormattedCitation":"33–38","previouslyFormattedCitation":"^34–39"},"properties":{"noteIndex":0},"schema":""}33–38 When interacting with water, a high density of gas phase plasma electrons become solvated in the liquid, creating a rapid cascade of transient non-linear chemical reactions and highly reactive radicals (e.g., H· and OH·).ADDIN CSL_CITATION {"citationItems":[{"id":"ITEM-1","itemData":{"DOI":"10.1088/0963-0252/25/5/053002","ISBN":"0963-0252","ISSN":"13616595","abstract":"Plasma–liquid interactions represent a growing interdisciplinary area of research involving plasma science, fluid dynamics, heat and mass transfer, photolysis, multiphase chemistry and aerosol science. This review provides an assessment of the state-of-the-art of this multidisciplinary area and identifies the key research challenges. The developments in diagnostics, modeling and further extensions of cross section and reaction rate databases that are necessary to address these challenges are discussed. The review focusses on non- equilibrium plasmas. Keywords:","author":[{"dropping-particle":"","family":"Bruggeman","given":"P. J.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Kushner","given":"M. J.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Locke","given":"B. R.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Gardeniers","given":"J. G.E.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Graham","given":"W. 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While nanoparticle formation via high energy radiolysis or transmission electron microscopy-based electron bombardment is well-understood, we have developed a source of electrons with energies close to thermal which leads to a number of important and unique benefits. The charged species, including the growing nanoparticles, are held in an ultrathin surface reaction zone which enables extremely rapid precursor reduction. In a proof-of-principle demonstration, we obtain small-diameter Au nanoparticles (～4 nm) with tight control of polydispersity, in under 150 μs. The precursor was almost completely reduced in this period, and the resultant nanoparticles were water-soluble and free of surfactant or additional ligand chemistry. Nanoparticle synthesis rates within the droplets were many orders of magnitude greater than equivalent rates reported for radiolysis, electron beam irradiation, or colloidal chemical synthesis where reaction times vary from seconds to hours. In our device, a stream of precursor loaded microdroplets, ～15 μm in diameter, were transported rapidly through a cold atmospheric pressure plasma with a high charge concentration. A high electron flux, electron and nanoparticle confinement at the surface of the droplet, and the picoliter reactor volume are thought to be responsible for the remarkable enhancement in nanoparticle synthesis rates. While this approach exhibits considerable potential for scale-up of synthesis rates, it also offers the more immediate prospect of continuous on-demand delivery of high-quality nanomaterials directly to their point of use by avoiding the necessity of collection, recovery, and purification. A range of new applications can be envisaged, from theranostics and biomedical imaging in tissue to inline catalyst production for pollution remediation in automobiles.","author":[{"dropping-particle":"","family":"Maguire","given":"Paul","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Rutherford","given":"David","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Macias-Montero","given":"Manuel","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Mahony","given":"Charles","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Kelsey","given":"Colin","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Tweedie","given":"Mark","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Pérez-Martin","given":"Fátima","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"McQuaid","given":"Harold","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Diver","given":"Declan","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Mariotti","given":"Davide","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Nano Letters","id":"ITEM-2","issue":"3","issued":{"date-parts":[["2017"]]},"page":"1336-1343","title":"Continuous In-Flight Synthesis for On-Demand Delivery of Ligand-Free Colloidal Gold Nanoparticles","type":"article-journal","volume":"17"},"uris":["",""]}],"mendeley":{"formattedCitation":"^39,40","plainTextFormattedCitation":"39,40","previouslyFormattedCitation":"^40,41"},"properties":{"noteIndex":0},"schema":""}39,40 Solvated electrons and/or reactive species are responsible for the successful synthesis of various nanomaterials, such as AuNPs, AgNPs, Fe3O4 NPs, Cu2O NPs, and alloyed NPs such as AuxAg1-x in aqueous solutions.ADDIN CSL_CITATION {"citationItems":[{"id":"ITEM-1","itemData":{"DOI":"10.1088/0957-4484/24/24/245604","ISBN":"1361-6528 (Electronic)\\r0957-4484 (Linking)","ISSN":"0957-4484","PMID":"23696315","abstract":"Plasma-induced non-equilibrium liquid chemistry is used to synthesize gold nanoparticles (AuNPs) without using any reducing or capping agents. The morphology and optical properties of the synthesized AuNPs are characterized by transmission electron microscopy (TEM) and ultraviolet-visible spectroscopy. Plasma processing parameters affect the particle shape and size and the rate of the AuNP synthesis process. Particles of different shapes (e.g. spherical, triangular, hexagonal, pentagonal, etc) are synthesized in aqueous solutions. In particular, the size of the AuNPs can be tuned from 5 nm to several hundred nanometres by varying the initial gold precursor (HAuCl4) concentration from 2.5 μM to 1 mM. In order to reveal details of the basic plasma-liquid interactions that lead to AuNP synthesis, we have measured the solution pH, conductivity and hydrogen peroxide (H2O2) concentration of the liquid after plasma processing, and conclude that H2O2 plays the role of the reducing agent which converts Au(+3) ions to Au(0) atoms, leading to nucleation growth of the AuNPs.","author":[{"dropping-particle":"","family":"Patel","given":"J","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Němcová","given":"L","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Maguire","given":"P","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Graham","given":"W G","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Mariotti","given":"D","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Nanotechnology","id":"ITEM-1","issue":"24","issued":{"date-parts":[["2013"]]},"page":"245604","title":"Synthesis of surfactant-free electrostatically stabilized gold nanoparticles by plasma-induced liquid chemistry","type":"article-journal","volume":"24"},"uris":[""]},{"id":"ITEM-2","itemData":{"DOI":"10.1088/0957-4484/24/9/095604","ISSN":"1361-6528","PMID":"23403974","abstract":"Atmospheric-pressure microplasma-assisted electrochemistry was used to synthesize Ag nanoparticles (NPs) for plasmonic applications. It is shown that the size and dispersion of the nanoparticles can be controlled by variation of the microplasma-assisted electrochemical process parameters such as electrolyte concentration and temperature. Moreover, Ag NP synthesis is also achieved in the absence of a stabilizer, with additional control over the dispersion and NP formation possible. As the microplasma directly reduces Ag ions in solution, the incorporation of toxic reducing agents into the electrolytic solution is unnecessary, making this an environmentally friendly fabrication technique with strong potential for the design and growth of plasmonic nanostructures for a variety of applications. These experiments therefore link microplasma-assisted electrochemical synthesis parameters with plasmonic characteristics.","author":[{"dropping-particle":"","family":"Huang","given":"X Z","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Zhong","given":"X X","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Lu","given":"Y","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Li","given":"Y S","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Rider","given":"a E","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Furman","given":"S a","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Ostrikov","given":"K","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Nanotechnology","id":"ITEM-2","issued":{"date-parts":[["2013"]]},"page":"095604","title":"Plasmonic Ag nanoparticles via environment-benign atmospheric microplasma electrochemistry","type":"article-journal","volume":"24"},"uris":[""]},{"id":"ITEM-3","itemData":{"DOI":"10.1002/ppap.201300168","ISSN":"16128869","author":[{"dropping-particle":"","family":"Wang","given":"Ruixue","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Zuo","given":"Shasha","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Zhu","given":"Weidong","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Zhang","given":"Jue","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Fang","given":"Jing","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Plasma Processes and Polymers","id":"ITEM-3","issue":"5","issued":{"date-parts":[["2014"]]},"page":"448-454","title":"Rapid synthesis of aqueous-phase magnetite nanoparticles by atmospheric pressure non-thermal microplasma and their application in magnetic resonance imaging","type":"article-journal","volume":"11"},"uris":[""]},{"id":"ITEM-4","itemData":{"DOI":"10.1038/srep07339","ISSN":"20452322","PMID":"25475085","abstract":"A simple microplasma method was used to synthesize cuprous oxide (Cu2O) nanoparticles in NaCl-NaOH-NaNO3 electrolytic system. Microplasma was successfully used as the cathode and copper plate was used as the anode. The Cu2O products are characterized by X-ray powder diffraction (XRD), field emission scanning electron microscope (FESEM) and transmission electron microscope (TEM). The results show that the morphology of Cu2O nanocrystals obtained by this technology is mainly dependent on the electrolytic media, stirring, current density and reaction temperature. The uniform and monodisperse sphere Cu2O nanoparticles with the size about 400 ~ 600 nm can be easily obtained in H2O-ethylene glycol mix-solvent (volume ratio 1:1) and appropriate current density with stirring at room temperature. In addition, the possible mechanism has been reported in the article. And the average energy consumed in producing 1 g Cu2O nanoparticles is 180 kJ. For the flexibility and effectiveness of this microplasma technology, it will have broad application prospects in the realm of nanoscience, energy and environment.","author":[{"dropping-particle":"","family":"Du","given":"Changming","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Xiao","given":"Mudan","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Scientific Reports","id":"ITEM-4","issued":{"date-parts":[["2014"]]},"title":"Cu2O nanoparticles synthesis by microplasma","type":"article-journal","volume":"4"},"uris":["",""]},{"id":"ITEM-5","itemData":{"DOI":"10.1039/c3cc48846b","ISBN":"1364-548X (Electronic)\\r1359-7345 (Linking)","ISSN":"1364-548X","PMID":"24519646","abstract":"Tunable synthesis of bimetallic AuxAg1-x alloyed nanoparticles and in situ monitoring of their plasmonic responses is presented. This is a new conceptual approach based on green and energy efficient, reactive, and highly-non-equilibrium microplasma chemistry.","author":[{"dropping-particle":"","family":"Yan","given":"T","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Zhong","given":"X","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Rider","given":"a E","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Lu","given":"Y","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Furman","given":"S a","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Ostrikov","given":"K K","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Chem Commun (Camb)","id":"ITEM-5","issue":"24","issued":{"date-parts":[["2014"]]},"page":"3144-3147","title":"Microplasma-chemical synthesis and tunable real-time plasmonic responses of alloyed AuxAg1-x nanoparticles","type":"article-journal","volume":"50"},"uris":[""]}],"mendeley":{"formattedCitation":"^41–45","plainTextFormattedCitation":"41–45","previouslyFormattedCitation":"^42–46"},"properties":{"noteIndex":0},"schema":""}41–45 2387606962775Table 1. Nomenclatures of samples and their preparation methods0Table 1. Nomenclatures of samples and their preparation methodsIn this work, we report the proof-of-concept of using of a facile and rapid direct current (DC), room temperature APP technique for the one-step synthesis of AuNP/CNT nanohybrids in aqueous solution. Stable and uniformly dispersed hybrid samples can be achieved unhindered by solvents or surfactants. Great insight has been developed for the interfacial interaction between AuNPs and different CNT systems (with different surface functionality), which helps to elucidate the underlining mechanisms of different photothermal conversion capability seen in different AuNP/CNT hybrid systems. The potential of our synthesized hybrid structures in applications such as cancer photothermal therapy and Raman sensing have been also discussed. 2. EXPERIMENTAL SECTION2.1 Materials. Three different types of surface functionalized multiwall carbon nanotubes (CNTs) were purchased from Cheap Tubes Inc., including carboxyl (-COOH) functionalized CNT with higher (1.2 %) -COOH density (namely CNT-COOH-H, purity > 95 wt%, length 10-30 μm, diameter 20-30 nm, according to manufacturer’s data sheet), carboxyl (-COOH) functionalized CNT with lower (0.73 %) -COOH density (namely CNT-COOH-L, purity > 95 wt%, length 0.5-2.0 μm, diameter 30-50 nm), and hydroxyl (-OH) functionalized CNT with 1.0 % OH density (namely, CNT-OH, purity > 95 wt%, length 0.5-2.0 μm, diameter 30-50 nm). HAuCl4 (Sigma Aldrich) aqueous solutions (2.5 μM, 0.1 mM, and 0.2 mM) were prepared by mixing chloroauric acid trihydrate (HAuCl4.3H2O,?> 99.9%, Sigma-Aldrich) with appropriate amount of deionized water (Millipore Milli-Q machine (18.2 MΩ· cm-1).2.2 APP set-up. The APP set-up deployed in this work, as shown in Scheme 1, consists of a graphite rod as anode and a stainless-steel capillary (250 ?m inner diameter) as cathode. The graphite rod was immersed in the aqueous solution, while the stainless steel capillary was placed approx. 1 mm above the liquid surface. The approximate distance between the anode and cathode was 2 cm. Helium (He) gas (25 sccm flow rate) was supplied through the capillary and the plasma can be triggered and maintained at ~2 kV voltage and 5 mA current. All samples mentioned in this work were treated for 10 min under a static condition. 2.3 Synthesis of AuNP/CNT hybrids. 0.1 mg/ mL CNTs/ water mixture was sonicated (140 W) for 6 hours and centrifuged at 5000 rpm for 4 hours, and the supernatant with dispersed CNTs was collected. The supernatants were diluted by adding appropriated amount of deionized water to obtain dispersed CNT solutions with a concentration of 50 ± 3 ?g/mL. Appropriate amount of concentrated (5 mM) HAuCl4 solution was added to different CNTs dispersion samples, to obtain aqueous mixtures of CNT with different HAuCl4 concentrations (2.5 μM, 0.1 mM, and 0.2 mM were used in this work). The resultant mixtures were settled for 0.5 hour prior to APP processing.The samples were named after the type of CNT functional groups and the HAuCl4 precursor concentration used (see Table 1)and all samples were stored in glass vials (see Figure S1 in SI);13398594615Table 2. Nomenclatures of other samples for comparison and their preparation methods00Table 2. Nomenclatures of other samples for comparison and their preparation methods For comparison and to provide further details for the discussion and analysis, a range of other samples were considered and these are summarized in Table 2. right6493758Figure 1. UV-Vis spectra of the untreated CNT-COOH-H, APP treated CNT-COOH-H, and in-situ synthesized AuNP/CNT-COOH-H hybrids. 00Figure 1. UV-Vis spectra of the untreated CNT-COOH-H, APP treated CNT-COOH-H, and in-situ synthesized AuNP/CNT-COOH-H hybrids. 2.4 Characterization. Ultraviolet-visible (UV-Vis) absorption spectra of the solutions were recorded using an Agilent spectrometer (Cary 60 UV-Vis, Agilent Technologies). The morphologies and sizes of the nanostructures were investigated by transmission electron microscopy (TEM; Philips Tecnai F20D), along with ImageJ software for the particle size analysis (more than 100 particles were analyzed). Samples for TEM characterization were all prepared by depositing a 25 ?L droplet of sample solution onto a TEM sample grid. ζ-potential measurements were carried out using a Zeta Potential Analyser (Omni, Brookhaven). X-ray photoelectron spectroscopy (XPS) results were obtained from a Kratos Axis Ultra XPS system (monochromatic Al Kα X-rays, 1486 eV) which was run at a current of 10 mA and a voltage of 15 kV, respectively. The conducting environment base pressure was 1 × 10?9 mbar. The samples were prepared by drop casting aqueous solutions on neat and intrinsic silicon wafer and thoroughly dried under room temperature. High-resolution (0.05 eV) XPS spectra including C 1s and Au 4f peaks were performed at a pass energy of 40 eV. The C 1s peak located at 284.5 eV was used for the calibration of the obtained spectra. An open source software (CasaXPS) was deployed for the data analysis. Samples for Raman analysis were prepared by drop casting 100 μL of liquid sample on neat and intrinsic silicon wafer with a pre-fabricated 6 mm × 6 mm square well. After completely dried under room temperature, Raman scattering spectra of all samples were measured under ambient condition by Raman spectroscopy (LabRAM 300, Horiba, UK with a 632 nm source), which is equipped with a 632 nm N2-H2 laser excitation source. The output of the laser box is 3.7 kV and 7 mA, and 1 % of the output was chosen for characterization. Each scan was divided into three segments with a total irradiation time of 45 s. 2.5 Photothermal conversion tests. The photothermal effect of the hybrids was tested under the irradiation of an 852 nm continuous wavelength (CW) diode laser source with a power of 1.5 W (B4-852-1500-15C, Sheaumann Laser Inc). 100 μL of each solution was placed in a 96-wellP plated container, which was irradiated by the laser and the temperature of the solution was monitored by an IR temperature sensor (CSL-CF2 High performance pyrometer, Micro-Epsilon).3. RESULTS AND DISCUSSION The optical properties of all samples were analysed by UV-Vis spectroscopy, see Figure 1. The APP treatment had no influence on the absorption spectra of the CNT-COOH-H when they were processed without added HAuCl4. However, for samples containing HAuCl4, APP treatment had led to a well dispersed colloid solution with changed colour (Figure S1, SI), indicating the formation of AuNP with different particle sizes.ADDIN CSL_CITATION {"citationItems":[{"id":"ITEM-1","itemData":{"DOI":"10.1051/epjap/2011110203","ISBN":"2011110203","ISSN":"1286-0042","abstract":"Two different atmospheric pressure microplasma systems are discussed and used for the synthesis and surface engineering of a range of nanomaterials. Specifically a gas-phase approach from vaporized tetramethylsilane has been used to synthesize silicon carbide nanoparticles with diameters below 10 nm. A different microplasma system that interfaces with a liquid solution has then been used for the synthesis of surfactant-free electrically stabilized gold nanoparticles with varying size. A similar microplasma-liquid system has been finally successfully used to tailor surface properties of silicon nanoparticles and to reduce graphene oxide into graphene. The synthesis and surface engineering mechanisms are also discussed.","author":[{"dropping-particle":"","family":"McKenna","given":"J.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Patel","given":"J.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Mitra","given":"S.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Soin","given":"N.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"?vr?ek","given":"V.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Maguire","given":"P.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Mariotti","given":"D.","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"The European Physical Journal Applied Physics","id":"ITEM-1","issue":"2","issued":{"date-parts":[["2011"]]},"page":"24020","title":"Synthesis and surface engineering of nanomaterials by atmospheric-pressure microplasmas","type":"article-journal","volume":"56"},"uris":["",""]},{"id":"ITEM-2","itemData":{"DOI":"10.1088/0957-4484/24/24/245604","ISBN":"1361-6528 (Electronic)\\r0957-4484 (Linking)","ISSN":"0957-4484","PMID":"23696315","abstract":"Plasma-induced non-equilibrium liquid chemistry is used to synthesize gold nanoparticles (AuNPs) without using any reducing or capping agents. The morphology and optical properties of the synthesized AuNPs are characterized by transmission electron microscopy (TEM) and ultraviolet-visible spectroscopy. Plasma processing parameters affect the particle shape and size and the rate of the AuNP synthesis process. Particles of different shapes (e.g. spherical, triangular, hexagonal, pentagonal, etc) are synthesized in aqueous solutions. In particular, the size of the AuNPs can be tuned from 5 nm to several hundred nanometres by varying the initial gold precursor (HAuCl4) concentration from 2.5 μM to 1 mM. In order to reveal details of the basic plasma-liquid interactions that lead to AuNP synthesis, we have measured the solution pH, conductivity and hydrogen peroxide (H2O2) concentration of the liquid after plasma processing, and conclude that H2O2 plays the role of the reducing agent which converts Au(+3) ions to Au(0) atoms, leading to nucleation growth of the AuNPs.","author":[{"dropping-particle":"","family":"Patel","given":"J","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Němcová","given":"L","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Maguire","given":"P","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Graham","given":"W G","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Mariotti","given":"D","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Nanotechnology","id":"ITEM-2","issue":"24","issued":{"date-parts":[["2013"]]},"page":"245604","title":"Synthesis of surfactant-free electrostatically stabilized gold nanoparticles by plasma-induced liquid chemistry","type":"article-journal","volume":"24"},"uris":[""]}],"mendeley":{"formattedCitation":"^35,41","plainTextFormattedCitation":"35,41","previouslyFormattedCitation":"^36,42"},"properties":{"noteIndex":0},"schema":""}35,41 The emergence of peaks at 531 nm for 0.1 mM AuNP/CNT-COOH-H and 554 nm for 0.2 mM AuNP/CNT-COOH-H shown in Figure 1 can be attributed to the typical localized surface plasmon resonance (LSPR) effects of AuNPs.ADDIN CSL_CITATION {"citationItems":[{"id":"ITEM-1","itemData":{"DOI":"10.1021/la201938u","ISBN":"0743-7463","ISSN":"07437463","PMID":"21728302","abstract":"Monodisperse citrate-stabilized gold nanoparticles with a uniform quasi-spherical shape of up to ～200 nm and a narrow size distribution were synthesized following a kinetically controlled seeded growth strategy via the reduction of HAuCl(4) by sodium citrate. The inhibition of any secondary nucleation during homogeneous growth was controlled by adjusting the reaction conditions: temperature, gold precursor to seed particle concentration, and pH. This method presents improved results regarding the traditional Frens method in several aspects: (i) it produces particles of higher monodispersity; (ii) it allows better control of the gold nanoparticle size and size distribution; and (iii) it leads to higher concentrations. Gold nanoparticles synthesized following this method can be further functionalized with a wide variety of molecules, hence this method appears to be a promising candidate for application in the fields of biomedicine, photonics, and electronics, among others.","author":[{"dropping-particle":"","family":"Bastús","given":"Neus G.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Comenge","given":"Joan","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Puntes","given":"Víctor","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Langmuir","id":"ITEM-1","issue":"17","issued":{"date-parts":[["2011"]]},"page":"11098-11105","title":"Kinetically controlled seeded growth synthesis of citrate-stabilized gold nanoparticles of up to 200 nm: Size focusing versus ostwald ripening","type":"article-journal","volume":"27"},"uris":["",""]}],"mendeley":{"formattedCitation":"⁴⁶","plainTextFormattedCitation":"46","previouslyFormattedCitation":"⁴⁷"},"properties":{"noteIndex":0},"schema":""}46 The red shift of LSPR peak can be related to the increase of the NP size as a result of greater HAuCl4 concentration.ADDIN CSL_CITATION {"citationItems":[{"id":"ITEM-1","itemData":{"DOI":"10.1021/ac0702084","ISBN":"0003-2700","ISSN":"00032700","PMID":"17458937","abstract":"The dependence of the optical properties of spherical gold nanoparticles on particle size and wavelength were analyzed theoretically using multipole scattering theory, where the complex refractive index of gold was corrected for the effect of a reduced mean free path of the conduction electrons in small particles. To compare these theoretical results to experimental data, gold nanoparticles in the size range of 5 to 100 nm were synthesized and characterized with TEM and UV?vis. Excellent agreement was found between theory and experiment. It is shown that the data produced here can be used to determine both size and concentration of gold nanoparticles directly from UV?vis spectra. Equations for this purpose are derived, and the precision of various methods is discussed. The major aim of this work is to provide a simple and fast method to determine size and concentration of nanoparticles.","author":[{"dropping-particle":"","family":"Haiss","given":"Wolfgang","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Thanh","given":"Nguyen T K","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Aveyard","given":"Jenny","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Fernig","given":"David G.","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Analytical Chemistry","id":"ITEM-1","issue":"11","issued":{"date-parts":[["2007"]]},"page":"4215-4221","title":"Determination of size and concentration of gold nanoparticles from UV-Vis spectra","type":"article-journal","volume":"79"},"uris":["",""]}],"mendeley":{"formattedCitation":"⁴⁷","plainTextFormattedCitation":"47","previouslyFormattedCitation":"⁴⁸"},"properties":{"noteIndex":0},"schema":""}47 However, the LSPR peak for 2.5 μM 219710461176Figure 2. TEM images of AuNP/CNT-COOH-H synthesized from different HAuCl4 precursor concentrations (a) 2.5 ?M, (b) 0.1 mM, and (c) 0.2 mM AuNP/CNT-COOH-H hybrids, respectively; insets: corresponding higher magnification images; and (d) - (f) average AuNPs particle sizes within the three hybrids.(c)(b)(a)(d)00Figure 2. TEM images of AuNP/CNT-COOH-H synthesized from different HAuCl4 precursor concentrations (a) 2.5 ?M, (b) 0.1 mM, and (c) 0.2 mM AuNP/CNT-COOH-H hybrids, respectively; insets: corresponding higher magnification images; and (d) - (f) average AuNPs particle sizes within the three hybrids.(c)(b)(a)(d)AuNP/CNT-COOH-H hybrid is not visible. With very low gold precursor concentration (2.5 μM), the plasmonic absorption may be very low due to the very low concentration of the synthesized AuNPs. The morphologies of the AuNP/CNT-COOH-H hybrids have been investigated by TEM, see Figure 2. CNT-COOH-H after plasma treatment do not show any morphological changes (e.g. length; see also Figure S2 in SI for TEM of untreated CNT-COOH-H). However, AuNPs are found to attach on CNTs surfaces without obvious agglomerations, demonstrating that the plasma induced liquid chemistry is effective in producing AuNP/CNT-COOH-H hybrids. As it is shown in Figure 2a-c, the AuNPs within all the nanohybrids are mostly spherical (the shape projections of AuNP within AuNP/CNT-COOH hybrids can be found in Figure S3, SI), though NPs in the 0.2 mM AuNP/CNT-COOH-H hybrids start to show signs of heterogeneous growth (e.g. triangles, rods, etc., also see Figure S3 in SI). In contrast, pure AuNPs synthesized under the same plasma conditions (i.e., without the presence of CNT-COOH-H and using the respective HAuCl4 concentrations) tend to exhibit more irregular shapes (e.g. triangles, hexagons, and rods) (See the shape projections of AuNPs in Figure S4 a-c, SI). Detailed examination of each sample (Figure 2a-c insets) suggests some form of interactions between AuNPs and CNT-COOH-H interface as, for all samples, there is no evidence of any AuNP remaining un-attached. Particle sizes and distributions are analysed by “ImageJ”, and more than 100 NPs were studied for each sample. The size of spherical NPs is determined by diameter, while that of other shapes are determined by the longest length; the average size and distribution is fitted with a Gaussian function. As can be seen from Figure 2d, the average NP size (corresponding size distribution can be seen in Figure S3) increases with increasing HAuCl4 concentration, which is consistent with the UV-Vis results discussed earlier (Figure 1). In order to gain more insight into the chemical composition and bonding arrangements, a comparison of the element chemical states between the untreated CNTs and 0.1 mM AuNP/CNT-COOH-H hybrid was investigated by XPS, and the mediate mixture 0.1 mM HAuCl4/CNT-COOH-H was considered for comparison. Firstly, we looked at the difference between the survey spectra of CNT-COOH-H and 0.1 mM AuNP/CNT-COOH-H. As shown in Figure 3a, spectra of the 0.1 mM AuNP/CNT-COOH-H hybrid showed distinct Au peaks and a significant decrease in the oxygen peak intensity, indicating the presence of Au element as compared to pure CNT-COOH-H sample. High-resolution scan on C 1s and Au 4f spectra were then carried out to compare the changes in the states of elements for CNT-COOH-H, 0.1 mM HAuCl4/CNT-COOH-H and 0.1 mM AuNP/CNT-COOH-H after APP treatment. Before mixing with HAuCl4 aqueous, there is no Au 4f peak detected for pure CNT-COOH-H as shown in the survey spectrum; the C 1s peak lefttop(d)(b)(a)Figure 3. (a) Survey XPS spectra of untreated CNT and 0.1 mM AuNP/CNT-COOH-H hybrid; (b) C 1s core XPS spectrum of CNT-COOH-H; Au 4f core XPS spectrum of (c) 0.1 mM HAuCl4/CNT-COOH-H mixture and (d) 0.1 mM AuNP/CNT-COOH-H hybrid; and C 1s core XPS spectrum of (e) 0.1 mM HAuCl4/CNT-COOH-H mixture and (f) 0.1 mM AuNP/CNT-COOH-H hybrid.(c)(e)(f)C 1s Au 4f C 1s Au 4f C 1s 00(d)(b)(a)Figure 3. (a) Survey XPS spectra of untreated CNT and 0.1 mM AuNP/CNT-COOH-H hybrid; (b) C 1s core XPS spectrum of CNT-COOH-H; Au 4f core XPS spectrum of (c) 0.1 mM HAuCl4/CNT-COOH-H mixture and (d) 0.1 mM AuNP/CNT-COOH-H hybrid; and C 1s core XPS spectrum of (e) 0.1 mM HAuCl4/CNT-COOH-H mixture and (f) 0.1 mM AuNP/CNT-COOH-H hybrid.(c)(e)(f)C 1s Au 4f C 1s Au 4f C 1s of pure CNT-COOH-H (Figure 3b) can be detected and de-convoluted into six components due to the different carbon elemental environments: the sp2- hybridized carbon (C=C), the sp3-hybridized carbon (C-C), the oxygen-containing functionalities including C-O, C=O, and O-C=O, and the satellite peak due to π-π interactions.ADDIN CSL_CITATION {"citationItems":[{"id":"ITEM-1","itemData":{"DOI":"10.1016/j.carbon.2008.02.012","ISBN":"0008-6223","ISSN":"00086223","PMID":"9986945","abstract":"The effect of oxidation on the structural integrity of multiwalled carbon nanotubes through acidic (nitric acid and a mixture of sulfuric acid and hydrogen peroxide) and basic (ammonium hydroxide/hydrogen peroxide) agents has been studied. In order to purify the as-received material, a non-oxidative treatment (with hydrochloric acid) was also applied. Electron microscopy and thermogravimetric analysis clearly revealed that the nitric acid-treated material under reflux conditions suffered the highest degree of degradation, such as, nanotube shortening and additional defect generation in the graphitic network. Basic oxidative treatment led to the complete removal of amorphous carbon and metal oxide impurities but the structural integrity was found to be intact. X-ray photoelectron spectroscopy was employed to confirm the different functionalities produced for each oxidation agent, whereas titration measurements determined the relative concentration of carboxylic functions onto the graphitic surface. Moreover, a general relationship between the chemical treatment and the amount of non-graphitic carbon was established by means of Raman spectroscopy measurements. The possibility of controlling the required amount of functionality, carboxylic and hydroxyl, via these oxidation procedures is discussed. ? 2008 Elsevier Ltd. All rights reserved.","author":[{"dropping-particle":"","family":"Datsyuk","given":"V.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Kalyva","given":"M.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Papagelis","given":"K.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Parthenios","given":"J.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Tasis","given":"D.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Siokou","given":"A.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Kallitsis","given":"I.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Galiotis","given":"C.","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Carbon","id":"ITEM-1","issue":"6","issued":{"date-parts":[["2008"]]},"page":"833-840","title":"Chemical oxidation of multiwalled carbon nanotubes","type":"article-journal","volume":"46"},"uris":[""]}],"mendeley":{"formattedCitation":"⁴⁸","plainTextFormattedCitation":"48","previouslyFormattedCitation":"⁴⁹"},"properties":{"noteIndex":0},"schema":""}48 When the CNT-COOH-H was mixed with HAuCl4 prior to the APP, an Au 4f peak emerged as shown in Figure 3c; the spectrum can be clearly fitted into two doublets centred at the BE of 84.7/88.3 eV and 86.9/90.6 eV that correspond to the BE of ionic Au state, i.e., Au+ and Au3+ in the unreduced salt, respectively.ADDIN CSL_CITATION {"citationItems":[{"id":"ITEM-1","itemData":{"DOI":"10.1088/0022-3727/49/18/185304","ISSN":"13616463","abstract":"? 2016 IOP Publishing Ltd. The graphite-encapsulated gold nanoparticles (Au@C NPs) fabricated by a direct current arc discharge method were surface-functionalized by an inductively-coupled radio frequency ammonia plasma with a particle explosion technique for enhancing surface modification efficiency. To investigate the structural and surface properties of Au@C NPs, characterizations using x-ray diffraction, high resolution transmission electron microscopy and x-ray photoelectron spectroscopy have been conducted on the untreated and plasma treated Au@C NPs. Based on the experimental results, we give insight into the possible formation of Au ions in the interface between the graphite layers and gold core particles of the Au@C NPs. Finally, the role of the plasma treatment on the surface functionalization of Au@C NPs with amino groups is discussed.","author":[{"dropping-particle":"","family":"Yang","given":"E.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Chou","given":"H.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Tsumura","given":"S.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Nagatsu","given":"M.","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Journal of Physics D: Applied Physics","id":"ITEM-1","issued":{"date-parts":[["2016"]]},"title":"Surface properties of plasma-functionalized graphite-encapsulated gold nanoparticles prepared by a direct current arc discharge method","type":"article-journal"},"uris":["",""]},{"id":"ITEM-2","itemData":{"DOI":"10.1016/S0926-3373(01)00221-1","ISSN":"09263373","abstract":"This paper reports a study on the influence of calcination pretreatments on the catalytic behaviour of the Au/iron oxide system towards the combustion of some representative volatile organic compounds (2-propanol, ethanol, methanol, acetone and toluene). The catalytic activity of Au/Fe2O3samples towards the total oxidation to CO2has been found to be strongly dependent on the catalyst pretreatment, decreasing on increasing the calcination temperature. On the basis of characterisation data (XPS, FT-IR, XRD, BET surface area) it has been proposed that the catalytic behaviour is related to the gold state and/or the iron oxide phase. It appears plausible to suggest that the gold oxidation state and/or the particle size play a key role in the catalytic combustion of volatile organic compounds. ? 2001 Elsevier Science B.V. All rights reserved.","author":[{"dropping-particle":"","family":"Minicò","given":"Simona","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Scirè","given":"Salvatore","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Crisafulli","given":"Carmelo","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Galvagno","given":"Signorino","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Applied Catalysis B: Environmental","id":"ITEM-2","issued":{"date-parts":[["2001"]]},"title":"Influence of catalyst pretreatments on volatile organic compounds oxidation over gold/iron oxide","type":"article-journal"},"uris":["",""]},{"id":"ITEM-3","itemData":{"DOI":"10.1039/b909354k","ISBN":"1364-548X (Electronic)\r1359-7345 (Linking)","ISSN":"13597345","PMID":"19652815","abstract":"Isolated cationic gold deposited on sulfated lanthanum oxide has been shown to exhibit remarkable stability opening a promising way of stabilising ionic gold for catalytic reactions.","author":[{"dropping-particle":"","family":"Goguet","given":"Alexandre","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Ace","given":"Matthew","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Saih","given":"Youssef","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Sa","given":"Jacinto","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Kavanagh","given":"Joy","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Hardacre","given":"Christopher","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Chemical Communications","id":"ITEM-3","issued":{"date-parts":[["2009"]]},"title":"Remarkable stability of ionic gold supported on sulfated lanthanum oxide","type":"article-journal"},"uris":["",""]}],"mendeley":{"formattedCitation":"^49–51","plainTextFormattedCitation":"49–51","previouslyFormattedCitation":"^50–52"},"properties":{"noteIndex":0},"schema":""}49–51 After treated by APP, the Au 4f core spectrum of 0.1 mM AuNP/CNT-COOH-H presents two Au 4f7/2 and Au 4f5/2 core peaks centred at the binding energy (BE) of 84.0 eV and 87.7 eV, respectively; these two element states of Au 4f are in accordance with the profiles of reduced metallic Au0, respectively.ADDIN CSL_CITATION {"citationItems":[{"id":"ITEM-1","itemData":{"DOI":"10.1126/science.1076248","ISBN":"1095-9203 (Electronic)\\n0036-8075 (Linking)","ISSN":"00368075","PMID":"12202824","abstract":"Gold nanoparticles ranging in diameter from 1 to 8 nanometers were prepared on top of silicon wafers in order to study the size dependence of their oxidation behavior when exposed to atomic oxygen. X-ray photoelectron spectroscopy showed a maximum oxidation resistance for \"magic-number\" clusters containing 55 gold atoms. This inertness is not related to electron confinement leading to a size-induced metal-to-insulator transition, but rather seems to be linked to the closed-shell structure of such magic clusters. The result additionally suggests that gold-55 clusters may act as especially effective oxidation catalysts, such as for oxidizing carbon monoxide.","author":[{"dropping-particle":"","family":"Boyen","given":"H. G.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"K?stle","given":"G.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Weigl","given":"F.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Koslowski","given":"B.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Dietrich","given":"C.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Ziemann","given":"P.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Spatz","given":"J. P.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Riethmüller","given":"S.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Hartmann","given":"C.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"M?ller","given":"M.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Schmid","given":"G.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Garnier","given":"M. G.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Oelhafen","given":"P.","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Science","id":"ITEM-1","issue":"5586","issued":{"date-parts":[["2002"]]},"page":"1533-1536","title":"Oxidation-resistant gold-55 clusters","type":"article-journal","volume":"297"},"uris":["",""]}],"mendeley":{"formattedCitation":"⁵²","plainTextFormattedCitation":"52","previouslyFormattedCitation":"⁵³"},"properties":{"noteIndex":0},"schema":""}52 The changes seen in the Au 4f states clearly indicate the formation of the AuNPs on CNT-COOH-H surfaces due to the reduction of ionic Au after the APP treatment. In addition, there are also some changes observed in the C 1s core peak of CNT-COOH-H following the mixing with HAuCl4 as well as after the APP treatment. Specifically, the C 1s of the 0.1 mM HAuCl4/CNT-COOH-H sample lefttopTable 3. C 1s peaks analysis results for CNT-COOH-H, 0.1 mM HAuCl4/CNT-COOH-H mixture and 0.1 mM AuNP/CNT-COOH-H hybrid.00Table 3. C 1s peaks analysis results for CNT-COOH-H, 0.1 mM HAuCl4/CNT-COOH-H mixture and 0.1 mM AuNP/CNT-COOH-H hybrid.(Figure 3e) and the 0.1 mM AuNP/CNT-COOH-H sample (Figure 3f) can be both deconvoluted into six peaks, similar to that of the pure CNT-COOH-H sample; the detailed BE and percentage of each fitted peak for all samples are listed in Table pared to pure CNT-COOH-H, the fractions of oxygen-containing -C-O, -C=O and -O-C=O peaks all decreased significantly for both the 0.1 mM HAuCl4/CNT-COOH-H mixture and the 0.1 mM AuNP/CNT-COOH-H hybrid C 1s peak. The result is consistent with the report by Suarez-Martinez et al., where AuNPs formed on the CNT with -COOH terminations had led to a decreased fraction of oxygen-containing carbon species in the C 1s core XPS peak.ADDIN CSL_CITATION {"citationItems":[{"id":"ITEM-1","itemData":{"DOI":"10.1016/j.carbon.2009.02.002","ISBN":"0008-6223","ISSN":"00086223","abstract":"The interaction between evaporated gold and pristine or oxygen plasma treated multi-walled carbon nanotubes (MWCNTs) is investigated. Experimental and theoretical results indicate that gold nucleation occurs at defect sites, whether initially present or introduced by oxygen plasma treatment. Uniform gold cluster dispersion is observed on plasma treated carbon nanotubes (CNTs) and associated with the presence of uniformly dispersed oxidized vacancy centres on the CNT surface. ? 2009 Elsevier Ltd. All rights reserved.","author":[{"dropping-particle":"","family":"Suarez-Martinez","given":"I.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Bittencourt","given":"C.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Ke","given":"X.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Felten","given":"A.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Pireaux","given":"J. J.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Ghijsen","given":"J.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Drube","given":"W.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Tendeloo","given":"G.","non-dropping-particle":"Van","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Ewels","given":"C. P.","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Carbon","id":"ITEM-1","issue":"6","issued":{"date-parts":[["2009"]]},"page":"1549-1554","title":"Probing the interaction between gold nanoparticles and oxygen functionalized carbon nanotubes","type":"article-journal","volume":"47"},"uris":["",""]}],"mendeley":{"formattedCitation":"⁵³","plainTextFormattedCitation":"53","previouslyFormattedCitation":"⁵⁴"},"properties":{"noteIndex":0},"schema":""}53The formation mechanisms leading to reduction and growth of AuNPs can now be discussed. Firstly we should note that when the COOH-functionalized CNTs are dispersed in water, CNTs become negatively charged due to deprotonation and the surface terminations effectively become -COO-.ADDIN CSL_CITATION {"citationItems":[{"id":"ITEM-1","itemData":{"DOI":"10.1016/j.carbon.2007.04.028","ISBN":"0008-6223","ISSN":"00086223","abstract":"The aggregation of acid-treated carbon nanotubes (CNTs) as a solid and their solubility in solvents of different polarity and in water of different pH were investigated as a function of acid treatment conditions. The CNTs were found to form solid hydrogen-bonded aggregates, with a higher content of COOH groups resulting in a denser aggregate. The untreated CNTs were non-polar in nature and could dissolve, or be easily dispersed, in non-polar or low polar solvents such as acetone and alcohols (methanol and ethanol), but precipitated from deionized water, a highly polar solvent. In contrast, the acid-treated CNTs dissolved or were well dispersed in the deionized water, but not in acetone or alcohols. The treated CNTs were insoluble in an aqueous solution of pH 0, but soluble in those of pH 4 and higher with their solubility monotonically increasing with pH up to pH 10. The considerable ionic bond strength between carboxylate anions and sodium cations could be a reason for a decrease of their solubility in an aqueous solution of pH 12. ? 2007 Elsevier Ltd. All rights reserved.","author":[{"dropping-particle":"","family":"Shieh","given":"Yeong Tarng","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Liu","given":"Gin Lung","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Wu","given":"Hou Hsi","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Lee","given":"Chung Chieh","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Carbon","id":"ITEM-1","issue":"9","issued":{"date-parts":[["2007"]]},"page":"1880-1890","title":"Effects of polarity and pH on the solubility of acid-treated carbon nanotubes in different media","type":"article-journal","volume":"45"},"uris":["",""]}],"mendeley":{"formattedCitation":"⁵⁴","plainTextFormattedCitation":"54","previouslyFormattedCitation":"⁵⁵"},"properties":{"noteIndex":0},"schema":""}54 At this point, the CNT aqueous dispersion has pH of ~ 6.3 and the ζ-potential is about -40 mV (Table 4), confirming the surface negative charge and stability of the colloid. Upon addition of the gold salt, the pH is immediately reduced to ~2.3 and also the ζ-potential decreases in absolute values (Table 4). HAuCl4 in water is present in its ionic state (i.e. [AuCl4]- + H+), which justifies the acidity of the solution; here the solution was not buffered at any point of the process and therefore we did not use the pH to control or vary reaction paths. It has been shown that [AuCl4]- undergoes a partial reduction via ion exchange reaction on the CNT surface through chemical binding with the de-protonated -COO- terminationsADDIN CSL_CITATION {"citationItems":[{"id":"ITEM-1","itemData":{"DOI":"10.1038/179723b0","ISBN":"978-94-007-1699-5","ISSN":"00280836","PMID":"25246403","abstract":"This monograph contains 75 chapters divided into 5 parts which cover water treatment, fundamentals, special applications, ion exchange developments, and hydrometallurgy. Topics presented include water purification, anion exchange resins, demineralization, regeneration, condensate polishing, mine water, boiler feed water, selectivity, thermodynamics, activity coefficients, kinetics, colorimetry, enthalpies, EXAFS spectroscopy, computer models, membranes, ion diffusion, electrodialysis, mass transfer, gels, electrolytes, transport properties, resin degradation, alcohol synthesis, aldol condensations, deionization, crown ethers, disinfection, catalysis, ion chromatography, halomethylation, osmosis, chelating resins, eluants, zeolites, ferrierite, microencapsulation, adsorbents, spectrophotometry, platinum metals, hydrometallurgy, noble metals, gold, cyanide liquors, silver, copper, uranium, in-pulp contactors, mining effluents, and tungsten. Refs.","author":[{"dropping-particle":"","family":"Hale","given":"D. K.","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Nature","id":"ITEM-1","issued":{"date-parts":[["1957"]]},"title":"Ion exchange technology","type":"article"},"uris":["",""]}],"mendeley":{"formattedCitation":"⁵⁵","plainTextFormattedCitation":"55","previouslyFormattedCitation":"⁵⁶"},"properties":{"noteIndex":0},"schema":""}55,ADDIN CSL_CITATION {"citationItems":[{"id":"ITEM-1","itemData":{"DOI":"10.1016/j.colsurfa.2007.06.041","ISBN":"0927-7757","ISSN":"09277757","abstract":"The growth of uncoated gold nanoparticles on the surface of multiwalled carbon nanotubes (MWCNTs) through the UV irradiation method was investigated. TEM observations showed that the size and the growth behavior of nanoparticles were primarily affected by the diameter of MWCNTs and solution pH values. The possible mechanisms were also discussed. ? 2007 Elsevier B.V. All rights reserved.","author":[{"dropping-particle":"","family":"Zhang","given":"Ruili","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Wang","given":"Qingfeng","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Zhang","given":"Lu","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Yang","given":"Shengchun","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Yang","given":"Zhimao","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Ding","given":"Bingjun","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Colloids and Surfaces A: Physicochemical and Engineering Aspects","id":"ITEM-1","issue":"2-3","issued":{"date-parts":[["2008"]]},"page":"136-141","title":"The growth of uncoated gold nanoparticles on multiwalled carbon nanotubes","type":"article-journal","volume":"312"},"uris":["",""]}],"mendeley":{"formattedCitation":"⁵⁶","plainTextFormattedCitation":"56","previouslyFormattedCitation":"⁵⁷"},"properties":{"noteIndex":0},"schema":""}56, in particular-COO- + [AuCl4]- → [-COOAuCl3]- + Cl- (1)right6402070Figure 4. The effect of UV–vis spectra of HAuCl4 on the CNT-COOH-H UV-vis absorption profiles.00Figure 4. The effect of UV–vis spectra of HAuCl4 on the CNT-COOH-H UV-vis absorption profiles.right1304925Table 4. ζ- potentials of the CNT-COOH-H solutions before and after the addition of HAuCl4.00Table 4. ζ- potentials of the CNT-COOH-H solutions before and after the addition of HAuCl4.The reduction in the ζ-potential (in absolute values), as observed experimentally (Table 4), is the result of -COO- sites on the surface of CNTs that are now surrounded by Au3+. UV-Vis has been also used to support reaction (1), see Figure 4. For pure HAuCl4 aqueous solution, two absorption bands are present at approximately 220 nm and 288 nm, corresponding to the pπ5dx2?y2 and pσ5dx2?y2 ligand-metal transition modes in the [AuCl4]– complex structures, respectively.ADDIN CSL_CITATION {"citationItems":[{"id":"ITEM-1","itemData":{"DOI":"10.1021/cm034932o","ISBN":"0897-4756","ISSN":"08974756","abstract":"Highly monodisperse, 1-2-nm diameter Au nanoparticles were prepared using poly(amidoamine) (PAMAM) dendrimers as templates. The synthesis is carried out in water, takes less than 30 min, and requires no subsequent purification. Au nanoparticles having diameters of 1.3 0.3 and 1.6 0.3 nm were obtained when 55 and 140 equiv, respectively, of HAuCl4 per dendrimer were used. For unpurified Au nanoparticles in this size range, this represents more than a 200% improvement in size distribution compared to previous reports. The high monodispersity is a function of the template synthesis, which avoids size variations arising from random nucleation and growth phenomena, and the use of magic number equivalent ratios of AuCl4-/dendrimer. When a nonmagic number of AuCl4- equivalents per dendrimer was used, a significantly more polydisperse distribution of Au nanoparticles was obtained.","author":[{"dropping-particle":"","family":"Kim","given":"Yong Gu","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Oh","given":"Sang Keun","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Crooks","given":"Richard M.","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Chemistry of Materials","id":"ITEM-1","issue":"1","issued":{"date-parts":[["2004"]]},"page":"167-172","title":"Preparation and Characterization of 1-2 nm Dendrimer-Encapsulated Gold Nanoparticles Having Very Narrow Size Distributions","type":"article-journal","volume":"16"},"uris":[""]}],"mendeley":{"formattedCitation":"⁵⁷","plainTextFormattedCitation":"57","previouslyFormattedCitation":"⁵⁸"},"properties":{"noteIndex":0},"schema":""}57 The absorption peaks of free [AuCl4]– (220 nm and 280 nm) both decreased and blue shifted when UV-Vis was taken from the 0.1 mM HAuCl4/CNT-COOH-H solution prior to APP processing. This transition can be attributed to the interaction between the [AuCl4]– complex and the de-protonated carboxylic groups as per reaction (1).Our results therefore corroborate surface reaction (1) whereby pH, ζ-potential, UV-Vis and also the reduction of the oxygen-containing carbon species in the C 1s core XPS peak (Table 3) are all in agreement with the literature.ADDIN CSL_CITATION {"citationItems":[{"id":"ITEM-1","itemData":{"DOI":"10.1016/j.colsurfa.2007.06.041","ISBN":"0927-7757","ISSN":"09277757","abstract":"The growth of uncoated gold nanoparticles on the surface of multiwalled carbon nanotubes (MWCNTs) through the UV irradiation method was investigated. TEM observations showed that the size and the growth behavior of nanoparticles were primarily affected by the diameter of MWCNTs and solution pH values. The possible mechanisms were also discussed. ? 2007 Elsevier B.V. All rights reserved.","author":[{"dropping-particle":"","family":"Zhang","given":"Ruili","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Wang","given":"Qingfeng","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Zhang","given":"Lu","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Yang","given":"Shengchun","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Yang","given":"Zhimao","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Ding","given":"Bingjun","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Colloids and Surfaces A: Physicochemical and Engineering Aspects","id":"ITEM-1","issue":"2-3","issued":{"date-parts":[["2008"]]},"page":"136-141","title":"The growth of uncoated gold nanoparticles on multiwalled carbon nanotubes","type":"article-journal","volume":"312"},"uris":["",""]},{"id":"ITEM-2","itemData":{"DOI":"10.1016/j.carbon.2009.02.002","ISBN":"0008-6223","ISSN":"00086223","abstract":"The interaction between evaporated gold and pristine or oxygen plasma treated multi-walled carbon nanotubes (MWCNTs) is investigated. Experimental and theoretical results indicate that gold nucleation occurs at defect sites, whether initially present or introduced by oxygen plasma treatment. Uniform gold cluster dispersion is observed on plasma treated carbon nanotubes (CNTs) and associated with the presence of uniformly dispersed oxidized vacancy centres on the CNT surface. ? 2009 Elsevier Ltd. All rights reserved.","author":[{"dropping-particle":"","family":"Suarez-Martinez","given":"I.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Bittencourt","given":"C.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Ke","given":"X.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Felten","given":"A.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Pireaux","given":"J. J.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Ghijsen","given":"J.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Drube","given":"W.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Tendeloo","given":"G.","non-dropping-particle":"Van","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Ewels","given":"C. P.","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Carbon","id":"ITEM-2","issue":"6","issued":{"date-parts":[["2009"]]},"page":"1549-1554","title":"Probing the interaction between gold nanoparticles and oxygen functionalized carbon nanotubes","type":"article-journal","volume":"47"},"uris":["",""]}],"mendeley":{"formattedCitation":"^53,56","plainTextFormattedCitation":"53,56","previouslyFormattedCitation":"^54,57"},"properties":{"noteIndex":0},"schema":""}53,56 It follows that the aqueous samples subjected to the plasma treatment are therefore formed by CNTs with a hybrid surface functionalization (i.e. [-COOAuCl3]-) and with the remaining of the gold salt still in solution. The subsequent formation of the AuNP has taken place through APP induced chemistry, where we believe that [-COOAuCl3]- on the surface of the CNTs served as preferential sites for further reduction and growth. We should note that the mechanisms leading to particle growth in this type of plasma-assisted processes are different, but in some aspects closely related to nanoparticle formation using more standard methods (e.g. wet chemistry), which are still source of great debates; for instance, the formation mechanism of the so-called “Turkevich synthesis”ADDIN CSL_CITATION {"citationItems":[{"id":"ITEM-1","itemData":{"DOI":"10.1039/DF9511100055","ISBN":"0366-9033","ISSN":"0366-9033","abstract":"After a preliminary survey with the electron microscope of various preparations of colloidal gold, a study was made of the process of nucleation and growth in gold colloids. It was shown that nucleating agents may be identified with reducing agents which form a mixed polymer with chlorauric ion before the reduction to the nucleus takes place. It was also shown that the law of growth is exponential. The average size, the deviation from the average size and the character of the particle size distribution curve are determined by the amount of gold, the nucleation process and the law of growth.","author":[{"dropping-particle":"","family":"Turkevich","given":"J.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Stevenson","given":"P. Cooper","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Hillier","given":"J.","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Discuss. Faraday Soc.","id":"ITEM-1","issue":"c","issued":{"date-parts":[["1951"]]},"page":"55-75","title":"A study of the nucleation and growth processes in the synthesis of colloidal gold","type":"article-journal","volume":"11"},"uris":[""]}],"mendeley":{"formattedCitation":"⁵⁸","plainTextFormattedCitation":"58","previouslyFormattedCitation":"⁵⁹"},"properties":{"noteIndex":0},"schema":""}58, which was initially proposed in 1951, is still largely under investigation.ADDIN CSL_CITATION {"citationItems":[{"id":"ITEM-1","itemData":{"DOI":"10.1039/c5cp02219c","ISBN":"1463-9084 (Electronic)\r1463-9076 (Linking)","ISSN":"14639076","PMID":"26165172","abstract":"<p>The growth process of various colloidal metal nanoparticles is illustrated using a novel concept based on colloidal stability.</p>","author":[{"dropping-particle":"","family":"Wuithschick","given":"M.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Witte","given":"S.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Kettemann","given":"F.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Rademann","given":"K.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Polte","given":"J.","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Physical Chemistry Chemical Physics","id":"ITEM-1","issued":{"date-parts":[["2015"]]},"title":"Illustrating the formation of metal nanoparticles with a growth concept based on colloidal stability","type":"article-journal"},"uris":["",""]},{"id":"ITEM-2","itemData":{"DOI":"10.1021/acsnano.5b01579","ISBN":"1936-0851","ISSN":"1936086X","PMID":"26147899","abstract":"This contribution provides a comprehensive mechanistic picture of the gold nanoparticle synthesis by citrate reduction of HAuCl4, known as Turkevich method, by addressing five key questions. The synthesis leads to monodisperse final particles as a result of a seed-mediated growth mechanism. In the initial phase of the synthesis, seed particles are formed onto which the residual gold is distributed during the course of reaction. It is shown that this mechanism is a fortunate coincidence created by a favorable interplay of several chemical and physicochemical processes which initiate but also terminate the formation of seed particles and prevent the formation of further particles at later stages of reaction. Since no further particles are formed after seed particle formation, the number of seeds defines the final total particle number and therefore the final size. The gained understanding allows illustrating the influence of reaction conditions on the growth process and thus the final size distribution.","author":[{"dropping-particle":"","family":"Wuithschick","given":"Maria","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Birnbaum","given":"Alexander","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Witte","given":"Steffen","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Sztucki","given":"Michael","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Vainio","given":"Ulla","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Pinna","given":"Nicola","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Rademann","given":"Klaus","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Emmerling","given":"Franziska","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Kraehnert","given":"Ralph","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Polte","given":"J?rg","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"ACS Nano","id":"ITEM-2","issue":"7","issued":{"date-parts":[["2015"]]},"page":"7052-7071","title":"Turkevich in New Robes: Key Questions Answered for the Most Common Gold Nanoparticle Synthesis","type":"article-journal","volume":"9"},"uris":["",""]},{"id":"ITEM-3","itemData":{"DOI":"10.1021/la201938u","ISBN":"0743-7463","ISSN":"07437463","PMID":"21728302","abstract":"Monodisperse citrate-stabilized gold nanoparticles with a uniform quasi-spherical shape of up to ～200 nm and a narrow size distribution were synthesized following a kinetically controlled seeded growth strategy via the reduction of HAuCl(4) by sodium citrate. The inhibition of any secondary nucleation during homogeneous growth was controlled by adjusting the reaction conditions: temperature, gold precursor to seed particle concentration, and pH. This method presents improved results regarding the traditional Frens method in several aspects: (i) it produces particles of higher monodispersity; (ii) it allows better control of the gold nanoparticle size and size distribution; and (iii) it leads to higher concentrations. Gold nanoparticles synthesized following this method can be further functionalized with a wide variety of molecules, hence this method appears to be a promising candidate for application in the fields of biomedicine, photonics, and electronics, among others.","author":[{"dropping-particle":"","family":"Bastús","given":"Neus G.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Comenge","given":"Joan","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Puntes","given":"Víctor","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Langmuir","id":"ITEM-3","issue":"17","issued":{"date-parts":[["2011"]]},"page":"11098-11105","title":"Kinetically controlled seeded growth synthesis of citrate-stabilized gold nanoparticles of up to 200 nm: Size focusing versus ostwald ripening","type":"article-journal","volume":"27"},"uris":[""]},{"id":"ITEM-4","itemData":{"DOI":"10.1021/jp061667w","ISBN":"1520-6106","ISSN":"15206106","PMID":"16898714","abstract":"The growth of gold nanoparticles by reduction by citrate and ascorbic acid has been examined in detail to explore the parameter space of reaction conditions. It is found that gold particles can be produced in a wide range of sizes, from 9 to 120 nm, with defined size distribution, following the earlier work of Turkevich and Frens. The reaction is initiated thermally or in comparison by UV irradiation, which results in similar final products. The kinetics of the extinction spectra show the multiple steps of primary and secondary clustering leading to polycrystallites.","author":[{"dropping-particle":"","family":"Kimling","given":"J.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Maier","given":"M.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Okenve","given":"B.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Kotaidis","given":"V.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Ballot","given":"H.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Plech","given":"A.","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Journal of Physical Chemistry B","id":"ITEM-4","issue":"32","issued":{"date-parts":[["2006"]]},"page":"15700-15707","title":"Turkevich method for gold nanoparticle synthesis revisited","type":"article-journal","volume":"110"},"uris":[""]}],"mendeley":{"formattedCitation":"^46,59–61","plainTextFormattedCitation":"46,59–61","previouslyFormattedCitation":"^47,60–62"},"properties":{"noteIndex":0},"schema":""}46,59–61 It is convenient at this point to discuss separately the reduction/supply of Au monomers and the AuNP growth. The reduction and supply of Au monomer under plasma treatment can take place through different pathways (see Scheme 2). Solvated electrons (Scheme 2-I) and hydrogen peroxide (Scheme 2-II), both formed at the plasma-liquid interface, are known to be the main reducing agents as demonstrated by the relevant literature for comparable systems.ADDIN CSL_CITATION {"citationItems":[{"id":"ITEM-1","itemData":{"DOI":"10.1088/0957-4484/24/24/245604","ISBN":"1361-6528 (Electronic)\\r0957-4484 (Linking)","ISSN":"0957-4484","PMID":"23696315","abstract":"Plasma-induced non-equilibrium liquid chemistry is used to synthesize gold nanoparticles (AuNPs) without using any reducing or capping agents. The morphology and optical properties of the synthesized AuNPs are characterized by transmission electron microscopy (TEM) and ultraviolet-visible spectroscopy. Plasma processing parameters affect the particle shape and size and the rate of the AuNP synthesis process. Particles of different shapes (e.g. spherical, triangular, hexagonal, pentagonal, etc) are synthesized in aqueous solutions. In particular, the size of the AuNPs can be tuned from 5 nm to several hundred nanometres by varying the initial gold precursor (HAuCl4) concentration from 2.5 μM to 1 mM. In order to reveal details of the basic plasma-liquid interactions that lead to AuNP synthesis, we have measured the solution pH, conductivity and hydrogen peroxide (H2O2) concentration of the liquid after plasma processing, and conclude that H2O2 plays the role of the reducing agent which converts Au(+3) ions to Au(0) atoms, leading to nucleation growth of the AuNPs.","author":[{"dropping-particle":"","family":"Patel","given":"J","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Němcová","given":"L","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Maguire","given":"P","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Graham","given":"W G","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Mariotti","given":"D","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Nanotechnology","id":"ITEM-1","issue":"24","issued":{"date-parts":[["2013"]]},"page":"245604","title":"Synthesis of surfactant-free electrostatically stabilized gold nanoparticles by plasma-induced liquid chemistry","type":"article-journal","volume":"24"},"uris":[""]},{"id":"ITEM-2","itemData":{"DOI":"10.1021/acs.nanolett.6b03440","ISSN":"15306992","PMID":"28139927","abstract":"? 2017 American Chemical Society. We demonstrate an entirely new method of nanoparticle chemical synthesis based on liquid droplet irradiation with ultralow ( < 0.1 eV) energy electrons. While nanoparticle formation via high energy radiolysis or transmission electron microscopy-based electron bombardment is well-understood, we have developed a source of electrons with energies close to thermal which leads to a number of important and unique benefits. The charged species, including the growing nanoparticles, are held in an ultrathin surface reaction zone which enables extremely rapid precursor reduction. In a proof-of-principle demonstration, we obtain small-diameter Au nanoparticles (～4 nm) with tight control of polydispersity, in under 150 μs. The precursor was almost completely reduced in this period, and the resultant nanoparticles were water-soluble and free of surfactant or additional ligand chemistry. Nanoparticle synthesis rates within the droplets were many orders of magnitude greater than equivalent rates reported for radiolysis, electron beam irradiation, or colloidal chemical synthesis where reaction times vary from seconds to hours. In our device, a stream of precursor loaded microdroplets, ～15 μm in diameter, were transported rapidly through a cold atmospheric pressure plasma with a high charge concentration. A high electron flux, electron and nanoparticle confinement at the surface of the droplet, and the picoliter reactor volume are thought to be responsible for the remarkable enhancement in nanoparticle synthesis rates. While this approach exhibits considerable potential for scale-up of synthesis rates, it also offers the more immediate prospect of continuous on-demand delivery of high-quality nanomaterials directly to their point of use by avoiding the necessity of collection, recovery, and purification. A range of new applications can be envisaged, from theranostics and biomedical imaging in tissue to inline catalyst production for pollution remediation in automobiles.","author":[{"dropping-particle":"","family":"Maguire","given":"Paul","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Rutherford","given":"David","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Macias-Montero","given":"Manuel","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Mahony","given":"Charles","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Kelsey","given":"Colin","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Tweedie","given":"Mark","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Pérez-Martin","given":"Fátima","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"McQuaid","given":"Harold","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Diver","given":"Declan","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Mariotti","given":"Davide","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Nano Letters","id":"ITEM-2","issue":"3","issued":{"date-parts":[["2017"]]},"page":"1336-1343","title":"Continuous In-Flight Synthesis for On-Demand Delivery of Ligand-Free Colloidal Gold Nanoparticles","type":"article-journal","volume":"17"},"uris":[""]},{"id":"ITEM-3","itemData":{"DOI":"10.1021/jp207447c","ISBN":"1932-7447","ISSN":"19327447","abstract":"Size-controlled gold nanoparticles (NPs) have been synthesized using an electrical discharge in a liquid environment, termed solution plasma processing (SPP). The gold NPs exhibit sizes from 1 to 2 to 10 nm when the solution pH was adjusted in the range from 12 to 3, respectively. The chemical environment surrounding the gold NPs depends on the preparation conditions and determines the electrostatic interaction among the nanoparticles, which alters their final size. Information obtained from XPS analysis, ToF-SIMS mass spectra, and UV?vis absorption spectroscopy were consistent and demonstrate that the gold NPs are partially oxidized on the surface, when synthesized in a pH 12 solution, and remain surrounded by gold chloride compounds when synthesized in a pH 3 solution. Plasma diagnostics shows that a high electron density contributes to generating a larger number of hydrogen radicals, which represent the main component in the reduction process of the gold ion into the neutral form.","author":[{"dropping-particle":"","family":"Bratescu","given":"Maria Antoaneta","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Cho","given":"Sung Pyo","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Takai","given":"Osamu","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Saito","given":"Nagahiro","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Journal of Physical Chemistry C","id":"ITEM-3","issue":"50","issued":{"date-parts":[["2011"]]},"page":"24569-24576","title":"Size-controlled gold nanoparticles synthesized in solution plasma","type":"article-journal","volume":"115"},"uris":[""]},{"id":"ITEM-4","itemData":{"DOI":"10.1039/C3CC48846B","ISBN":"1364-548X (Electronic)\\r1359-7345 (Linking)","ISSN":"1359-7345","PMID":"24519646","abstract":"<p>A new conceptual microplasma-based approach is developed to produce AuAg alloyed crystalline nanoparticles at atmospheric pressure and low temperatures, in the absence of a chemical reducing agent. Real-time plasmonic monitoring is demonstrated.</p>","author":[{"dropping-particle":"","family":"Yan","given":"Tingting","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Zhong","given":"Xiaoxia","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Rider","given":"Amanda Evelyn","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Lu","given":"Yi","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Furman","given":"Scott A.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Ostrikov","given":"Kostya (Ken)","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Chem. Commun.","id":"ITEM-4","issue":"24","issued":{"date-parts":[["2014"]]},"page":"3144-3147","title":"Microplasma-chemical synthesis and tunable real-time plasmonic responses of alloyed Au _x Ag _1?x nanoparticles","type":"article-journal","volume":"50"},"uris":[""]}],"mendeley":{"formattedCitation":"^40,41,62,63","plainTextFormattedCitation":"40,41,62,63","previouslyFormattedCitation":"^41,42,63,64"},"properties":{"noteIndex":0},"schema":""}40,41,62,63 The reducing power of solvated electrons is limited to a volume close to the interface due to their short lifetime.ADDIN CSL_CITATION {"citationItems":[{"id":"ITEM-1","itemData":{"DOI":"10.1021/acs.nanolett.6b03440","ISSN":"15306992","PMID":"28139927","abstract":"? 2017 American Chemical Society. We demonstrate an entirely new method of nanoparticle chemical synthesis based on liquid droplet irradiation with ultralow ( < 0.1 eV) energy electrons. While nanoparticle formation via high energy radiolysis or transmission electron microscopy-based electron bombardment is well-understood, we have developed a source of electrons with energies close to thermal which leads to a number of important and unique benefits. The charged species, including the growing nanoparticles, are held in an ultrathin surface reaction zone which enables extremely rapid precursor reduction. In a proof-of-principle demonstration, we obtain small-diameter Au nanoparticles (～4 nm) with tight control of polydispersity, in under 150 μs. The precursor was almost completely reduced in this period, and the resultant nanoparticles were water-soluble and free of surfactant or additional ligand chemistry. Nanoparticle synthesis rates within the droplets were many orders of magnitude greater than equivalent rates reported for radiolysis, electron beam irradiation, or colloidal chemical synthesis where reaction times vary from seconds to hours. In our device, a stream of precursor loaded microdroplets, ～15 μm in diameter, were transported rapidly through a cold atmospheric pressure plasma with a high charge concentration. A high electron flux, electron and nanoparticle confinement at the surface of the droplet, and the picoliter reactor volume are thought to be responsible for the remarkable enhancement in nanoparticle synthesis rates. While this approach exhibits considerable potential for scale-up of synthesis rates, it also offers the more immediate prospect of continuous on-demand delivery of high-quality nanomaterials directly to their point of use by avoiding the necessity of collection, recovery, and purification. A range of new applications can be envisaged, from theranostics and biomedical imaging in tissue to inline catalyst production for pollution remediation in automobiles.","author":[{"dropping-particle":"","family":"Maguire","given":"Paul","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Rutherford","given":"David","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Macias-Montero","given":"Manuel","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Mahony","given":"Charles","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Kelsey","given":"Colin","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Tweedie","given":"Mark","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Pérez-Martin","given":"Fátima","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"McQuaid","given":"Harold","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Diver","given":"Declan","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Mariotti","given":"Davide","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Nano Letters","id":"ITEM-1","issue":"3","issued":{"date-parts":[["2017"]]},"page":"1336-1343","title":"Continuous In-Flight Synthesis for On-Demand Delivery of Ligand-Free Colloidal Gold Nanoparticles","type":"article-journal","volume":"17"},"uris":[""]},{"id":"ITEM-2","itemData":{"DOI":"10.1038/ncomms8248","ISBN":"2041-1733","ISSN":"20411723","PMID":"26088017","abstract":"Solvated electrons are typically generated by radiolysis or photoionization of solutes. While plasmas containing free electrons have been brought into contact with liquids in studies dating back centuries, there has been little evidence that electrons are solvated by this approach. Here we report direct measurements of solvated electrons generated by an atmospheric-pressure plasma in contact with the surface of an aqueous solution. The electrons are measured by their optical absorbance using a total internal reflection geometry. The measured absorption spectrum is unexpectedly blue shifted, which is potentially due to the intense electric field in the interfacial Debye layer. We estimate an average penetration depth of 2.5 ± 1.0 nm, indicating that the electrons fully solvate before reacting through second-order recombination. Reactions with various electron scavengers including H(+), NO2(-), NO3(-) and H2O2 show that the kinetics are similar, but not identical, to those for solvated electrons formed in bulk water by radiolysis.","author":[{"dropping-particle":"","family":"Rumbach","given":"Paul","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Bartels","given":"David M.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Sankaran","given":"R. Mohan","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Go","given":"David B.","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Nature Communications","id":"ITEM-2","issued":{"date-parts":[["2015"]]},"title":"The solvation of electrons by an atmospheric-pressure plasma","type":"article-journal","volume":"6"},"uris":["",""]}],"mendeley":{"formattedCitation":"^40,64","plainTextFormattedCitation":"40,64","previouslyFormattedCitation":"^41,65"},"properties":{"noteIndex":0},"schema":""}40,64 H2O2 on the other hand diffuses deeper into the bulk solution. The reducing power of hydrogen peroxide for HAuCl4 is generally believed to prefer basic solutions, however this does not necessarily mean that reduction is completely prevented in acid environment; in fact there is experimental evidence that reduction is effective within minutes even with pH < 3.ADDIN CSL_CITATION {"citationItems":[{"id":"ITEM-1","itemData":{"DOI":"10.1021/acs.nanolett.6b03440","ISSN":"15306992","PMID":"28139927","abstract":"? 2017 American Chemical Society. We demonstrate an entirely new method of nanoparticle chemical synthesis based on liquid droplet irradiation with ultralow ( < 0.1 eV) energy electrons. While nanoparticle formation via high energy radiolysis or transmission electron microscopy-based electron bombardment is well-understood, we have developed a source of electrons with energies close to thermal which leads to a number of important and unique benefits. The charged species, including the growing nanoparticles, are held in an ultrathin surface reaction zone which enables extremely rapid precursor reduction. In a proof-of-principle demonstration, we obtain small-diameter Au nanoparticles (～4 nm) with tight control of polydispersity, in under 150 μs. The precursor was almost completely reduced in this period, and the resultant nanoparticles were water-soluble and free of surfactant or additional ligand chemistry. Nanoparticle synthesis rates within the droplets were many orders of magnitude greater than equivalent rates reported for radiolysis, electron beam irradiation, or colloidal chemical synthesis where reaction times vary from seconds to hours. In our device, a stream of precursor loaded microdroplets, ～15 μm in diameter, were transported rapidly through a cold atmospheric pressure plasma with a high charge concentration. A high electron flux, electron and nanoparticle confinement at the surface of the droplet, and the picoliter reactor volume are thought to be responsible for the remarkable enhancement in nanoparticle synthesis rates. While this approach exhibits considerable potential for scale-up of synthesis rates, it also offers the more immediate prospect of continuous on-demand delivery of high-quality nanomaterials directly to their point of use by avoiding the necessity of collection, recovery, and purification. A range of new applications can be envisaged, from theranostics and biomedical imaging in tissue to inline catalyst production for pollution remediation in automobiles.","author":[{"dropping-particle":"","family":"Maguire","given":"Paul","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Rutherford","given":"David","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Macias-Montero","given":"Manuel","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Mahony","given":"Charles","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Kelsey","given":"Colin","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Tweedie","given":"Mark","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Pérez-Martin","given":"Fátima","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"McQuaid","given":"Harold","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Diver","given":"Declan","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Mariotti","given":"Davide","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Nano Letters","id":"ITEM-1","issue":"3","issued":{"date-parts":[["2017"]]},"page":"1336-1343","title":"Continuous In-Flight Synthesis for On-Demand Delivery of Ligand-Free Colloidal Gold Nanoparticles","type":"article-journal","volume":"17"},"uris":[""]}],"mendeley":{"formattedCitation":"⁴⁰","plainTextFormattedCitation":"40","previouslyFormattedCitation":"⁴¹"},"properties":{"noteIndex":0},"schema":""}40 A third possibility (Scheme 2-III), determined by the CNT electron affinity and high conductivity, is that negative charges are captured and transported to the CNT surface binding sites, contributing to the surface reduction.ADDIN CSL_CITATION {"citationItems":[{"id":"ITEM-1","itemData":{"DOI":"10.1021/jp1043706","ISBN":"1932-7447","ISSN":"1932-7447","abstract":"The electrodeposition mechanism of gold nanoparticles (NPs) on pristine single walled carbon nanotubes (SWNTs) at high driving forces has been elucidated using the microcapillary electrochemical method. Here, a small capillary (internal diameter ?50?100 ?m) filled with a gold plating solution, and positioned so that the capillary meniscus makes contact with a two-dimensional SWNT random network, was used to record current?time transients. Nucleation and growth transients were observed in which the current increased with time to a maximum value beyond which the current decreased (planar diffusion regime). With increased driving force, the current maximum shifted dramatically to increasingly shorter times. Atomic force microscopy (AFM) analysis indicated that this was not due to significant differences in NP growth rates, but rather to increased densities of NPs formed at more cathodic potentials. Detailed microscopic analysis showed that the size of the NPs initially increased with deposition time and the particle surface coverage was constant. However, at the highest driving forces the NP density decreased with deposition time and AFM revealed the presence of both larger and smaller particles at long times. This was attributed to electrochemically induced Ostwald ripening, whereby larger particles grow at the expense of smaller ones. As NP nucleation and growth on SWNT two dimensional network electrodes is highly directional and enforced in particular locations, it is inappropriate to analyze electrochemical data using conventional models. There is thus a need to complement chronoamperometric measurements with high resolution microscopy to fully interpret nucleation on complex electrode surfaces.","author":[{"dropping-particle":"V","family":"Dudin","given":"Petr","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Unwin","given":"Patrick R","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"V","family":"Macpherson","given":"Julie","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"The Journal of Physical Chemistry C","id":"ITEM-1","issue":"i","issued":{"date-parts":[["2010"]]},"page":"13241-13248","title":"Electrochemical Nucleation and Growth of Gold Nanoparticles on Single-Walled Carbon Nanotubes: New Mechanistic Insights","type":"article-journal","volume":"114"},"uris":["",""]}],"mendeley":{"formattedCitation":"⁶⁵","plainTextFormattedCitation":"65","previouslyFormattedCitation":"⁶⁶"},"properties":{"noteIndex":0},"schema":""}65 The mechanisms involved in the electron transport between CNT and AuNP has been reported by Khoo et al. using density function calculations and the details can be found elsewhere.ADDIN CSL_CITATION {"citationItems":[{"id":"ITEM-1","itemData":{"DOI":"10.1103/PhysRevB.79.205422","ISBN":"1098-0121\\r1550-235X","ISSN":"10980121","abstract":"In recent years, there has been extensive research on carbon nanotube networks owing to their potential for applications in transparent electronics. Several experimental studies have found that electrical conductivity across these networks can be increased by metal nanoparticle doping. To aid in understanding the mechanism of this conductance increase, we have performed first-principles calculations on nanotube junctions decorated with small Au nanoparticles. Our calculations show that the conductance of nanotube junctions is increased by the introduction of odd-numbered Au nanoparticles and electron transport is mediated by resonant tunneling through Au nanoparticle states. In addition, we find interesting interference effects that modulate conduction across doped nanotube junctions that connect near nanotube tips.","author":[{"dropping-particle":"","family":"Khoo","given":"K. H.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Chelikowsky","given":"James R.","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Physical Review B - Condensed Matter and Materials Physics","id":"ITEM-1","issue":"20","issued":{"date-parts":[["2009"]]},"title":"Electron transport across carbon nanotube junctions decorated with Au nanoparticles: Density functional calculations","type":"article-journal","volume":"79"},"uris":["",""]}],"mendeley":{"formattedCitation":"⁶⁶","plainTextFormattedCitation":"66","previouslyFormattedCitation":"⁶⁷"},"properties":{"noteIndex":0},"schema":""}66 We acknowledge that mechanism (III) is a speculation and would require a deeper in-depth investigation, however we believe it is worthwhile mentioning as it could open up interesting synthetic prospects.While it is difficult to quantitatively assess the dominant reduction mechanism, known reaction kinetic parameters can help to provide a qualitative description of the AuNP growth. The kinetics of electron-induced reaction is much faster than that of hydrogen peroxide and therefore we believe that the first pathway (i.e. due to solvated electrons) is mainly responsible for the initial growth through aggregation and coalescence close to the plasma-liquid interface. On the other hand, reduction due to H2O2 mainly drives coalescence and surface growth in the bulk of the solution.With respect to AuNPs growth, this is necessarily initiated by seed-formation through aggregation and coalescence, irrespective of the reduction pathways.ADDIN CSL_CITATION {"citationItems":[{"id":"ITEM-1","itemData":{"DOI":"10.1021/acsnano.5b01579","ISBN":"1936-0851","ISSN":"1936086X","PMID":"26147899","abstract":"This contribution provides a comprehensive mechanistic picture of the gold nanoparticle synthesis by citrate reduction of HAuCl4, known as Turkevich method, by addressing five key questions. The synthesis leads to monodisperse final particles as a result of a seed-mediated growth mechanism. In the initial phase of the synthesis, seed particles are formed onto which the residual gold is distributed during the course of reaction. It is shown that this mechanism is a fortunate coincidence created by a favorable interplay of several chemical and physicochemical processes which initiate but also terminate the formation of seed particles and prevent the formation of further particles at later stages of reaction. Since no further particles are formed after seed particle formation, the number of seeds defines the final total particle number and therefore the final size. The gained understanding allows illustrating the influence of reaction conditions on the growth process and thus the final size distribution.","author":[{"dropping-particle":"","family":"Wuithschick","given":"Maria","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Birnbaum","given":"Alexander","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Witte","given":"Steffen","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Sztucki","given":"Michael","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Vainio","given":"Ulla","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Pinna","given":"Nicola","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Rademann","given":"Klaus","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Emmerling","given":"Franziska","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Kraehnert","given":"Ralph","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Polte","given":"J?rg","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"ACS Nano","id":"ITEM-1","issue":"7","issued":{"date-parts":[["2015"]]},"page":"7052-7071","title":"Turkevich in New Robes: Key Questions Answered for the Most Common Gold Nanoparticle Synthesis","type":"article-journal","volume":"9"},"uris":[""]}],"mendeley":{"formattedCitation":"⁶⁰","plainTextFormattedCitation":"60","previouslyFormattedCitation":"⁶¹"},"properties":{"noteIndex":0},"schema":""}60 Aggregation initially leads to thermodynamically stable nuclei (a few Au atoms), which aggregate further or coalesce into stable seed particles. The formation of seed particles occurs both in the liquid phase as well as at the [-COOAuCl3]- sites, the latter after reduction by either solvated electrons or hydrogen peroxide. Seed formation is then followed by surface growth where the remaining gold ions tend to be attracted and reduced in the electronic double layer. Coalescence is limited by colloidal stability, while surface growth continues until the monomer supply terminates, i.e. when the salt is consumed. left11182Scheme 2. Potential reaction pathways in APP synthesis of AuNP/CNT-COOH-H hybrids. 00Scheme 2. Potential reaction pathways in APP synthesis of AuNP/CNT-COOH-H hybrids. This qualitative description of the growth mechanisms is drawn from studies of AuNPs formation via standard wet chemical methods, however it is supported by our findings. For instance, growth by coalescence ensures that NPs are grown at the CNT hybrid sites; this is because, without coalescence, NPs would be present also in solution, which is not what we have observed. The synthesis of AuNPs without CNTs (see Figure S3 in SI) shows that, for the concentrations considered here, colloidal stability is reached during coalescence and before agglomeration; this confirms that surface growth continues until the monomer supply is halted. AuNPs produced on the CNTs, for the same initial salt concentration, are generally smaller and more spherical than NPs produced without CNTs (also see Figure S3 in SI). This shows that CNTs impact the aggregation stage and cluster formationADDIN CSL_CITATION {"citationItems":[{"id":"ITEM-1","itemData":{"DOI":"10.1021/acsnano.5b01579","ISBN":"1936-0851","ISSN":"1936086X","PMID":"26147899","abstract":"This contribution provides a comprehensive mechanistic picture of the gold nanoparticle synthesis by citrate reduction of HAuCl4, known as Turkevich method, by addressing five key questions. The synthesis leads to monodisperse final particles as a result of a seed-mediated growth mechanism. In the initial phase of the synthesis, seed particles are formed onto which the residual gold is distributed during the course of reaction. It is shown that this mechanism is a fortunate coincidence created by a favorable interplay of several chemical and physicochemical processes which initiate but also terminate the formation of seed particles and prevent the formation of further particles at later stages of reaction. Since no further particles are formed after seed particle formation, the number of seeds defines the final total particle number and therefore the final size. The gained understanding allows illustrating the influence of reaction conditions on the growth process and thus the final size distribution.","author":[{"dropping-particle":"","family":"Wuithschick","given":"Maria","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Birnbaum","given":"Alexander","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Witte","given":"Steffen","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Sztucki","given":"Michael","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Vainio","given":"Ulla","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Pinna","given":"Nicola","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Rademann","given":"Klaus","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Emmerling","given":"Franziska","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Kraehnert","given":"Ralph","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Polte","given":"J?rg","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"ACS Nano","id":"ITEM-1","issue":"7","issued":{"date-parts":[["2015"]]},"page":"7052-7071","title":"Turkevich in New Robes: Key Questions Answered for the Most Common Gold Nanoparticle Synthesis","type":"article-journal","volume":"9"},"uris":[""]}],"mendeley":{"formattedCitation":"⁶⁰","plainTextFormattedCitation":"60","previouslyFormattedCitation":"⁶¹"},"properties":{"noteIndex":0},"schema":""}60 and this is because the presence of hybrid CNT-Au sites forces the formation of a higher number of clusters reducing the mobility of a fraction of the gold salt precursor.The main distinctive components of plasma-assisted synthesis are various: i) fast kinetics offered by electron-induced reduction, ii) on demand and localized production of the reducing agents (e.g. H2O2 and electrons), and iii) contained reaction volume with strong concentration gradients. These allow tailoring the reaction pathways and better controlling of the time/impact of the growth mechanisms, e.g. the reduction of the reaction volume can preclude surface growth.ADDIN CSL_CITATION {"citationItems":[{"id":"ITEM-1","itemData":{"DOI":"10.1021/acs.nanolett.6b03440","ISSN":"15306992","PMID":"28139927","abstract":"? 2017 American Chemical Society. We demonstrate an entirely new method of nanoparticle chemical synthesis based on liquid droplet irradiation with ultralow ( < 0.1 eV) energy electrons. While nanoparticle formation via high energy radiolysis or transmission electron microscopy-based electron bombardment is well-understood, we have developed a source of electrons with energies close to thermal which leads to a number of important and unique benefits. The charged species, including the growing nanoparticles, are held in an ultrathin surface reaction zone which enables extremely rapid precursor reduction. In a proof-of-principle demonstration, we obtain small-diameter Au nanoparticles (～4 nm) with tight control of polydispersity, in under 150 μs. The precursor was almost completely reduced in this period, and the resultant nanoparticles were water-soluble and free of surfactant or additional ligand chemistry. Nanoparticle synthesis rates within the droplets were many orders of magnitude greater than equivalent rates reported for radiolysis, electron beam irradiation, or colloidal chemical synthesis where reaction times vary from seconds to hours. In our device, a stream of precursor loaded microdroplets, ～15 μm in diameter, were transported rapidly through a cold atmospheric pressure plasma with a high charge concentration. A high electron flux, electron and nanoparticle confinement at the surface of the droplet, and the picoliter reactor volume are thought to be responsible for the remarkable enhancement in nanoparticle synthesis rates. While this approach exhibits considerable potential for scale-up of synthesis rates, it also offers the more immediate prospect of continuous on-demand delivery of high-quality nanomaterials directly to their point of use by avoiding the necessity of collection, recovery, and purification. A range of new applications can be envisaged, from theranostics and biomedical imaging in tissue to inline catalyst production for pollution remediation in automobiles.","author":[{"dropping-particle":"","family":"Maguire","given":"Paul","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Rutherford","given":"David","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Macias-Montero","given":"Manuel","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Mahony","given":"Charles","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Kelsey","given":"Colin","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Tweedie","given":"Mark","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Pérez-Martin","given":"Fátima","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"McQuaid","given":"Harold","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Diver","given":"Declan","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Mariotti","given":"Davide","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Nano Letters","id":"ITEM-1","issue":"3","issued":{"date-parts":[["2017"]]},"page":"1336-1343","title":"Continuous In-Flight Synthesis for On-Demand Delivery of Ligand-Free Colloidal Gold Nanoparticles","type":"article-journal","volume":"17"},"uris":[""]}],"mendeley":{"formattedCitation":"⁴⁰","plainTextFormattedCitation":"40","previouslyFormattedCitation":"⁴¹"},"properties":{"noteIndex":0},"schema":""}40 In the context of this part of work, we believe that the reaction kinetics of electron-induced reduction contributes to prevent seed particle formation in the solution.In the following step, to further prove the proposed mechanisms, CNTs with a lower surface -COOH density (0.73 %) (CNT-COOH-L, details see experiment section) and CNTs with –OH functional groups (CNT-OH, details see experiment section) were chosen for the synthesis of AuNP/CNT hybrids (see Table 2) following the same APP processing parameters. The UV-Vis and TEM results of these 0.1 mM AuNP/CNT-COOH-L hybrid and 0.1 mM AuNP/CNT-OH hybrid are shown in Figure 5. The UV-Vis spectrum of 0.1 mM AuNP/CNT-COOH-L in Figure 5a shows that the LSPR peak wavelength of AuNP/CNT-COOH-L (552 nm) is red-shifted as compared to the 0.1 mM AuNP/CNT-COOH-H hybrid (531 nm). Similar to the 0.1 mM AuNP/CNT-COOH-H hybrid, the TEM image of 0.1 mM AuNP/CNT-COOH-L (Figure 5b) and corresponding shape projection analysis of AuNPs in this hybrid (See Figure S6, SI) also indicate that spherical AuNPs are uniformly attached to the surfaces of CNT-COOH-L. The average AuNPs size on CNT-COOH-L (95.1 ± 25.1 nm, see Figure S5 in SI) is much greater than that on CNT-COOH-H (28.7 ± 14.1 nm), which correlates to the red-shift of the LSPR peak. Observation from multiple TEM images of different magnifications (see Figure S6 in SI) also indicate there are less number of AuNPs formed on the surfaces of CNTs in 0.1 mM AuNP/CNT-COOH-L hybrid than in the 0.1 mM AuNP/CNT-COOH-H. As discussed earlier, AuCl3 on the surface of the CNT-COOH through ion exchange reaction with –COO- is believed to be preferential reduction and growth sites for AuNPs under such APP-assisted process. The much lower -COOH density of CNT-COOH-L provided much less sites compared to CNT-COOH-H, AuNPs with greater sizes could therefore be formed on the CNT-COOH-L surfaces by coalescence under the same initial HAuCl4 concentration (same amount of monomers supplied to less CNT-Au sites). However, when the surface functionalities of CNT was changed from –COOH to –OH groups, the formation mechanism of AuNP/CNT seems different from the results. Though a typical LSPR peak of AuNPs is still observed at 536 nm (Figure 5c), the AuNPs formed in the 0.1 mM AuNP/CNT-OH hybrid are presented in irregular shapes (hexagons, trapezoids, triangles, rods, etc.) with an average size of 50.3 ± 15.2 nm (see Figure S7 in SI) and some of them are loosely adsorbed /unattached to the CNT-OH (see NPs in red dash circles in Figure 5d). Figure 3 and literature have supported that [AuCl4]- could react with CNT-COOH by ion exchanging reaction, due to the ionization of -COOH in water as –COO- and H+. While ion exchange is expected for CNT-COOH, no ion exchanging should in principle take place between CNT-OH and [AuCl4]- because –OH 33393276467807Figure 6. The effect of UV–vis spectra of HAuCl4 on the CNT-OH UV-vis absorption profiles.00Figure 6. The effect of UV–vis spectra of HAuCl4 on the CNT-OH UV-vis absorption profiles.cannot be ionized in water. This is confirmed by UV-Vis spectra in Figure 6 when compared with Figure 4. With the addition of CNT-OH into the 0.1 mM HAuCl4 solution, both the 220 nm and 288 nm peaks remain constant in terms of the peak position and the intensity. The reduction and growth of AuNPs in this case mainly took place within the bulk solution, where centertop(b)(a)(c)(d)Figure 5. (a) and (c) UV-vis spectra of the 0.1 mM AuNP/CNT-COOH-L hybrid and 0.1 mM AuNP/CNT-OH hybrid; corresponding CNTs were used as references; (b) and (d) TEM images of 0.1 mM AuNP/CNT-COOH-L hybrid and 0.1 mM AuNP/CNT-OH hybrid.0(b)(a)(c)(d)Figure 5. (a) and (c) UV-vis spectra of the 0.1 mM AuNP/CNT-COOH-L hybrid and 0.1 mM AuNP/CNT-OH hybrid; corresponding CNTs were used as references; (b) and (d) TEM images of 0.1 mM AuNP/CNT-COOH-L hybrid and 0.1 mM AuNP/CNT-OH hybrid.the as-produced AuNPs then physically absorbed on the CNT-OH surfaces. This also explains AuNPs within 0.1 mM AuNP/CNT-OH hybrid shows similar morphologies (irregular shapes) to those produced without CNTs (Figure S4 in SI). Both the analysis of 0.1 mM AuNP/CNT-COOH-L hybrid and 0.1 mM AuNP/CNT-OH hybrid support our proposed formation mechanisms leading to reduction and growth of AuNP in the presence of –COOH functionalized CNTs.We finally focus on the investigation of important properties of the AuNP/CNT hybrids. We firstly compared the Raman scattering of AuNP/CNT-COOH-H hybrids synthesized from different initial HAuCl4 concentrations (Figure 7 a). Typical disordered band (D band) (~1332 cm-1) and graphene-like band (G band) (~1592 cm-1) characteristic peaks are present for all samples and the APP treatment did not induce any further defects/modifications to the CNT-COOH-H. After the AuNPs formed on the CNT-COOH-H, samples exhibit significantly enhanced electromagnetic surface enhanced Raman scattering (SERS), which can be essentially attributed to the LSPR oscillations of AuNPs under laser irradiation.ADDIN CSL_CITATION {"citationItems":[{"id":"ITEM-1","itemData":{"DOI":"10.1021/ja9035972","ISBN":"0002-7863","ISSN":"00027863","PMID":"19764748","abstract":"An electroless deposition method comprised of seed formation and subsequent seeded growth is developed for the decoration of surface-grown single-walled carbon nanotubes (SWCNTs) with gold nanoparticles of controlled size and interparticle distance. The density of the gold nanoparticles is determined by the density of seeds. Gold seeds are used for the SWCNT arrays grown on SiO(x)/Si substrates. For the dense SWCNT arrays on quartz, palladium seeds are used because it is much easier to obtain higher quantities of seeds. Attributed to both the seed formation specified on SWCNTs and the succedent efficient seeded growth process, the gold nanoparticles deposit on SWCNTs with very high selectivity. This electroless method shows no selectivity on types, defects, and conductivity of the SWCNTs, and thus ensures the uniform decoration of all SWCNTs on the wafer. Most importantly, this method provides the possibility to realize the optimal configurations of gold nanoparticles on SWCNTs for obtaining maximal surface-enhanced effects and consequently surface-enhanced Raman spectrum (SERS) of each SWCNT. Thus, both the in situ Raman detection of every SWCNT including those nonresonant with laser energy and the observation of the radial breathing modes of SWCNTs originally undetectable with resonance Raman spectroscopy are achieved. Further investigations over the effect of the laser wavelength and the interparticle distance on the SERS enhancement factors of SWCNTs prove that the coupled surface plasmon resonance absorption of the high-density gold nanoparticles decorated on SWCNTs contributes most to the strong surface enhancement.","author":[{"dropping-particle":"","family":"Chu","given":"Haibin","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Wang","given":"Jinyong","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Ding","given":"Lei","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Yuan","given":"Dongning","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Zhang","given":"Yan","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Liu","given":"Jie","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Li","given":"Yan","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Journal of the American Chemical Society","id":"ITEM-1","issue":"40","issued":{"date-parts":[["2009"]]},"page":"14310-14316","title":"Decoration of gold nanoparticles on surface-grown single-walled carbon nanotubes for detection of every nanotube by surface-enhanced raman spectroscopy","type":"article-journal","volume":"131"},"uris":[""]}],"mendeley":{"formattedCitation":"⁶⁷","plainTextFormattedCitation":"67","previouslyFormattedCitation":"⁶⁸"},"properties":{"noteIndex":0},"schema":""}67 The greater SERS signal associated with samples produced from higher HAuCl4 concentration correlates well with sample’s greater particle size/number (also see Figure 2), as larger AuNPs normally possess higher SERS efficiency when the size of NPs falls in the range of 20 nm to 80 nm.ADDIN CSL_CITATION {"citationItems":[{"id":"ITEM-1","itemData":{"DOI":"10.1021/jp057170o","ISBN":"1520-6106 (Print)","ISSN":"1520-6106","PMID":"16599493","abstract":"The selection of nanoparticles for achieving efficient contrast for biological and cell imaging applications, as well as for photothermal therapeutic applications, is based on the optical properties of the nanoparticles. We use Mie theory and discrete dipole approximation method to calculate absorption and scattering efficiencies and optical resonance wavelengths for three commonly used classes of nanoparticles:? gold nanospheres, silica?gold nanoshells, and gold nanorods. The calculated spectra clearly reflect the well-known dependence of nanoparticle optical properties viz. the resonance wavelength, the extinction cross-section, and the ratio of scattering to absorption, on the nanoparticle dimensions. A systematic quantitative study of the various trends is presented. By increasing the size of gold nanospheres from 20 to 80 nm, the magnitude of extinction as well as the relative contribution of scattering to the extinction rapidly increases. Gold nanospheres in the size range commonly employed (?40 nm) show an absorption cross-section 5 orders higher than conventional absorbing dyes, while the magnitude of light scattering by 80-nm gold nanospheres is 5 orders higher than the light emission from strongly fluorescing dyes. The variation in the plasmon wavelength maximum of nanospheres, i.e., from ?520 to 550 nm, is however too limited to be useful for in vivo applications. Gold nanoshells are found to have optical cross-sections comparable to and even higher than the nanospheres. Additionally, their optical resonances lie favorably in the near-infrared region. The resonance wavelength can be rapidly increased by either increasing the total nanoshell size or increasing the ratio of the core-to-shell radius. The total extinction of nanoshells shows a linear dependence on their total size, however, it is independent of the core/shell radius ratio. The relative scattering contribution to the extinction can be rapidly increased by increasing the nanoshell size or decreasing the ratio of the core/shell radius. Gold nanorods show optical cross-sections comparable to nanospheres and nanoshells, however, at much smaller effective size. Their optical resonance can be linearly tuned across the near-infrared region by changing either the effective size or the aspect ratio of the nanorods. The total extinction as well as the relative scattering contribution increases rapidly with the effective size, however, they are independent of the aspect ratio. To compare the…","author":[{"dropping-particle":"","family":"Jain","given":"Prashant K.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Lee","given":"Kyeong Seok","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"El-Sayed","given":"Ivan H.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"El-Sayed","given":"Mostafa A.","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"The Journal of Physical Chemistry B","id":"ITEM-1","issue":"14","issued":{"date-parts":[["2006"]]},"page":"7238-7248","title":"Calculated Absorption and Scattering Properties of Gold Nanoparticles of Different Size, Shape, and Composition:? Applications in Biological Imaging and Biomedicine","type":"article-journal","volume":"110"},"uris":[""]}],"mendeley":{"formattedCitation":"⁶⁸","plainTextFormattedCitation":"68","previouslyFormattedCitation":"⁶⁹"},"properties":{"noteIndex":0},"schema":""}68 Similar to the 0.1 mM AuNP/CNT-COOH-H hybrid sample, the 0.1 mM AuNP/CNT-COOH-L hybrid (Figure 7 b) and 0.1 mM AuNP/CNT-OH hybrid (Figure 7c) also demonstrated enhanced SERS properties comparing to corresponding pure CNT samples due to the presence of AuNPs 36830532737Figure 7. Raman spectra of (a) pure CNT-COOH-H and AuNP/CNT-COOH-H hybrids synthesized from different initial HAuCl4 concentrations, (b) pure CNT-COOH-L and 0.1 mM AuNP/CNT-COOH-L hybrid, and (c) pure CNT-OH and 0.1 mM AuNP/CNT-OH hybrid.G(a)(b)(c)DG00Figure 7. Raman spectra of (a) pure CNT-COOH-H and AuNP/CNT-COOH-H hybrids synthesized from different initial HAuCl4 concentrations, (b) pure CNT-COOH-L and 0.1 mM AuNP/CNT-COOH-L hybrid, and (c) pure CNT-OH and 0.1 mM AuNP/CNT-OH hybrid.G(a)(b)(c)DGon their surface after APP treatment. Raman spectroscopy is widely used for medical diagnostic applications, such as sensing and imaging.ADDIN CSL_CITATION {"citationItems":[{"id":"ITEM-1","itemData":{"DOI":"10.1016/j.addr.2015.03.009","ISBN":"1872-8294 (Electronic)\\r0169-409X (Linking)","ISSN":"18728294","PMID":"25809988","abstract":"Raman spectroscopy is an optical technique based on inelastic scattering of light by vibrating molecules and can provide chemical fingerprints of cells, tissues or biofluids. The high chemical specificity, minimal or lack of sample preparation and the ability to use advanced optical technologies in the visible or near-infrared spectral range (lasers, microscopes, fibre-optics) have recently led to an increase in medical diagnostic applications of Raman spectroscopy. The key hypothesis underpinning this field is that molecular changes in cells, tissues or biofluids, that are either the cause or the effect of diseases, can be detected and quantified by Raman spectroscopy. Furthermore, multivariate calibration and classification models based on Raman spectra can be developed on large \"training\" datasets and used subsequently on samples from new patients to obtain quantitative and objective diagnosis. Historically, spontaneous Raman spectroscopy has been known as a low signal technique requiring relatively long acquisition times. Nevertheless, new strategies have been developed recently to overcome these issues: non-linear optical effects and metallic nanoparticles can be used to enhance the Raman signals, optimised fibre-optic Raman probes can be used for real-time in-vivo single-point measurements, while multimodal integration with other optical techniques can guide the Raman measurements to increase the acquisition speed and spatial accuracy of diagnosis. These recent efforts have advanced Raman spectroscopy to the point where the diagnostic accuracy and speed are compatible with clinical use. This paper reviews the main Raman spectroscopy techniques used in medical diagnostics and provides an overview of various applications.","author":[{"dropping-particle":"","family":"Kong","given":"Kenny","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Kendall","given":"Catherine","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Stone","given":"Nicholas","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Notingher","given":"Ioan","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Advanced Drug Delivery Reviews","id":"ITEM-1","issued":{"date-parts":[["2015"]]},"page":"121-134","title":"Raman spectroscopy for medical diagnostics - From in-vitro biofluid assays to in-vivo cancer detection","type":"article","volume":"89"},"uris":["",""]}],"mendeley":{"formattedCitation":"⁶⁹","plainTextFormattedCitation":"69","previouslyFormattedCitation":"⁷⁰"},"properties":{"noteIndex":0},"schema":""}69 Due to their distinctive SERS signals, CNTs have attracted great research attention in the field of Raman spectrometric sensorsADDIN CSL_CITATION {"citationItems":[{"id":"ITEM-1","itemData":{"DOI":"10.1038/nnano.2008.231","ISBN":"1748-3395 (Electronic)\\r1748-3387 (Linking)","ISSN":"1748-3387","PMID":"18772918","abstract":"Photoacoustic imaging of living subjects offers higher spatial resolution and allows deeper tissues to be imaged compared with most optical imaging techniques. As many diseases do not exhibit a natural photoacoustic contrast, especially in their early stages, it is necessary to administer a photoacoustic contrast agent. A number of contrast agents for photoacoustic imaging have been suggested previously, but most were not shown to target a diseased site in living subjects. Here we show that single-walled carbon nanotubes conjugated with cyclic Arg-Gly-Asp (RGD) peptides can be used as a contrast agent for photoacoustic imaging of tumours. Intravenous administration of these targeted nanotubes to mice bearing tumours showed eight times greater photoacoustic signal in the tumour than mice injected with non-targeted nanotubes. These results were verified ex vivo using Raman microscopy. Photoacoustic imaging of targeted single-walled carbon nanotubes may contribute to non-invasive cancer imaging and monitoring of nanotherapeutics in living subjects.","author":[{"dropping-particle":"","family":"la Zerda","given":"A","non-dropping-particle":"De","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Zavaleta","given":"C","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Keren","given":"S","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Vaithilingam","given":"S","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Bodapati","given":"S","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Liu","given":"Z","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Levi","given":"J","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Smith","given":"B R","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Ma","given":"T J","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Oralkan","given":"O","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Cheng","given":"Z","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Chen","given":"X","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Dai","given":"H","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Khuri-Yakub","given":"B T","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Gambhir","given":"S S","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Nat Nanotechnol","id":"ITEM-1","issue":"9","issued":{"date-parts":[["2008"]]},"page":"557-562","title":"Carbon nanotubes as photoacoustic molecular imaging agents in living mice","type":"article-journal","volume":"3"},"uris":[""]},{"id":"ITEM-2","itemData":{"DOI":"10.1007/s12274-009-9009-8","ISBN":"1998-0124","ISSN":"19980124","PMID":"20174481","abstract":"Carbon nanotubes exhibit many unique intrinsic physical and chemical properties and have been intensively explored for biological and biomedical applications in the past few years. In this comprehensive review, we summarize the main results from our and other groups in this field and clarify that surface functionalization is critical to the behavior of carbon nanotubes in biological systems. Ultrasensitive detection of biological species with carbon nanotubes can be realized after surface passivation to inhibit the non-specific binding of biomolecules on the hydrophobic nanotube surface. Electrical nanosensors based on nanotubes provide a label-free approach to biological detection. Surface-enhanced Raman spectroscopy of carbon nanotubes opens up a method of protein microarray with detection sensitivity down to 1 fmol/L. In vitro and in vivo toxicity studies reveal that highly water soluble and serum stable nanotubes are biocompatible, nontoxic, and potentially useful for biomedical applications. In vivo biodistributions vary with the functionalization and possibly also size of nanotubes, with a tendency to accumulate in the reticuloendothelial system (RES), including the liver and spleen, after intravenous administration. If well functionalized, nanotubes may be excreted mainly through the biliary pathway in feces. Carbon nanotube-based drug delivery has shown promise in various In vitro and in vivo experiments including delivery of small interfering RNA (siRNA), paclitaxel and doxorubicin. Moreover, single-walled carbon nanotubes with various interesting intrinsic optical properties have been used as novel photoluminescence, Raman, and photoacoustic contrast agents for imaging of cells and animals. Further multidisciplinary explorations in this field may bring new opportunities in the realm of biomedicine.","author":[{"dropping-particle":"","family":"Liu","given":"Zhuang","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Tabakman","given":"Scott","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Welsher","given":"Kevin","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Dai","given":"Hongjie","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Nano Research","id":"ITEM-2","issue":"2","issued":{"date-parts":[["2009"]]},"page":"85-120","title":"Carbon nanotubes in biology and medicine: In vitro and in vivo detection, imaging and drug delivery","type":"article-journal","volume":"2"},"uris":[""]}],"mendeley":{"formattedCitation":"^11,70","plainTextFormattedCitation":"11,70","previouslyFormattedCitation":"^12,71"},"properties":{"noteIndex":0},"schema":""}11,70. From our Raman scattering results, the AuNP/CNT hybrids herein demonstrated greatly enhanced SERS signal as compared to untreated CNTs, hence these hybrids would be promising materials to be used for medical diagnostic applications such as bio-imaging and sensingADDIN CSL_CITATION {"citationItems":[{"id":"ITEM-1","itemData":{"DOI":"10.1039/C6TB02755E","ISBN":"2050-750X\\r2050-7518","ISSN":"2050-750X","abstract":"Combining doxorubicin with thermal therapy in the clinic has led to startling results in the treatment of problematic cancers. Here, we describe a multimodal multi-walled carbon nanotube material that combines tumor targeting, doxorubicin delivery, and photothermal therapy for localized cancer treatment. The agent was constructed layer-by-layer from polypyrrole and gold nanoparticles on multi-walled carbon nanotubes. The gold surface was modified with tumor targeting folic acid terminated PEGylated chains, which also provide water-dispersibility, biocompatibility and should extend the half-life in blood. The material has a high loading/unloading capacity for the cytotoxic agent doxorubicin. Release of the doxorubicin, combined with the photothermal properties of the material that induces localized hyperthermia, leads to efficient cancer cell death.","author":[{"dropping-particle":"","family":"Wang","given":"Daquan","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Hou","given":"Chen","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Meng","given":"Lingjie","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Long","given":"Jiangang","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Jing","given":"Jiange","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Dang","given":"Dongfeng","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Fei","given":"Zhaofu","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Dyson","given":"Paul J.","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"J. Mater. Chem. B","id":"ITEM-1","issue":"7","issued":{"date-parts":[["2017"]]},"page":"1380-1387","publisher":"Royal Society of Chemistry","title":"Stepwise growth of gold coated cancer targeting carbon nanotubes for the precise delivery of doxorubicin combined with photothermal therapy","type":"article-journal","volume":"5"},"uris":[""]},{"id":"ITEM-2","itemData":{"DOI":"10.1039/c2cc32313c","ISBN":"1364-548X (Electronic)\\r1359-7345 (Linking)","ISSN":"1359-7345","PMID":"22627619","abstract":"This communication reports the design of a novel aptamer conjugated gold nanocage decorated SWCNTs hybrid nanomaterial for targeted imaging and selective photothermal destruction of the prostate cancer cells.","author":[{"dropping-particle":"","family":"Khan","given":"Sadia Afrin","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Kanchanapally","given":"Rajashekhar","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Fan","given":"Zhen","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Beqa","given":"Lule","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Singh","given":"Anant Kumar","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Senapati","given":"Dulal","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Ray","given":"Paresh Chandra","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Chemical Communications","id":"ITEM-2","issue":"53","issued":{"date-parts":[["2012"]]},"page":"6711","title":"A gold nanocage–CNT hybrid for targeted imaging and photothermal destruction of cancer cells","type":"article-journal","volume":"48"},"uris":[""]},{"id":"ITEM-3","itemData":{"DOI":"10.1021/jacs.5b13475","ISBN":"1520-5126 (Electronic) 0002-7863 (Linking)","ISSN":"15205126","PMID":"27193381","abstract":"We report a new type of carbon nanotube ring (CNTR) coated with gold nanoparticles (CNTR@AuNPs) using CNTR as a template and surface attached redox-active polymer as a reducing agent. This nanostructure of CNTR bundle embedded in the gap of closely attached AuNPs can play multiple roles as a Raman probe to detect cancer cells and a photoacoustic (PA) contrast agent for imaging-guided cancer therapy. The CNTR@AuNP exhibits substantially higher Raman and optical signals than CNTR coated with a complete Au shell (CNTR@ AuNS) and straight CNT@AuNP. The extinction intensity of CNTR@AuNP is about 120-fold higher than that of CNTR at 808 nm, and the surface enhanced Raman scattering (SERS) signal of CNTR@AuNP is about 110 times stronger than that of CNTR, presumably due to the combined effects of enhanced coupling between the embedded CNTR and the plasmon mode of the closely attached AuNPs, and the strong electromagnetic field in the cavity of the AuNP shell originated from the intercoupling of AuNPs. The greatly enhanced PA signal and photothermal conversion property of CNTR@AuNP were successfully employed for imaging and imaging-guided cancer therapy in two tumor xenograft models. Experimental observations were further supported by numerical simulations and perturbation theory analysis.","author":[{"dropping-particle":"","family":"Song","given":"Jibin","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Wang","given":"Feng","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Yang","given":"Xiangyu","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Ning","given":"Bo","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Harp","given":"Mary G.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Culp","given":"Stephen H.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Hu","given":"Song","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Huang","given":"Peng","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Nie","given":"Liming","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Chen","given":"Jingyi","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Chen","given":"Xiaoyuan","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Journal of the American Chemical Society","id":"ITEM-3","issue":"22","issued":{"date-parts":[["2016"]]},"page":"7005-7015","title":"Gold Nanoparticle Coated Carbon Nanotube Ring with Enhanced Raman Scattering and Photothermal Conversion Property for Theranostic Applications","type":"article-journal","volume":"138"},"uris":[""]}],"mendeley":{"formattedCitation":"^24–26","plainTextFormattedCitation":"24–26","previouslyFormattedCitation":"^25–27"},"properties":{"noteIndex":0},"schema":""}24–26.Another very important property of our AuNP/CNT hybrids is their photothermal effect. The photothermal conversion efficiency of our hybrids was assessed in their aqueous media under the irradiation of laser. An 852 nm CW diode laser was selected due to its skin-penetrating ability within the biological window.ADDIN CSL_CITATION {"citationItems":[{"id":"ITEM-1","itemData":{"DOI":"10.1021/nn900904h","ISBN":"1936-0851","ISSN":"19360851","PMID":"19877694","abstract":"The photothermal therapy using nanomaterials has been recently attracted as an efficient strategy for the next generation of cancer treatments. Single walled carbon nanotube (SWNT) is an upcoming potent candidate for the photothermal therapeutic agent since it generates significant amounts of heat upon excitation with near-infrared light (NIR, lambda = 700-1100 nm) which is transparent to biological systems including skins. Such a photothermal effect can be employed to induce thermal cell death in a noninvasive manner. Here, we demonstrate in vivo obliteration of solid malignant tumors by the combined treatments of SWNTs and NIR irradiation. The photothermally treated mice displayed complete destruction of the tumors without harmful side effects or recurrence of tumors over 6 months, while the tumors treated in other control groups were continuously grown until the death of the mice. Most of the injected SWNTs were almost completely excreted from mice bodies in about 2 months through biliary or urinary pathway. These results suggest that SWNTs may potentially serve as an effective photothermal agent and pave the way to future cancer therapeutics.","author":[{"dropping-particle":"","family":"Moon","given":"Hye Kyung","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Lee","given":"Sang Ho","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Choi","given":"Hee Cheul","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"ACS Nano","id":"ITEM-1","issue":"11","issued":{"date-parts":[["2009"]]},"page":"3707-3713","title":"In vivo near-infrared mediated tumor destruction by photothermal effect of carbon nanotubes","type":"article-journal","volume":"3"},"uris":[""]}],"mendeley":{"formattedCitation":"⁷¹","plainTextFormattedCitation":"71","previouslyFormattedCitation":"⁷²"},"properties":{"noteIndex":0},"schema":""}71 The photothermal conversion results of different AuNP/CNT-COOH-H hybrids are shown in Figure 8a, and corresponding pure AuNP colloids and CNT-COOH-H were used for comparison. The observed temperature increase represents the heat transfer from AuNP/CNT-COOH-H hybrids to the solution. All samples heated up from room temperature under the laser irradiation following the trend 0.1 mM AuNP/CNT-COOH-H > 0.2 mM AuNP/CNT-COOH-H > 2.5 μM AuNP/CNT-COOH-H > CNT-COOH-H > 0.2 mM AuNP> 0.1 mM AuNP > 2.5 μM AuNP. In particular, 0.1 mM and 0.2 mM AuNP/CNT-COOH-H hybrids heated up most rapidly (over 48 °C in 60 s), reaching the temperature range valid for photothermal cancer therapies.ADDIN CSL_CITATION {"citationItems":[{"id":"ITEM-1","itemData":{"DOI":"10.1039/C4NR00708E","ISBN":"2040-3364","ISSN":"2040-3364","PMID":"25030381","abstract":"<p>The state of the art regarding the use of nanoparticles for photothermal therapies is reviewed in detail.</p>","author":[{"dropping-particle":"","family":"Jaque","given":"D.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Martínez Maestro","given":"L.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Rosal","given":"B.","non-dropping-particle":"del","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Haro-Gonzalez","given":"P.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Benayas","given":"A.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Plaza","given":"J. L.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Martín Rodríguez","given":"E.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"García Solé","given":"J.","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Nanoscale","id":"ITEM-1","issue":"16","issued":{"date-parts":[["2014"]]},"page":"9494-9530","title":"Nanoparticles for photothermal therapies","type":"article-journal","volume":"6"},"uris":["",""]}],"mendeley":{"formattedCitation":"⁷²","plainTextFormattedCitation":"72","previouslyFormattedCitation":"⁷³"},"properties":{"noteIndex":0},"schema":""}72 It can also be clearly seen that all AuNP/CNT-COOH-H hybrids demonstrated enhanced photothermal conversion when compared to pure AuNP and as-received CNT-COOH-H under all of the three HAuCl4 concentrations.According to the TEM analysis (Figure 2), the presence of CNTs has a significant influence on the resultant AuNP shape and their distribution in the samples. Zedan et al. has shown that the photothermal effect of AuNP/nanocarbon hybrids can be affected by the shape and size of the AuNPs.ADDIN CSL_CITATION {"citationItems":[{"id":"ITEM-1","itemData":{"DOI":"10.1021/nn304775h","ISBN":"1936-0851","ISSN":"19360851","PMID":"23194145","abstract":"In this work we demonstrate the coupling of the photothermal effects of gold nanostructures of controlled size and shape with graphene oxide nanosheets dispersed in water. The enhanced photothermal effects can be tuned by controlling the shape and size of the gold nanostructures, which result in a remarkable increase in the heating efficiency of the laser-induced size reduction of gold nanostructures. The Raman spectra of the Au-graphene nanosheets provide direct evidence for the presence of more structural defects in the graphene lattice induced by laser irradiation of graphene oxide nanosheets in the presence of Au nanostructures. The large surface areas of the laser-reduced graphene oxide nanosheets with multiple defect sites and vacancies provide efficient nucleation sites for the ultrasmall gold nanoparticles with diameters of 2-4 nm to be anchored to the graphene surface. This defect filling mechanism decreases the mobility of the ultrasmall gold nanoparticles and, thus, stabilizes the particles against the Ostwald ripening process, which leads to a broad size distribution of the laser-size-reduced gold nanoparticles. The Au nanostructures/graphene oxide solutions and the ultrasmall gold-graphene nanocomposites are proposed as promising materials for photothermal therapy and for the efficient conversion of solar energy into usable heat for a variety of thermal, thermochemical, and thermomechanical applications. 2012 American Chemical Society.","author":[{"dropping-particle":"","family":"Zedan","given":"Abdallah F.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Moussa","given":"Sherif","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Terner","given":"James","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Atkinson","given":"Garrett","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"El-Shall","given":"M. Samy","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"ACS Nano","id":"ITEM-1","issue":"1","issued":{"date-parts":[["2013"]]},"page":"627-636","title":"Ultrasmall gold nanoparticles anchored to graphene and enhanced photothermal effects by laser irradiation of gold nanostructures in graphene oxide solutions","type":"article-journal","volume":"7"},"uris":[""]}],"mendeley":{"formattedCitation":"⁷³","plainTextFormattedCitation":"73","previouslyFormattedCitation":"⁷⁴"},"properties":{"noteIndex":0},"schema":""}73 A more uniform distribution of the AuNPs on the CNTs with a tighter spherical shape distribution can therefore contribute to a more enhanced photothermal effects. It is also worth noting that 0.2 mM AuNP/CNT-COOH-H hybrid shows a lower photothermal conversion efficiency as compared to the 0.1 mM AuNP/CNT-COOH-H hybrid. Due to the LSPR of AuNPs, the incident light irradiation on AuNPs could result in both light absorption and light scattering.ADDIN CSL_CITATION {"citationItems":[{"id":"ITEM-1","itemData":{"DOI":"10.1016/j.jare.2010.02.002","ISBN":"2090-1232","ISSN":"20901232","abstract":"Currently a popular area in nanomedicine is the implementation of plasmonic gold nanoparticles for cancer diagnosis and photothermal therapy, attributed to the intriguing optical properties of the nanoparticles. The surface plasmon resonance, a unique phenomenon to plasmonic (noble metal) nanoparticles leads to strong electromagnetic fields on the particle surface and consequently enhances all the radiative properties such as absorption and scattering. Additionally, the strongly absorbed light is converted to heat quickly via a series of nonradiative processes. In this review, we discuss these important optical and photothermal properties of gold nanoparticles in different shapes and structures and address their recent applications for cancer imaging, spectroscopic detection and photothermal therapy. ? 2009 University of Cairo.","author":[{"dropping-particle":"","family":"Huang","given":"Xiaohua","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"El-Sayed","given":"Mostafa A.","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Journal of Advanced Research","id":"ITEM-1","issue":"1","issued":{"date-parts":[["2010"]]},"page":"13-28","title":"Gold nanoparticles: Optical properties and implementations in cancer diagnosis and photothermal therapy","type":"article","volume":"1"},"uris":[""]}],"mendeley":{"formattedCitation":"⁷⁴","plainTextFormattedCitation":"74","previouslyFormattedCitation":"⁷⁵"},"properties":{"noteIndex":0},"schema":""}74 According to El-Sayed’s calculation based on the Mie theory, larger AuNPs tend to have less light absorption but more scattering.ADDIN CSL_CITATION {"citationItems":[{"id":"ITEM-1","itemData":{"DOI":"10.1021/jp057170o","ISBN":"1520-6106 (Print)","ISSN":"1520-6106","PMID":"16599493","abstract":"The selection of nanoparticles for achieving efficient contrast for biological and cell imaging applications, as well as for photothermal therapeutic applications, is based on the optical properties of the nanoparticles. We use Mie theory and discrete dipole approximation method to calculate absorption and scattering efficiencies and optical resonance wavelengths for three commonly used classes of nanoparticles:? gold nanospheres, silica?gold nanoshells, and gold nanorods. The calculated spectra clearly reflect the well-known dependence of nanoparticle optical properties viz. the resonance wavelength, the extinction cross-section, and the ratio of scattering to absorption, on the nanoparticle dimensions. A systematic quantitative study of the various trends is presented. By increasing the size of gold nanospheres from 20 to 80 nm, the magnitude of extinction as well as the relative contribution of scattering to the extinction rapidly increases. Gold nanospheres in the size range commonly employed (?40 nm) show an absorption cross-section 5 orders higher than conventional absorbing dyes, while the magnitude of light scattering by 80-nm gold nanospheres is 5 orders higher than the light emission from strongly fluorescing dyes. The variation in the plasmon wavelength maximum of nanospheres, i.e., from ?520 to 550 nm, is however too limited to be useful for in vivo applications. Gold nanoshells are found to have optical cross-sections comparable to and even higher than the nanospheres. Additionally, their optical resonances lie favorably in the near-infrared region. The resonance wavelength can be rapidly increased by either increasing the total nanoshell size or increasing the ratio of the core-to-shell radius. The total extinction of nanoshells shows a linear dependence on their total size, however, it is independent of the core/shell radius ratio. The relative scattering contribution to the extinction can be rapidly increased by increasing the nanoshell size or decreasing the ratio of the core/shell radius. Gold nanorods show optical cross-sections comparable to nanospheres and nanoshells, however, at much smaller effective size. Their optical resonance can be linearly tuned across the near-infrared region by changing either the effective size or the aspect ratio of the nanorods. The total extinction as well as the relative scattering contribution increases rapidly with the effective size, however, they are independent of the aspect ratio. To compare the…","author":[{"dropping-particle":"","family":"Jain","given":"Prashant K.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Lee","given":"Kyeong Seok","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"El-Sayed","given":"Ivan H.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"El-Sayed","given":"Mostafa A.","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"The Journal of Physical Chemistry B","id":"ITEM-1","issue":"14","issued":{"date-parts":[["2006"]]},"page":"7238-7248","title":"Calculated Absorption and Scattering Properties of Gold Nanoparticles of Different Size, Shape, and Composition:? Applications in Biological Imaging and Biomedicine","type":"article-journal","volume":"110"},"uris":[""]}],"mendeley":{"formattedCitation":"⁶⁸","plainTextFormattedCitation":"68","previouslyFormattedCitation":"⁶⁹"},"properties":{"noteIndex":0},"schema":""}68 The decreased photothermal efficiency of 0.2 mM AuNP/CNT-COOH-H hybrid might be caused by the enhanced light scattering due to the larger AuNP size within the sample.ADDIN CSL_CITATION {"citationItems":[{"id":"ITEM-1","itemData":{"DOI":"10.1021/jp409067h","ISBN":"1932-7447","ISSN":"19327447","abstract":"We report the light-to-heat energy transfer efficiencies of gold nanoparticles with variable sizes by assessing the temperature profiles of laser-activated particle suspensions in water. Gold nanoparticles with sizes ranging from 5 to 50 nm were synthesized by chemical reduction methods using sodium borohydride, sodium citrate, or hydroquinone as reducing agents. As-synthesized gold nanoparticle solution (1 mL) was loaded into a quartz cuvette and exposed to a CW green laser (532 nm). Heat input into the system by energy transfer from nanoparticles equals heat dissipation at thermal equilibrium. The transducing efficiency was then determined by plotting temperature increase as a function of laser power extinction. The efficiency increases from 0.650 ± 0.012 to 0.803 ± 0.008 as the particle size decreases from 50.09 ± 2.34 to 4.98 ± 0.59 nm, respectively. The results indicate that the photothermal properties of gold nanoparticles are size-tunable, and the variation of efficiency can be correlated to the absorption/extinction ratios calculated by Mie theory for different particle sizes. We further expanded our Mie theory calculations of absorption/extinction ratios to a broader range of diameters and wavelengths. These studies are crucial for practical applications of gold nanoparticles in nanotechnology and bioengineering, such as enhancing the treatment efficiency of laser surgery.\\nWe report the light-to-heat energy transfer efficiencies of gold nanoparticles with variable sizes by assessing the temperature profiles of laser-activated particle suspensions in water. Gold nanoparticles with sizes ranging from 5 to 50 nm were synthesized by chemical reduction methods using sodium borohydride, sodium citrate, or hydroquinone as reducing agents. As-synthesized gold nanoparticle solution (1 mL) was loaded into a quartz cuvette and exposed to a CW green laser (532 nm). Heat input into the system by energy transfer from nanoparticles equals heat dissipation at thermal equilibrium. The transducing efficiency was then determined by plotting temperature increase as a function of laser power extinction. The efficiency increases from 0.650 ± 0.012 to 0.803 ± 0.008 as the particle size decreases from 50.09 ± 2.34 to 4.98 ± 0.59 nm, respectively. The results indicate that the photothermal properties of gold nanoparticles are size-tunable, and the variation of efficiency can be correlated to the absorption/extinction ratios calculated by Mie theory for different parti…","author":[{"dropping-particle":"","family":"Jiang","given":"Ke","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Smith","given":"David A.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Pinchuk","given":"Anatoliy","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Journal of Physical Chemistry C","id":"ITEM-1","issue":"51","issued":{"date-parts":[["2013"]]},"page":"27073-27080","title":"Size-dependent photothermal conversion efficiencies of plasmonically heated gold nanoparticles","type":"article-journal","volume":"117"},"uris":["",""]}],"mendeley":{"formattedCitation":"⁷⁵","plainTextFormattedCitation":"75","previouslyFormattedCitation":"⁷⁶"},"properties":{"noteIndex":0},"schema":""}75 We also compared the photothermal effects of the 0.1 mM AuNP/CNT hybrid synthesized from different CNTs. In Figure 8a, the 0.1 mM AuNP/CNT-COOH-H hybrid shows a temperature rise (?T) as high as 52.5 °C, which is higher than the sum of the ?T of pure CNT-COOH-H (23.4 °C) and the ?T of 0.1 mM AuNP (10.6 °C). When CNT-COOH-H was changed to the CNT-COOH-L, the 0.1 mM AuNP/CNT-COOH-L hybrid also presents a reasonably high ?T (~ 31.4 °C, see Figure 8b); but considering that pure CNT-COOH-L alone showed a ?T of 26.3 °C, the contribution of AuNPs to the photothermal enhancement within the hybrid is 5.1 °C - much lower than for the 0.1 mM AuNP/CNT-COOH-H hybrid (19.1 °C). The observed trend appears to be again relevant to the size of AuNPs within these two hybrids; according to Figure 2 and Figure 6, the AuNPs within 0.1 mM AuNP/CNT-COOH-L hybrid has a much greater size than within 0.1 mM AuNP/CNT-COOH-H hybrid and the enhanced light scattering of greater AuNPs could lead to decreased photothermal efficiency.ADDIN CSL_CITATION {"citationItems":[{"id":"ITEM-1","itemData":{"DOI":"10.1021/jp409067h","ISBN":"1932-7447","ISSN":"19327447","abstract":"We report the light-to-heat energy transfer efficiencies of gold nanoparticles with variable sizes by assessing the temperature profiles of laser-activated particle suspensions in water. Gold nanoparticles with sizes ranging from 5 to 50 nm were synthesized by chemical reduction methods using sodium borohydride, sodium citrate, or hydroquinone as reducing agents. As-synthesized gold nanoparticle solution (1 mL) was loaded into a quartz cuvette and exposed to a CW green laser (532 nm). Heat input into the system by energy transfer from nanoparticles equals heat dissipation at thermal equilibrium. The transducing efficiency was then determined by plotting temperature increase as a function of laser power extinction. The efficiency increases from 0.650 ± 0.012 to 0.803 ± 0.008 as the particle size decreases from 50.09 ± 2.34 to 4.98 ± 0.59 nm, respectively. The results indicate that the photothermal properties of gold nanoparticles are size-tunable, and the variation of efficiency can be correlated to the absorption/extinction ratios calculated by Mie theory for different particle sizes. We further expanded our Mie theory calculations of absorption/extinction ratios to a broader range of diameters and wavelengths. These studies are crucial for practical applications of gold nanoparticles in nanotechnology and bioengineering, such as enhancing the treatment efficiency of laser surgery.\\nWe report the light-to-heat energy transfer efficiencies of gold nanoparticles with variable sizes by assessing the temperature profiles of laser-activated particle suspensions in water. Gold nanoparticles with sizes ranging from 5 to 50 nm were synthesized by chemical reduction methods using sodium borohydride, sodium citrate, or hydroquinone as reducing agents. As-synthesized gold nanoparticle solution (1 mL) was loaded into a quartz cuvette and exposed to a CW green laser (532 nm). Heat input into the system by energy transfer from nanoparticles equals heat dissipation at thermal equilibrium. The transducing efficiency was then determined by plotting temperature increase as a function of laser power extinction. The efficiency increases from 0.650 ± 0.012 to 0.803 ± 0.008 as the particle size decreases from 50.09 ± 2.34 to 4.98 ± 0.59 nm, respectively. The results indicate that the photothermal properties of gold nanoparticles are size-tunable, and the variation of efficiency can be correlated to the absorption/extinction ratios calculated by Mie theory for different parti…","author":[{"dropping-particle":"","family":"Jiang","given":"Ke","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Smith","given":"David A.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Pinchuk","given":"Anatoliy","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Journal of Physical Chemistry C","id":"ITEM-1","issue":"51","issued":{"date-parts":[["2013"]]},"page":"27073-27080","title":"Size-dependent photothermal conversion efficiencies of plasmonically heated gold nanoparticles","type":"article-journal","volume":"117"},"uris":["",""]}],"mendeley":{"formattedCitation":"⁷⁵","plainTextFormattedCitation":"75","previouslyFormattedCitation":"⁷⁶"},"properties":{"noteIndex":0},"schema":""}75 In contrast to –COOH functionalized CNTs, there is only a slight enhancement of the photothermal effect 0.1 mM AuNP/CNT-OH hybrid in Figure 8c due to the formation of the AuNPs (?T = 1.5 °C). AuNPs LSPR is reported to promote the photo-absorption of nanocarbon and induce their plasmons,ADDIN CSL_CITATION {"citationItems":[{"id":"ITEM-1","itemData":{"DOI":"10.1126/science.1253202","ISBN":"1095-9203 (Electronic) 0036-8075 (Linking)","ISSN":"10959203","PMID":"24855026","abstract":"Graphene plasmons promise unique possibilities for controlling light in nanoscale devices and for merging optics with electronics. Here,we introduce a versatile platform technology based on resonant optical antennas and conductivity patterns for launching and controlling of propagating graphene plasmons, constituting an essential step for the development of graphene plasmonic circuits. We demonstrate the launching and focusing of infrared graphene plasmons with geometrically tailored antennas, and how they refract when passing through a 2-dimensional conductivity pattern, here a prism-shaped bilayer. To that end, we directly map the graphene plasmon wavefronts using an imaging method that will also benefit the testing of future design concepts for nanoscale graphene plasmonic circuits and devices.","author":[{"dropping-particle":"","family":"Alonso-González","given":"P.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Nikitin","given":"A. Y.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Golmar","given":"F.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Centeno","given":"A.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Pesquera","given":"A.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Vélez","given":"S.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Chen","given":"J.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Navickaite","given":"G.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Koppens","given":"F.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Zurutuza","given":"A.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Casanova","given":"F.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Hueso","given":"L. E.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Hillenbrand","given":"R.","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Science","id":"ITEM-1","issue":"6190","issued":{"date-parts":[["2014"]]},"page":"1369-1373","title":"Controlling graphene plasmons with resonant metal antennas and spatial conductivity patterns","type":"article-journal","volume":"344"},"uris":[""]}],"mendeley":{"formattedCitation":"⁷⁶","plainTextFormattedCitation":"76","previouslyFormattedCitation":"⁷⁷"},"properties":{"noteIndex":0},"schema":""}76 therefore contributing to the overall enhanced photothermal effects. For –COOH functionalized CNTs, the surface binding sites facilitated the charge transfer between AuNPs and CNTs through these sites. However, for AuNPs physically adsorbed on the surface of CNT-OH, the chances for electrons transfer would be negligible.CONCLUSION8255544195Figure 8. Photothermal effects of (a) AuNP/CNT-COOH-H hybrids synthesized from different initial HAuCl4 concentrations, (b) 0.1 mM AuNP-CNT-COOH-L and (c) 0.1 mM AuNP-CNT-OH under the irradiation of 852 nm laser. Data points correspond to average values for three different measurements with corresponding standard deviation in the error bars.(a)(b)(c)00Figure 8. Photothermal effects of (a) AuNP/CNT-COOH-H hybrids synthesized from different initial HAuCl4 concentrations, (b) 0.1 mM AuNP-CNT-COOH-L and (c) 0.1 mM AuNP-CNT-OH under the irradiation of 852 nm laser. Data points correspond to average values for three different measurements with corresponding standard deviation in the error bars.(a)(b)(c)In summary, we have successfully demonstrated a single-step preparation of AuNP/CNT hybrids through a facile and rapid APP processing technology. The complicated interaction between multi-phase materials (gas phase plasma, liquid and solid state nanomaterials) and the associated plasma-chemistry contributed to the formation of AuNP/CNT-COOH hybrids via multiple reaction pathways have been elucidated in detail. The [AuCl4]– and –COOH bindings serve as nucleation sites for the growth of AuNPs on the CNT-COOH surface and the resulting AuNP size increases with gold salt precursor concentration. The resulting hybrid structures, AuNP/CNT-COOH hybrids, demonstrated enhanced Raman scattering and high photothermal conversion efficiency, which are highly desirable for potential applications such as future multi-modal cancer theranostic. The study also moves forward to the establishment of “process-structure-property relationship” for APP nanomaterials processing, which may help to provide important guidance for optimizing the fabrication process of a wide range of nanocomposite/hybrid materials for healthcare applications and beyond. ASSOCIATED CONTENTSupporting InformationAdditional figures. AUTHOR INFORMATIONCorresponding Author*E-mail: d.sun@qub.ac.ukNotesThe authors declare no competing financial interest.ACKNOWLEDGMENTThe authors would like to acknowledge the Engineering and Physical Sciences Research Council (EPSRC) for funding support (EP/P00394X/1, EP/M015211/1). Mr. Daye Sun thanks the China Scholarship Council (CSC) for the financial support. REFERENCESADDIN Mendeley Bibliography CSL_BIBLIOGRAPHY (1) Anselmo, A. C.; Mitragotri, S. Nanoparticles in the Clinic. Bioeng. Transl. Med. 2016, 1 (1), 10–29.(2) Tournebize, J.; Boudier, A.; Sapin-Minet, A.; Maincent, P.; Leroy, P.; Schneider, R. Role of Gold Nanoparticles Capping Density on Stability and Surface Reactivity to Design Drug Delivery Platforms. ACS Appl. Mater. Interfaces 2012, 4 (11), 5790–5799.(3) Popovtzer, R.; Popovtzer, R.; Agrawal, A.; Agrawal, A.; Kotov, N. A.; Kotov, N. A.; Popovtzer, A.; Popovtzer, A.; Balter, J.; Balter, J.; et al. 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