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The Chemistry of Anilines by Zvi Rappoport Softcover - 1,180 pages Shipped in CLICK HERE Cat.# JW-ORC2 $1,159.05 BUY Published:  2007   ISBN:  9780470871713

Aniline is the parent molecule of a vast family of aromatic amines. Since its discovery in 1826 it has become one of the hundred most important building blocks in chemistry. Aniline is used as an intermediate in many different fields of applications, such as isocyanates, rubber processing chemicals, dyes and pigments, agricultural chemicals and pharmaceuticals.

The understanding of functional groups is key for the understanding of all organic chemistry. In the tradition of the Patai Series, this volume treats all aspects of this functional group. It contains chapters on the theoretical and computational foundations; on analytical and spectroscopical aspects with dedicated chapters on Mass Spectrometry, NMR, IR/UV, etc.; on reaction mechanisms; on applications in syntheses.

Table of Contents:

1. Anilines: Historical background
2. General and theoretical aspects of anilines
3. Structural chemistry of anilines
4. Thermochemistry of anilines
5. Mass spectrometry and gas-phase chemistry of anilines
6. NMR spectra of anilines
7. Substituted anilines as solvatochromic probes
8. Hydrogen bonds of anilines
9. Synthesis of anilines
10. Anilines as nucleophiles
11. Rearrangements of anilines and their derivatives
12. Analytical aspects of aromatic amines
13. Manufacture and uses of the anilines: A vast array of processes and products
14. The spectroscopy, photophysics and photochemistry of anilines
15. Toxicological and environmental aspects of anilines
16. Electrochemistry of anilines
17. Proton sponges

Author index
Subject index

The Claisen Rearrangement, Methods and Applications by Martin Hiersemann, and Udo Nubbemeyer Hardcover - 591 pages Shipped in CLICK HERE Cat.# JW-ORC3 $237.25 BUY Published:  2007   ISBN:  9783527308255

The first comprehensive coverage of all facets of the Claisen rearrangement and its variants. As such, this book helps synthetic chemists to exploit the vast potential of this elegant C-C linking reaction, discusses a wealth of catalytic options, and gives those more theory-minded chemists a detailed insight into the mechanistic aspects of the Claisen rearrangement. An invaluable source of information and a ready reference for all organic and catalytic chemists, as well as those working with/on organometallics, and in industry.

Table of Contents:

Preface
List of Contributors

1. Chorismate-Mutase-Catalyzed Claisen Rearrangement (Hong Guo and Niny Rao)

1.1 Introduction
1.2 Experimental Studies
1.3 Catalytic Mechanism of Chorismate Mutase
1.4 Conclusion

2. Chiral-Metal-Complex-Catalyzed Aliphatic Claisen Rearrangement

2.1 Introduction
2.2 Binding Modes of Main-group and Late Transition Metals
2.3 Aluminum(III)-promoted Claisen Rearrangement
2.4 Copper(II)-catalyzed Claisen Rearrangement
2.5 Palladium(II)-catalyzed Claisen Rearrangement

3. Aliphatic and Aromatic Claisen Rearrangement

3.1 Aliphatic Claisen Rearrangement
3.1.1 Introduction
3.1.2 Synthesis of Allyl Vinyl Ethers
3.1.3 Acyclic Aliphatic Claisen Rearrangement
3.1.4 Claisen Rearrangement of Cyclic Allyl Vinyl Ethers
3.1.5 Cyclic Vinyl Ethers
3.1.6 Cyclic Allyl Ethers
3.1.7 Tandem Reactions Including Aliphatic Claisen Rearrangement
3.1.8 The Carbanion-Accelerated Claisen Rearrangement
3.1.9 Conclusion
3.2 Aromatic Claisen Rearrangement
3.2.1 Introduction
3.2.2 Mechanism
3.2.3 Substrate and Substituent Effect
3.2.4 Reaction Conditions
3.2.5 Thio-, Amino-, and Related Claisen Rearrangement
3.2.6 Asymmetric Synthesis
3.2.7 Synthetic Applications

4. The Ireland–Claisen Rearrangement (1972–2004)

4.1 Introduction
4.2 History
4.3 Numbering and Nomenclature
4.4 Rearrangement Temperature, Substituent Effects and Catalysis
4.5 Transition State Structure
4.6 Stereochemical Aspects
4.7 Methods of Ketene Acetal Formation
4.8 Structural Variations in Allylic Esters
4.9 Applications to Natural Product Synthesis
4.10 Propargyl Esters
4.11 Conclusion

5. Simple and Chelate Enolate Claisen Rearrangement

5.1 Simple Enolate Claisen Rearrangement
5.1.1 Introduction
5.1.2 History
5.1.3 Simple Enolates of Allylic Esters
5.1.4 Stereoselectivity in Enolate Formation
5.1.5 Simple Enolates of Allylic Esters of a-Hetero Acids
5.1.6 Simple Enolates of N-Allyl Amides
5.1.7 Miscellaneous Enolates
5.1.8 Conclusion
5.2 Chelate Enolate Claisen Rearrangement
5.2.1 Introduction
5.2.2 Claisen Rearrangements of Substrates with Chelating Substituents in the a-Position
5.2.3 Claisen Rearrangements of Substrates Bearing Chelating Substituents in the β-Position
5.2.4 Chelation Controlled Aza-Claisen Rearrangements

6. Claisen–Johnson Orthoester Rearrangement

6.1 Introduction
6.2 Historical Overview
6.3 Mechanistic Aspects
6.4 Synthetic Applications
6.5 Conclusion

7. The Meerwein–Eschenmoser–Claisen Rearrangement

7.1 Definition, Discovery and Scope
7.2 Formation of Ketene N,O-Acetals
7.3 Selectivity
7.4 Applications in Synthesis

8. The Carroll Rearrangement

8.1 Introduction
8.2 Mechanism
8.3 Synthetic Applications
8.4 Carroll Variants
8.5 Conclusion

9. Thio-Claisen Rearrangement

9.1 Introduction
9.2 Basic Versions
9.3 Rearrangement with Stereochemical Control
9.4 Applications in Organic Synthesis
9.5 Conclusion

10. Aza-Claisen Rearrangement

10.1 Introduction
10.2 Aromatic Simple Aza-Claisen Rearrangements
10.3 Aliphatic Simple Aza-Claisen Rearrangements
10.4 Amide Acetal and Amide Enolate Claisen Rearrangements
10.5 Zwitterionic Aza-Claisen Rearrangements
10.6 Alkyne Aza-Claisen Rearrangements
10.7 Iminoketene Claisen Rearrangements

11. Mechanistic Aspects of the Aliphatic Claisen Rearrangement

References
Subject Index

Essentials of Carbohydrate Chemistry and Biochemistry by Thisbe K. Lindhorst Softcover - 332 pages Shipped in CLICK HERE Cat.# JW-ORC4 $ 95.40 BUY Published:  2007   ISBN:  9783527315284

Concise yet complete, this is a succinct introduction to the topic, covering both basic chemistry as well as such advanced topics as high-throughput analytics and glycomics - in 250 pages. This improved and expanded 3rd edition features all-new material on combinatorial synthesis of carbohydrates and carbohydrate biodiversity, and each chapter now contains study questions for self-learning and classroom teaching. Didactically written by an experienced lecturer and graduate student advisor, the text is backed by practical examples and many study questions tailored to students' needs.

Table of Contents:

Introduction to Carbohydrates
Structure of Saccharides
Protecting Groups for Carbohydrates
O-Glycoside Synthesis
Modifications and Functionalizations of the Sugar Ring
Glycoconjugates
Structure and Biosynthesis
Combinatorial Synthesis of Carbohydrates
Glycobiology and Glycomics
Purification and Analysis of Carbohydrates
The Literature of Carbohydrate Chemistry

Appendix:
-List of Experimental Procedures
-Solutions to Problems

Functional Organic Materials by Thomas J. J. Müller, and Uwe H. F. Bunz Hardcover - 612 pages Shipped in CLICK HERE Cat.# JW-ORC5 $376.30 BUY Published:  2007   ISBN:  9783527313020

Syntheses, Strategies and Applications

This timely, two-volume overview of the syntheses for functional pi-systems focuses on target molecules that have shown interesting properties as materials or models in physics, biology and chemistry. The unique concept allows readers to select the right synthetic strategy for success, making it invaluable for a number of industrial applications.

A "must have" for everyone working in this new and rapidly expanding field.

Table of Contents:

Preface
List of Contributors

Part I 3-D Carbon-rich π-Systems – Nanotubes and Segments

1. Functionalization of Carbon Nanotubes

1.1 Introduction to Carbon Nanotubes – A New Carbon Allotrope
1.2 Functionalization of Carbon Nanotubes
1.3 Covalent Functionalization
1.4 Noncovalent Exohedral Functionalization–Functionalization with Biomolecules
1.5 Endohedral Functionalization
1.6 Conclusions
1.7 Experimental

2. Cyclophenacene Cut Out of Fullerene

2.1 Introduction
2.2 Synthesis of [10]Cyclophenacene π-Conjugated Systems from [60]Fullerene
2.3 Conclusion
2.4 Experimental

Part II Strategic Advances in Chromophore and Materials Synthesis

3. Cruciform π-Conjugated Oligomers

3.1 Introduction
3.2 Oligomers with a Tetrahedral Core Unit
3.3 Oligomers with a Tetrasubstituted Benzene Core
3.4 Oligomers with a Tetrasubstituted Biaryl Core
3.5 Conclusion
3.6 Experimental

4. Design of π-Conjugated Systems Using Organophosphorus Building Blocks

4.1 Introduction
4.2 Phosphole-containing π-Conjugated Systems
4.3 Phosphine-containing π-Conjugated Systems
4.4 Phosphaalkene- and Diphosphene-containing πjugated Systems
4.5 Conclusion
4.6 Selected Experimental Procedures

5. Diversity-oriented Synthesis of Chromophores by Combinatorial Strategies and Multi-component Reactions

5.1 Introduction
5.2 Combinatorial Syntheses of Chromophores
5.3 Novel Multi-component Syntheses of Chromophores
5.4 Conclusion and Outlook
5.5 Experimental Procedures

6. High-yield Synthesis of Shape-persistent Phenylene–Ethynylene Macrocycles

6.1 Introduction
6.2 Synthesis
6.3 Conclusion
6.4 Experimental Procedures

7. Functional Materials via Multiple Noncovalent Interactions

7.1 Introduction
7.2 Biologically Inspired Materials via Multi-step Self-assembly
7.3 Small Molecule-based Multi-step Self-assembly
7.4 Polymer-based Self-assembly
7.5 Conclusion and Outlook

Part III Molecular Muscles, Switches and Electronics

8. Molecular Motors and Muscles

8.1 Introduction
8.2 Mechanically Interlocked Molecules as Artificial Molecular Machines
8.3 Chemically Induced Switching of the Bistable Rotaxanes
8.4 Electrochemically Controllable Bistable Rotaxanes
8.5 Photochemically Powered Molecular Switches
8.6 Conclusions

9. Diarylethene as a Photoswitching Unit of Intramolecular Magnetic Interaction

9.1 Introduction
9.2 Photochromic Spin Coupler
9.3 Synthesis of Diarylethene Biradicals
9.4 Photoswitching Using Bis(3-thienyl)ethene
9.5 Reversed Photoswitching Using Bis(2-thienyl)ethene
9.6 Photoswitching Using an Array of Photochromic Molecules
9.7 Development of a New Switching Unit
9.8 Conclusions
9.9 Experimental Procedures

10. Thiol End-capped Molecules for Molecular Electronics: Synthetic Methods, Molecular Junctions and Structure–Property Relationships

10.1 Introduction
10.2 Synthetic Procedures
10.3 Electron Transport in Two- and Three-terminal Molecular Devices
10.4 Summary and Outlook
10.5 Experimental

11. Nonlinear Optical Properties of Organic Materials

11.1 Introduction to Nonlinear Optics
11.2 Second-order Chromophores for Electrooptic Applications
11.3 Design and Application of Two-photon Absorbing Chromophores
11.4 Appendix: Units in NLO

Part IV Electronic Interaction and Structure

12. Photoinduced Electron Transfer Processes in Synthetically Modified DNA

12.1 DNA as a Bioorganic Material for Electron Transport
12.2 Mechanism of Hole Transfer and Hole Hopping in DNA
12.3 Reductive Electron Transfer and Excess Electron Transport in DNA
12.4 Results from the Electron Transfer Studies
12.5 Outlook: Towards Synthetic Nanostructures Based on DNA-like Architecture

13. Electron Transfer of p-Functional Systems and Applications

13.1 Introduction
13.2 Efficient Electron-transfer Properties of Zinc Porphyrins
13.3 Efficient Electron-transfer Properties of Fullerenes
13.4 Photoinduced Electron Transfer in Electron Donor-Acceptor Linked Molecules Mimicking the Photosynthetic Reaction Center
13.5 An Orthogonal p-Donor-Acceptor Dyad Affording an Infinite CS Lifetime
13.6 A Long-lived ET State Acting as an Efficient ET Photocatalyst
13.7 Organic Solar Cells Using Simple Donor-Acceptor Dyads
13.8 Organic Solar Cells Composed of Multi-porphyrin/C60 Supramolecular Assemblies
13.9 Conclusion

14. Induced p-Stacking in Acenes

14.1 Introduction
14.2 Anthracene
14.3 Tetracene (Naphthacene)
14.4 Pentacene
14.5 Higher Acenes
14.6 Conclusion

15. Synthesis and Characterization of Novel Chiral Conjugated Materials

15.1 Introduction
15.2 Synthetic Approaches to Highly Annelated Chiral π-Conjugated Systems
15.3 Barriers for Racemization of Chiral p-Conjugated Systems
15.4 Strong Chiroptical Properties in Absorption, Emission and Refraction
15.5 Conclusion

Index

Hydrogen-Transfer Reactions by James T. Hynes, Judith P. Klinman, Hans-Heinrich Limbach, and Richard L. Schowen Hardcover - 1,603 pages Shipped in CLICK HERE Cat.# JW-ORC6 $759.95 BUY Published:  2006   ISBN:  9783527307777

This multivolume work is the only comprehensive, up-to-date reference work on the theory, occurrence and application of hydrogen transfer processes. Adopting an integrated approach, this handy reference includes essential information on the theoretical basis, the fundamental types, and the latest techniques used to reveal, monitor, as well as measure hydrogen transfer reactions. Renowned experts from a number of disciplines provide a thorough overview on all aspects of hydrogen transfer in natural and artificial systems, thus aiding readers in their own research. Numerous tables and illustrations facilitate fast and easy access to the desired information, making this an indispensable source of knowledge for every research group working in the field.

Table of Contents:

Foreword
Preface
Preface to Volumes 1 and 2
List of Contributors to Volumes 1 and 2

I Physical and Chemical Aspects, Parts I–III

Part I Hydrogen Transfer in Isolated Hydrogen Bonded Molecules, Complexes and Clusters

1. Coherent Proton Tunneling in Hydrogen Bonds of Isolated Molecules: Malonaldehyde and Tropolone

1.1 Introduction
1.2 Coherent Tunneling Splitting Phenomena in Malonaldehyde
1.3 Coherent Tunneling Phenomena in Tropolone
1.4 Tropolone Derivatives
1.5 Concluding Remarks

2. Coherent Proton Tunneling in Hydrogen Bonds of Isolated Molecules: Carboxylic Dimers

2.1 Introduction
2.2 Quantum Tunneling versus Classical Over Barrier Reactions
2.3 Carboxylic Dimers
2.4 Benzoic Acid Dimer
2.5 Formic Acid Dimer
2.6 Conclusion

3. Gas Phase Vibrational Spectroscopy of Strong Hydrogen Bonds

3.1 Introduction
3.2 Methods
3.3 Selected Systems
3.4 Outlook

4. Laser-driven Ultrafast Hydrogen Transfer Dynamics

4.1 Introduction
4.2 Theory
4.3 Laser Control
4.4 Conclusions and Outlook

Part II Hydrogen Transfer in Condensed Phases

5. Proton Transfer from Alkane Radical Cations to Alkanes

5.1 Introduction
5.2 Electronic Absorption of Alkane Radical Cations
5.3 Paramagnetic Properties of Alkane Radical Cations
5.4 The Brønsted Acidity of Alkane Radical Cations
5.5 The r-Basicity of Alkanes
5.6 Powder EPRSpectra of Alkyl Radicals
5.7 Symmetric Proton Transfer from Alkane Radical Cations to Alkanes: An Experimental Study in c-Irradiated n-Alkane Nanoparticles Embedded in a Cryogenic CCl3F Matrix
5.8 Asymmetric Proton Transfer from Alkane Radical Cations to Alkanes: An Experimental Study in c-Irradiated Mixed Alkane Crystals

6. Single and Multiple Hydrogen/Deuterium Transfer Reactions in Liquids and Solids

6.1 Introduction
6.2 Theoretical
6.3 Applications
6.4 Conclusions

7. Intra- and Intermolecular Proton Transfer and Related Processes in Confined Cyclodextrin Nanostructures

7.1 Introduction and Concept of Femtochemistry in Nanocavities
7.2 Overview of the Photochemistry and Photophysics of Cyclodextrin Complexes
7.3 Picosecond Studies of Proton Transfer in Cyclodextrin Complexes
7.4 Femtosecond Studies of Proton Transfer in Cyclodextrin Complexes
7.5.3 2-(2'-Hydroxyphenyl)-4-methyloxazole
7.5.4 Orange II
7.6 Concluding Remarks

8. Tautomerization in Porphycenes

8.1 Introduction
8.2 Tautomerization in the Ground Electronic State
8.3 Tautomerization in the Lowest Excited Singlet State
8.4 Tautomerization in the Lowest Excited Triplet State
8.5 Tautomerization in Single Molecules of Porphycene
8.6 Summary

9. Proton Dynamics in Hydrogen-bonded Crystals

9.1 Introduction
9.2 Tentative Study of Proton Dynamics in Crystals with Quasi-linear H-bonds
9.3 DFT Calculations with Periodic Boundary Conditions
9.4 Conclusions

Part III Hydrogen Transfer in Polar Environments

10. Theoretical Aspects of Proton Transfer Reactions in a Polar Environment

10.1 Introduction
10.2 Adiabatic Proton Transfer
10.3 Nonadiabatic JTunneling’ Proton Transfer
10.4 Concluding Remarks

11. Direct Observation of Nuclear Motion during Ultrafast Intramolecular Proton Transfer

11.1 Introduction
11.2 Time-resolved Absorption Measurements
11.3 Spectral Signatures of Ultrafast ESIPT
11.4 Reaction Mechanism
11.5 Reaction Path Specific Wavepacket Dynamics in Double Proton Transfer Molecules
11.6 Conclusions

12. Solvent Assisted Photoacidity

12.1 Introduction
12.2 Photoacids, Photoacidity and FLrster Cycle
12.3 Evidence for the General Validity of the FLrster Cycle and the K*a Scale
12.4 Factors Affecting Photoacidity
12.5 Solvent Assisted Photoacidity: The 1La, 1Lb Paradigm
12.6 Summary

13. Design and Implementation of “Super” Photoacids

13.1 Introduction.
13.2 Excited-state Proton Transfer (ESPT)
13.3 Nature of the Solvent
13.4 ESPT in Biological Systems
13.5 Conclusions

Foreword
Preface
Preface to Volumes 1 and 2
List of Contributors to Volumes 1 and 2

I Physical and Chemical Aspects, Parts IV–VII

Part IV Hydrogen Transfer in Protic Systems

14. Bimolecular Proton Transfer in Solution

14.1 Intermolecular Proton Transfer in the Liquid Phase
14.2 Photoacids as Ultrafast Optical Triggers for Proton Transfer
14.3 Proton Recombination and Acid–Base Neutralization
14.4 Reaction Dynamics Probing with Vibrational Marker Modes

15. Coherent Low-frequency Motions in Condensed Phase Hydrogen Bonding and Transfer

15.1 Introduction
15.2 Vibrational Excitations of Hydrogen Bonded Systems
15.3 Low-frequency Wavepacket Dynamics of Hydrogen Bonds in the Electronic Ground State
15.4 Low-frequency Motions in Excited State Hydrogen Transfer
15.5 Conclusions

16. Proton-Coupled Electron Transfer: Theoretical Formulation and Applications

16.1 Introduction
16.2 Theoretical Formulation for PCET
16.3 Applications
16.4 Conclusions

17. The Relation between Hydrogen Atom Transfer and Proton-coupled Electron Transfer in Model Systems

17.1 Introduction
17.2 Methods of HAT and PCET Study
17.3 Unidirectional PCET
17.4 Bidirectional PCET
17.5 The Different Types of PCET in Biology
17.6 Application of Emerging Ultrafast Spectroscopy to PCET

Part V Hydrogen Transfer in Organic and Organometallic Reactions

18. Formation of Hydrogen-bonded Carbanions as Intermediates in Hydrogen Transfer between Carbon and Oxygen

18.1 Proton Transfer from Carbon Acids to Methoxide Ion
18.2 Proton Transfer from Methanol to Carbanion Intermediates
18.3 Proton Transfer Associated with Methoxide Promoted Dehydrohalogenation Reactions
18.4 Conclusion

19. Theoretical Simulations of Free Energy Relationships in Proton Transfer

19.1 Introduction
19.2 Qualitative Models for FERs
19.3 FERs from MO Calculations of PESs
19.4 FERs from VB Studies of Free Energy Changes for PT in Condensed Phases
19.5 Concluding Remarks

20. The Extraordinary Dynamic Behavior and Reactivity of Dihydrogen and Hydride in the Coordination Sphere of Transition Metals

20.1 Introduction
20.2 H2 Rotation in Dihydrogen Complexes
20.3 NMR Studies of H2 Activation, Dynamics, and Transfer Processes
20.4 Intramolecular Hydrogen Rearrangement and Exchange
20.5 Summary

21. Dihydrogen Transfer and Symmetry: The Role of Symmetry in the Chemistry of Dihydrogen Transfer in the Light of NMR Spectroscopy

21.1 Introduction
21.2 Tunneling and Chemical Kinetics
21.3 Symmetry Effects on NMRLineshapes of Hydration Reactions
21.4 Symmetry Effects on NMRLineshapes of Intramolecular Dihydrogen Exchange Reactions
21.5 Summary and Conclusion

Part VI Proton Transfer in Solids and Surfaces

22. Proton Transfer in Zeolites

22.1 Introduction – The Active Sites of Acidic Zeolite Catalysts
22.2 Proton Transfer to Substrate Molecules within Zeolite Cavities
22.3 Formation of NH4+ ions on NH3 adsorption
22.4 Methanol Molecules and Dimers in Zeolites
22.5 Water Molecules and Clusters in Zeolites
22.6 Proton Jumps in Hydrated and Dry Zeolites
22.7 Stability of Carbenium Ions in Zeolites

23. Proton Conduction in Fuel Cells

23.1 Introduction
23.2 Proton Conducting Electrolytes and Their Application in Fuel Cells
23.3 Long-range Proton Transport of Protonic Charge Carriers in Homogeneous Media
23.4 Confinement and Interfacial Effects
23.5 Concluding Remarks

24. Proton Diffusion in Ice Bilayers

24.1 Introduction
24.2 Experimental Method
24.3 Spectral Analysis of the Diffusion Process
24.4 Summary

25. Hydrogen Transfer on Metal Surfaces

25.1 Introduction
25.2 The Principles of the Interaction of Hydrogen with Surfaces: Terms and Definitions
25.3 The Transfer of Hydrogen on Metal Surfaces
25.4 Alcohol and Water on Metal Surfaces: Evidence of H Bond Formation and H Transfer
25.5 Conclusion

26. Hydrogen Motion in Metals

26.1 Survey
26.2 Experimental Methods
26.3 Experimental Results on Diffusion Coefficients
26.4 Experimental Results on Hydrogen Jump Diffusion Mechanisms
26.5 Quantum Motion of Hydrogen
26.6 Concluding Remarks

Part VII Special Features of Hydrogen-Transfer Reactions

27. Variational Transition State Theory in the Treatment of Hydrogen Transfer Reactions

27.1 Introduction
27.2 Incorporation of Quantum Mechanical Effects in VTST
27.3 H-atom Transfer in Bimolecular Gas-phase Reactions
27.4 Intramolecular Hydrogen Transfer in Unimolecular Gas-phase Reactions
27.5 Liquid-phase and Enzyme-catalyzed Reactions
27.6 Examples of Condensed-phase Reactions
27.7 Another Perspective
27.8 Concluding Remarks

28. Quantum Mechanical Tunneling of Hydrogen Atoms in Some Simple Chemical Systems

28.1 Introduction
28.2 Unimolecular Reactions
28.3 Bimolecular Reactions

29. Multiple Proton Transfer: From Stepwise to Concerted

29.1 Introduction
29.2 Basic Model
29.3 Approaches to Proton Tunneling Dynamics
29.4 Tunneling Dynamics for Two Reaction Coordinates
29.5 Isotope Effects
29.6 Dimeric Formic Acid and Related Dimers
29.7 Other Dimeric Systems
29.8 Intramolecular Double Proton Transfer
29.9 Proton Conduits
29.10 Transfer of More Than Two Protons
29.11 Conclusion

Foreword
Preface
Preface to Volumes 3 and 4
List of Contributors to Volumes 3 and 4

II Biological Aspects, Parts I–II

Part I Models for Biological Hydrogen Transfer

1. Proton Transfer to and from Carbon in Model Reactions

1.1 Introduction
1.2 Rate and Equilibrium Constants for Carbon Deprotonation in Water
1.3 Substituent Effects on Equilibrium Constants for Deprotonation of Carbon
1.4 Substituent Effects on Rate Constants for Proton Transfer at Carbon
1.5 Small Molecule Catalysis of Proton Transfer at Carbon
1.6 Comments on Enzymatic Catalysis of Proton Transfer

2. General Acid–Base Catalysis in Model Systems

2.1 Introduction
2.2 Structural Requirements and Mechanism
2.3 Intramolecular Reactions
2.4 Proton Transfers to and from Carbon
2.5 Hydrogen Bonding, Mechanism and Reactivity

3. Hydrogen Atom Transfer in Model Reactions

3.1 Introduction
3.2 Oxygen-centered Radicals
3.3 Nitrogen-dentered Radicals
3.4 Sulfur-centered Radicals
3.5 Conclusion

4. Model Studies of Hydride-transfer Reactions

4.1 Introduction
4.2 The Design of Suitable Model Reactions
4.3 The Role of Model Reactions in Mechanistic Enzymology
4.4 Models for Nicotinamide-mediated Hydrogen Transfer
4.5 Models for Flavin-mediated Hydride Transfer
4.6 Models for Quinone-mediated Reactions
4.7 Summary and Conclusions
4.8 Appendix: The Use of Model Reactions to Estimate Enzyme Catalytic Power

5. Acid–Base Catalysis in Designed Peptides

5.1 Designed Polypeptide Catalysts
5.2 Catalysis of Ester Hydrolysis
5.3 Limits of Activity in Surface Catalysis
5.4 Computational Catalyst Design
5.5 Enzyme Design

Part II General Aspects of Biological Hydrogen Transfer

6. Enzymatic Catalysis of Proton Transfer at Carbon Atoms

6.1 Introduction
6.2 The Kinetic Problems Associated with Proton Abstraction from Carbon
6.3 Structural Strategies for Reduction of ΔGo
6.4 Experimental Paradigms for Enzyme-catalyzed Proton Abstraction from Carbon
6.5 Summary

7. Multiple Hydrogen Transfers in Enzyme Action

7.1 Introduction
7.2 Cofactor-Dependent with Activated Substrates
7.3 Cofactor-Dependent with Unactivated Substrates
7.4 Cofactor-Independent with Activated Substrates
7.5 Cofactor-Independent with Unactivated Substrates
7.6 Summary

8. Computer Simulations of Proton Transfer in Proteins and Solutions

8.1 Introduction
8.2 Simulating PT Reactions by the EVB and other QM/MM Methods
8.3 Simulating the Fluctuations of the Environment and Nuclear Quantum Mechanical Effects
8.4 The EVB as a Basis for LFERof PT Reactions
8.5 Demonstrating the Applicability of the Modified Marcus’ Equation
8.6 General Aspects of Enzymes that Catalyze PT Reactions
8.7 Dynamics, Tunneling and Related Nuclear Quantum Mechanical Effects
8.8 Concluding Remarks

Foreword
Preface
Preface to Volumes 3 and 4
List of Contributors to Volumes 3 and 4

II Biological Aspects, Parts III–V

Part III Quantum Tunneling and Protein Dynamics

9. The Quantum Kramers Approach to Enzymatic Hydrogen Transfer – Protein Dynamics as it Couples to Catalysis

9.1 Introduction
9.2 The Derivation of the Quantum Kramers Method
9.3 Promoting Vibrations and the Dynamics of Hydrogen Transfer
9.4 Hydrogen Transfer and Promoting Vibrations – Alcohol Dehydrogenase
9.5 Promoting Vibrations and the Kinetic Control of Enzymes – Lactate Dehydrogenase
9.6 The Quantum Kramers Model and Proton Coupled Electron Transfer
9.7 Promoting Vibrations and Electronic Polarization
9.8 Conclusions

10. Nuclear Tunneling in the Condensed Phase: Hydrogen Transfer in Enzyme Reactions

10.1 Introduction
10.2 Enzyme Kinetics: Extracting Chemistry from Complexity
10.3 Methodology for Detecting Nonclassical H-Transfers
10.4 Concepts and Theories Regarding Hydrogen Tunneling
10.5 Experimental Systems
10.6 Concluding Comments

11. Multiple-isotope Probes of Hydrogen Tunneling

11.1 Introduction
11.2 Background: H/D Isotope Effects as Probes of Tunneling
11.3 Swain–Schaad Exponents: H/D/T Rate Comparisons
11.4 Rule of the Geometric Mean: Isotope Effects on Isotope Effects
11.5 Saunders’ Exponents: Mixed Multiple Isotope Probes
11.6 Concluding Remarks

12. Current Issues in Enzymatic Hydrogen Transfer from Carbon: Tunneling and Coupled Motion from Kinetic Isotope Effect Studies

12.1 Introduction
12.2 The H-transfer Step in Enzyme Catalysis
12.3 Probing H-transfer in Complex Systems
12.4 Theoretical Models for H-transfer and Dynamic Effects in Enzymes
12.5 Concluding Comments

13. Hydrogen Tunneling in Enzyme-catalyzed Hydrogen Transfer: Aspects from Flavoprotein Catalysed Reactions

13.1 Introduction
13.2 Stopped-flow Methods to Access the Half-reactions of Flavoenzymes
13.3 Interpreting Temperature Dependence of Isotope Effects in Terms of H-Tunneling
13.4 H-Tunneling in Morphinone Reductase and Pentaerythritol Tetranitrate Reductase
13.5 H-Tunneling in Flavoprotein Amine Dehydrogenases: Heterotetrameric Sarcosine Oxidase and Engineering Gated Motion in Trimethylamine Dehydrogenase
13.6 Concluding Remarks

14. Hydrogen Exchange Measurements in Proteins

14.1 Introduction
14.2 Methods and Instrumentation
14.3 Applications of Hydrogen Exchange to Study Protein Conformations and Dynamics
14.4 Future Developments

15. Spectroscopic Probes of Hydride Transfer Activation by Enzymes

15.1 Introduction
15.2 Substrate Activation for Hydride Transfer
15.3 NAD(P) Cofactor Activation for Hydride Transfer by Enzymes
15.4 Dynamics of Protein Catalysis and Hydride Transfer Activation

Part IV Hydrogen Transfer in the Action of Specific Enzyme Systems

16. Hydrogen Transfer in the Action of Thiamin Diphosphate Enzymes

16.1 Introduction
16.2 The Mechanism of the C2-H Deprotonation of Thiamin Diphosphate in Enzymes
16.3 Proton Transfer Reactions during Enzymic Thiamin Diphosphate Catalysis
16.4 Hydride Transfer in Thiamin Diphosphate-dependent Enzymes

17. Dihydrofolate Reductase: Hydrogen Tunneling and Protein Motion

17.1 Reaction Chemistry and Catalysis
17.2 Structural Features of DHFR
17.3 Enzyme Motion in DHFRC atalysis
17.4 Conclusions

18. Proton Transfer During Catalysis by Hydrolases

18.1 Introduction
18.2 Proton Abstraction – Activation of Water or Amino Acid Nucleophiles
18.3 Proton Donation – Stabilization of Intermediates or Leaving Groups
18.4 Proton Transfer in Physical Steps of Hydrolase-catalyzed Reactions

19. Hydrogen Atom Transfers in B12 Enzymes

19.1 Introduction to B12 Enzymes
19.2 Overall Reaction Mechanisms of Isomerases
19.3 Isotope Effects in B12 Enzymes
19.4 Theoretical Approaches to Mechanisms of H-transfer in B12 Enzymes
19.5 Free Energy Profile for Cobalt–Carbon Bond Cleavage and H-atom Transfer Steps
19.6 Model Reactions
19.7 Summary

Part V Proton Conduction in Biology

20. Proton Transfer at the Protein/Water Interface

20.1 Introduction
20.2 The Membrane/Protein Surface as a Special Environment
20.3 The Electrostatic Potential Near the Surface
20.4 The Effect of the Geometry on the Bulk-surface Proton Transfer Reaction
20.5 Direct Measurements of Proton Transfer at an Interface
20.6 Proton Transfer at the Surface of a Protein
20.7 The Dynamics of Ions at an Interface
20.8 Concluding Remarks

Index