The hydrogen bond and the water molecule-



The hydrogen bond and the water molecule:

the physics and chemistry of water, aqueous and bio media

Acknowledgments

Preface

Part I: The hydrogen bond

Chapter 1 The hydrogen bond: formation, thermodynamic properties, classification

Chemical bonds

Intermolecular bonds

Van der Waals interactions,

Hydrogen bonds

The H-bond: historical and prospective aspects, general bibliography

Intermolecular and intramolecular H-bonds

Electronic structures of H-bonds

Thermodynamics of H-bonds: electronic and vibrational contributions to enthalpies

Examples of weak, intermediate strength and strong H-bonds

Weak H-bonds

Medium-strength H-bonds

Strong H-bonds

Non-conventional H-bonds

H/D substitutions in H-bonds

Appendix A: energies and related quantities.

Chapter 2 Geometrical properties of H-bonds and H-bonded organized supramolecular structures

Geometries of H-bonds at equilibrium

Equilibrium angles (0 and (0

Equilibrium distances Q0

Equilibrium distances q0

Organized supramolecular structures of macromolecules

Cellulose and amylose

Proteins

Composition: polypeptide backbone

Primary, secondary and tertiary structures of a protein

Pleated (-sheets

(-helices

tertiary structures and beyond

Stability of secondary structures and denaturation of proteins

DNA

Conclusion

Chapter 3 Methods to observe and describe H-bonds

Calorimetry

Modern experimental methods

Absorption of an electromagnetic wave

Microwave spectroscopy

IR spectra: rotational bonds

NMR spectroscopy

Principles

NMR of H-bonds established by small or medium-size molecules

NMR of macromolecules

Conclusion

X-ray absorption spectroscopy

Scattering of electromagnetic waves or particles

Coherent scattering (X-rays and neutrons)

Incoherent scattering

Incoherent light scattering

Incoherent neutron scattering (INS)

Theoretical descriptions of the electronic structures of H-bonds

Summary

Chapter 4 Infrared spectroscopy of H-bonded systems: experimental point of view

IR spectroscopy and H-bond vibrations

Intermonomer vibrations in the FIR region

Description

anharmonicities of intermonomer modes.

Intramonomer vibrations in the mid-infrared region

Stretching bands (s

Introduction

Integrated intensities

(s band centres

Shifts [pic]of (s and enthalpies (H of H-bonds

Shifts [pic]of (s and H-bond distances

Evidence of cooperativity between H-bonds

Conclusion

Widths of (s bands

The (s band of H-bonds: conclusion.

Other intramonomer bands

Stretching and bending vibrations of the donating X-H group

Carbonyl and carboxyl C=O groups

Multiphoton vibrational spectroscopy: Raman and nonlinear IR spectroscopies

Raman spectra

Time resolved non linear IR spectroscopies

Sum-frequency generation (SFG) spectroscopy

Conclusion

Chapter 5 Infrared spectroscopy of H-bonded systems: theoretical descriptions

Introduction

Integrated intensities of (s bands

(s bandshapes of isolated H-bonds: modulation by intermonomer modes

Modulation by intermonomer stretching modes

Modulation by intermonomer bending modes

(s bandshapes of non-isolated H-bonds

(s bandshapes of H-bonds: Fermi resonances

conclusion on (s bands

Appendix: IR spectroscopy

Experimental spectroscopy: measured quantities and set-ups

First moments of a distribution or of a spectral band

Normal modes in the harmonic approximation

Reduced masses, force constants and vibrational amplitudes

Centre and width of νs

Chapter 6 Reactivity of H-bonds: transfers of protons and of H-atoms

Great amplitude motions in isolated H-bonds

Proton transfers in a H-bond network

Ionization mechanism of an acid or a base

Diffusion of H3O+ and OH- ions in liquid water

Proton transfers in the electronic excited state

Photoacids

ESPT's in biology: photosynthesis and vision mechanisms.

H-bonded ferroelectrics

Hydrogen atom transfers by tautomerism

Conclusion

Chapter 7 H/D isotopic substitution in H-bonds

The H and D atoms: similarities and differences

Geometries and therrmodynamics of H-bonds and D-bonds

Geometries of H-bonds and D-bonds

Enthalpies of H-bonds and D-bonds

Dynamic properties of H-bonds and D-bonds

Vibrational spectra of H-bonds and D-bonds

Partial H/D substitution and isotopic dilution

H/D substitution in biology: a dramatic effect on reactivity

H-bonds and D-bonds as seen by methods sensitive to nuclear spins

Conclusion

Appendix

Part II: The water molecule

Chapter 8 The H2O molecule in water vapour and ice

H2O : an exceptional molecule.

Water vapour

The major greenhouse gas and its strong IR bands

Formation of rain drops.

Ice(s)

Ice Ih and Ice Ic

Crystal structures

IR spectrum

Structures of ice surfaces.

Other crystalline phases of ice.

Ice Ih/ liquid water interfaces.

Amorphous phases of ice.

Reactivity of ice

Ice in the atmosphere

Ozone depletion and polar stratospheric clouds

Mechanisms of ozone destruction.

Conclusion

Chapter 9 The H2O molecule in liquid water

H-bonds in liquid water

Thermodynamics

IR spectroscopy

O-H free groups?

IR spectra of liquid water and of ice

intermonomer bands

intramonomer bands

Structure of the H-bond network of liquid water.

The exceptional properties of liquid water

Exceptional chemical properties

Ionization and solvation of acids and bases

Ionization and solvation of salts

Solvation of organic molecules

Organized structures of amphiphile molecules

Micelles

Biological membranes

Langmuir-Blodgett layers

Exceptional physical properties

Our understanding of liquid water

Conclusion

Chapter 10 The water molecule in (bio)macromolecules

Water molecules and their dense hydrogen bond networks

Arrangements of water molecules in macromolecules

Hydration mechanisms

Hydration of a model biopolymer: hyaluronane (HA)

Dried state of HA

Successive hydration mechanisms

First hydration mechanism H1

Subsequent hydration mechanisms at higher hygrometries

Hydration of a synthetic polymer: a sulfonated polyimide

General features for hydration mechanisms?

Protection of biomacromolecules against external stress (cryo- and lyo-protections)

Survival under freezing temperatures or hydric stress

Protection mechanisms

Protein folding

Reactivity of water molecules in macromolecules

Conclusion

Chapter 11 Observing the water molecule

A difficult to observe molecule

Global methods

Classical molecular methods other than vibrational spectroscopy

X-ray scattering

Neutron scattering

NMR spectroscopy

Molecular Dynamics (MD)

Vibrational spectroscopy

IR spectroscopy to observe H2O molecules

ATR (Attenuated Total Reflection)

IR spectrometry on thin samples: hydration of macromolecules

Hydration spectra of hyaluronane HA

Analysis of hydration spectra

Bands due to H2O molecules: measurement of the water uptake

Intensities of the difference bands due to the macromolecule

Time-resolved non-linear IR spectroscopy

NIR and Raman spectroscopies

Conclusion

Part III: General conclusion

Chapter 12 Conclusion: the H-bond, the water molecule and life

................
................

In order to avoid copyright disputes, this page is only a partial summary.

Google Online Preview   Download