Comprehensive Chiroptical Spectroscopy, Volume 1 E-Book

Nina Berova

• Herausgeber: John Wiley & Sons
• Kategorie: Wissenschaft und neue Technologien
• Sprache: Englisch

Seitenzahl: 1581

Veröffentlichungsjahr: 2011

Beschreibung

This book provides an introduction to the important methods of chiroptical spectroscopy in general, and circular dichroism (CD) in particular, which are increasingly important in all areas of chemistry, biochemistry, and structural biology. The book can be used as a text for undergraduate and graduate students and as a reference for researchers in academia and industry, with or without the companion volume in this set. Experimental methods and instrumentation are described with topics ranging from the most widely used methods (electronic and vibrational CD) to frontier areas such as nonlinear spectroscopy and photoelectron CD, as well as the theory of chiroptical methods and techniques for simulating chiroptical properties. Each chapter is written by one or more leading authorities with extensive experience in the field.

Leseprobe

Table of Contents

Title Page

Copyright

Preface

Contributors

Part I: Introduction

Chapter 1: On the Interaction of Light with Molecules: Pathways to the Theoretical Interpretation of Chiroptical Phenomena

1.1 A Brief Historical Retrospective

1.2 Elements of the Semiclassical Theory

1.3 Chiroptical Phenomena

1.4 Concluding Remarks

References

Part II: Experimental Methods and Instrumentation

Chapter 2: Measurement of the Circular Dichroism of Electronic Transitions

2.1 Introduction

2.2 Theory

2.3 Operations

Acknowledgments

References

Chapter 3: Circularly Polarized Luminescence Spectroscopy and Emission-Detected Circular Dichroism

3.1 Introduction

3.2 Theoretical Principles

3.3 Measurement Techniques

3.4 Standards for CPL

3.5 Artifacts

3.6 Example Applications

3.7 Summary

Acknowledgments

References

Chapter 4: Solid-State Chiroptical Spectroscopy: Principles and Applications

4.1 Introduction

4.2 Theoretical Background [32]

4.3 Development of New Apparatuses

4.4 Application to Solid Samples

4.5 Multichannel (MC) CD Method: A Novel Method for Direct True CD Measurement [31]

4.6 Concluding Remarks

References

Chapter 5: Infrared Vibrational Optical Activity: Measurement and Instrumentation

5.1 Introduction

5.2 Stokes–Mueller Representations of Intensities

5.3 Fourier Transform Instrumentation

5.4 Advanced Methods for FT-VCD Measurement

5.5 Measurement of Dispersed Solids and Films

5.6 Conclusions

References

Chapter 6: Measurement of Raman Optical Activity

6.1 Introduction

6.2 Optical Activity Measured by Light Scattering

6.3 Scattering Zone, Light Collection, and Spectral Analysis

6.4 Signal Detection and Noise

6.5 Polarization Control and Detection

6.6 Final Remarks

References

Chapter 7: Nanosecond Time-Resolved Natural and Magnetic Chiroptical Spectroscopies

7.1 Introduction

7.2 Near-Null Ellipsometric CD Measurements

7.3 Near-Null Ellipsometric MCD Measurements

7.4 Near-Null Polarimetric ORD and MORD Measurements

7.5 Limitations of Near-Null Techniques

7.6 CD and MCD in Samples Oriented by Laser Photoselection

7.7 Applications of Nanosecond Chiroptical Spectroscopies

7.8 Other Approaches to Fast and Ultrafast TRCD Measurements

References

Chapter 8: Femtosecond Infrared Circular Dichroism and Optical Rotatory Dispersion

8.1 Introduction

8.2 Time Correlation Function Theory

8.3 Differential Intensity Measurement Method

8.4 Phase-and-Amplitude Measurement of IR Optical Activity

8.5 Active- and Self-Heterodyne Detections of IR Optical Activity

8.6 Experimental Demonstration: VCD and Vord Spectra of (1S)-β-Pinene

8.7 Summary and a Few Concluding Remarks

Acknowledgments

References

Chapter 9: Chiroptical Properties of Lanthanide Compounds in an Extended Wavelength Range

9.1 Introduction

9.2 The F Shell

9.3 Electronic Circular Dichroism and Circularly Polarized Luminescence

9.4 Coupling of Electronic and Vibrational States and VCD Enhancement

9.5 Applications

9.6 Conclusions

Acknowledgment

List of Abbreviations

References

Chapter 10: Near-Infrared Vibrational Circular Dichroism: NIR-VCD

10.1 Introduction

10.2 Acquiring and Interpreting NIR-VCD Spectra

10.3 A Worked-Out Example: Epichlorohydrin

10.4 Perspectives and Conclusions

References

Chapter 11: Optical Rotation and Intrinsic Optical Activity

11.1 Introduction

11.2 Theoretical Background

11.3 Experimental Methods

11.4 Intrinsic Optical Activity

11.5 Summary and Outlook

Acknowledgments

References

Chapter 12: Chiroptical Imaging of Crystals

12.1 Introduction

12.2 Differential Polarization Imaging

12.3 Complete versus Incomplete Polarimeters

12.4 Optical Rotation

12.5 Circular Dichroism/Extinction

12.6 Nanoscale

12.7 Mueller Matrix Microscopy

12.8 Artifacts

12.9 Outlook

References

Chapter 13: Nonlinear Optical Spectroscopy of Chiral Molecules

13.1 Introduction

13.2 Linear Chiroptics in Liquids: χ(1)

13.3 Nonlinear Chiroptics in Liquids

13.4 Nonlinear Chiroptics at Surfaces

13.5 Computation

13.6 Conclusions

13.7 Appendix

Acknowledgments

References

Chapter 14: In Situ Measurement of Chirality of Molecules and Molecular Assemblies with Surface Nonlinear Spectroscopy

14.1 Introduction

14.2 Theory and Formalism of SHG-LD and SFG-LD

14.3 Application of SHG-LD and SFG-LD

14.4 Perspectives and Future Directions

References

Chapter 15: Photoelectron Circular Dichroism

15.1 Introduction

15.2 The Photoelectron Angular Distribution and Circular Dichroism

15.3 Experimental Approaches

15.4 Experimental Results and Discussion

15.5 Prospects

Acknowledgments

References

Chapter 16: Magnetochiral Dichroism and Birefringence

16.1 Introduction

16.2 MChD in Luminescence

16.3 MChD in Optical Absorption

16.4 Enantioselective MChD Photochemistry

16.5 Magnetochiral Dichroism in a Ferromagnet

16.6 Magnetochiral Birefringence

16.7 Other Manifestations of MChA

16.8 Conclusion

Acknowledgments

References

Chapter 17: X-Ray Detected Optical Activity

17.1 Phenomenological Bases

17.2 Instrumentation and Methods

17.3 XDOA: Illustrative Examples

17.4 Unifying Theories, First Principles Simulations

17.5 Concluding Remarks

Acknowledgments

References

Chapter 18: Linear Dichroism

18.1 Introduction

18.2 Flow Linear Dichroism for Structure Analysis

18.3 LD to Follow Kinetic Processes

18.4 LD to Determine DNA Bending, Stiffening, and Relaxation

18.5 Practicalities of LD Spectroscopy

18.6 Orientation Methods of Samples for LD Spectroscopy

18.7 Some Derivations

18.8 Interplay of Theory and Experiment

References

Chapter 19: Electro-Optical Absorption Spectroscopy

19.1 Introduction

19.2 Working Equations for Polarized Spectroscopy and Electro-Optical Absorption Spectroscopy

19.3 Experimentals

19.4 Quantitative Analysis

19.5 Discussion

19.6 Summary

Acknowledgments

19.8 Appendix

References

Part III: Theoretical Simulations

Chapter 20: Independent Systems Theory for Predicting Electronic Circular Dichroism

20.1 Introduction

20.2 The Tinoco Theory

20.3 The Matrix Method

20.4 Classical Polarizability (DeVoe) Theory

20.5 Applications

20.6 Software Available

Appendix A

Appendix B

Supplement To Chapter 20: Derivation of Tinoco'S Equation in Dipole Velocity Form

References

Chapter 21: Ab Initio Electronic Circular Dichroism and Optical Rotatory Dispersion: From Organic Molecules to Transition Metal Complexes

21.1 Introduction

21.2 Calculating ECD and ORD Starting From First Principles

21.3 ECD and ORD Calculations for Organic Molecules

21.4 Metal Complexes and Metal Clusters

21.5 Concluding Remarks

Acknowledgments

References

Chapter 22: Theoretical Electronic Circular Dichroism Spectroscopy of Large Organic and Supramolecular Systems

22.1 Introduction

22.2 Theory

22.3 Examples

22.4 Summary

Acknowledgments

References

Chapter 23: High-Accuracy Quantum Chemistry and Chiroptical Properties

23.1 Introduction

23.2 Coupled Cluster Theory

23.3 Response Theory for Chiroptical Properties

23.4 Performance

23.5 Future Directions

Acknowledgments

References

Chapter 24: Ab Initio Methods for Vibrational Circular Dichroism and Raman Optical Activity

24.1 Introduction

24.2 Energy Derivative Theory and Perturbation-Dependent Basis Sets

24.3 The Theory Of Vibrational Circular Dichroism and Raman Optical Activity

24.4 The AB Initio Theory of Vibrational Circular Dichroism and Raman Optical Activity

24.5 Concluding Remarks and Outlook

Acknowledgments

24.7 Appendix: Determination of the Perturbed Density Matrices

References

Chapter 25: Modeling of Solvation Effects on Chiroptical Spectra

25.1 Introduction

25.2 Solvent models

25.3 Solvent Effects on Electronic Circular Dichroism and Natural Optical Rotation

25.4 Solvent Effects on Vibrational Circular Dichroism and Raman Optical Activity

25.5 Concluding Remarks

References

Chapter 26: Complexation, Solvation, and Chirality Transfer in Vibrational Circular Dichroism

26.1 Introduction

26.2 Concept of Robustness in VCD Spectroscopy

26.3 Effects of Molecular Complex Formation in VCD Spectra

26.4 Conclusions

26.5 Acknowledgment

References

Index

Color Plates

Copyright © 2011 by John Wiley & Sons, Inc. All rights reserved

Published by John Wiley & Sons, Inc., Hoboken, New Jersey

Published simultaneously in Canada

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Library of Congress Cataloging-in-Publication Data:

Advances in chiroptical methods/edited by Nina Berova . . . [et al.].

p. cm.

ISBN 978-0-470-64135-4 (hardback : set)—ISBN 978-1-118-01293-2 (v. 1)—ISBN 978-1-118-01292-5 (v. 2)

1. Chirality. 2. Spectrum analysis. 3. Circular dichroism. I. Berova, Nina.

Includes index.

QP517.C57A384 2012

541.7—dc23

2011021418

Preface

Chirality is a phenomenon that is manifested throughout the natural world, ranging from fundamental particles through the realm of molecules and biological organisms to spiral galaxies. Thus, chirality is of interest to physicists, chemists, biologists, and astronomers. Chiroptical spectroscopy utilizes the differential response of chiral objects to circularly polarized electromagnetic radiation. Applications of chiroptical spectroscopy are widespread in chemistry, biochemistry, biology, and physics. It is indispensable for stereochemical elucidation of organic and inorganic molecules. Nearly all biomolecules and natural products are chiral, as are the majority of drugs. This has led to crucial applications of chiroptical spectroscopy ranging from the study of protein folding to characterization of small molecules, pharmaceuticals, and nucleic acids.

The first chiroptical phenomenon to be observed was optical rotation (OR) and its wavelength dependence, namely, optical rotatory dispersion (ORD), in the early nineteenth century. Circular dichroism associated with electronic transitions (ECD), currently the most widely used chiroptical method, was discovered in the mid-nineteenth century, and its relationship to ORD and absorption was elucidated at the end of the nineteenth century. Circularly polarized luminescence (CPL) from chiral crystals was observed in the 1940s. The introduction of commercial instrumentation for measuring ORD in the 1950s and ECD in the 1960s led to a rapid expansion of applications of these forms of chiroptical spectroscopy to various branches of science, and especially to organic and inorganic chemistry and to biochemistry.

Until the 1970s, chiroptical spectroscopy was confined to the study of electronic transitions, but vibrational transitions became accessible with the development of vibrational circular dichroism (VCD) and Raman optical activity (ROA). Other major extensions of chiroptical spectroscopy include differential ionization of chiral molecules by circularly polarized light (photoelectron CD), measurement of optical activity in the X-ray region, magnetochiral dichroism, and nonlinear forms of chiroptical spectroscopy.

The theory of chiroptical spectroscopy also goes back many years, but has recently made spectacular advances. Classical theories of optical activity were formulated in the early twentieth century, and the quantum mechanical theory of optical rotation was described in 1929. Approximate formulations of the quantum mechanical models were developed in the 1930s and more extensively with the growth of experimental ORD and ECD studies, starting in the late 1950s. The quantum mechanical methods for calculations of chiroptical spectroscopic properties reached a mature stage in the 1980s and 1990s. Ab initio calculations of VCD, ECD, ORD, and ROA have proven highly successful and are now widely used for small and medium-sized molecules.

Many books have been published on ORD, ECD, and VCD/ROA. The present two volumes are the first comprehensive treatise covering the whole field of chiroptical spectroscopy. Volume 1 covers the instrumentation, methodologies, and theoretical simulations for different chiroptical spectroscopic methods. In addition to an extensive treatment of ECD, VCD, and ROA, this volume includes chapters on ORD, CPL, photoelectron CD, X-ray-detected CD, magnetochiral dichroism, and nonlinear chiroptical spectroscopy. Chapters on the related techniques of linear dichroism, chiroptical imaging of crystals and electro-optic absorption, which sometimes supplement chiroptical interpretations, are also included. The coverage of theoretical methods is also extensive, including simulation of ECD, ORD, VCD, and ROA spectra of molecules ranging from small molecules to macromolecules. Volume 2 describes applications of ECD, VCD, and ROA in the stereochemical analysis of organic and inorganic compounds and to biomolecules such as natural products, proteins, and nucleic acids. The roles of chiroptical methods in the study of drug mechanisms and drug discovery are described.

Thus, this work is unique in presenting an extensive coverage of the instrumentation and techniques of chiroptical spectroscopy, theoretical methods and simulation of chiroptical spectra, and applications of chiroptical spectroscopy in inorganic and organic chemistry, biochemistry, and drug discovery. In each of these areas, leading experts have provided the background needed for beginners, such as undergraduates and graduate students, and a state-of-the-art treatment for active researchers in academia and industry.

We are grateful to the contributors to these two volumes who kindly accepted our invitations to contribute and who have met the challenges of presenting accessible, up-to-date treatments of their assigned topics in a timely fashion.

Nina Berova

Prasad L. Polavarapu

Koji Nakanishi

Robert W. Woody

Contributors

Sergio Abbate, Department of Biomedical Sciences and Biotechnologies, University of Brescia, Brescia, Italy and CNISM (Consorzio Nazionale Interuniversitario per le Scienze Fisiche della Materia), Rome, Italy

Jochen Autschbach, Department of Chemistry, University at Buffalo, The State University of New York, Buffalo, New York, USA

Evert Jan Baerends, Division of Theoretical Chemistry, Faculty FEW/Chemistry, VU University, Amsterdam, The Netherlands and WCU Program, Department of Chemistry, Pohang University of Science and Technology, Pohang, South Korea

Nina Berova, Department of Chemistry, Columbia University, New York, New York, USA

Christian Brouder, Institute of Mineralogy and Physics of Condensed Media, Universities of Paris VI-VII, Paris, France

Ettore Castiglioni, Jasco Corporation, Tokyo, Japan and Department of Biomedical Sciences and Biotechnologies, University of Brescia, Brescia, Italy

Eefei Chen, Department of Chemistry and Biochemistry, University of California, Santa Cruz, California, USA

Minhaeng Cho, Department of Chemistry, Korea University, Seoul, South Korea and Korea Basic Science Institute, Seoul, South Korea

T. Daniel Crawford, Department of Chemistry, Virginia Tech, Blacksburg, Virginia, USA

Lorenzo Di Bari, Department of Chemistry and Industrial Chemistry, University of Pisa, Pisa, Italy

Peer Fischer, Max-Planck-Institute for Intelligent Systems, Stuttgart, Germany

Joerg Fleischhauer, Institute of Organic Chemistry, RWTH Aachen University, Aachen, Germany

John Freudenthal, Department of Chemistry and Molecular Design Institute, New York University, New York, New York, USA

Lars Goerigk, Institute of Theoretical Organic Chemistry and Organic Chemistry, University of Muenster, Muenster, Germany and School of Chemistry, The University of Sydney, Sydney, New South Wales, Australia

Robert A. Goldbeck, Department of Chemistry and Biochemistry, University of California, Santa Cruz, California, USA

Jose Goulon, European Synchrotron Radiation Facility, Grenoble, France

Stefan Grimme, Institute of Theoretical Organic Chemistry and Organic Chemistry, University of Muenster, Muenster, Germany

Takunori Harada, Department of Life Sciences, Graduate School of Arts and Sciences, The University of Tokyo, Tokyo, Japan

Werner Hug, Department of Chemistry, University of Fribourg, Fribourg, Switzerland

Bart Kahr, Department of Chemistry and Molecular Design Institute, New York University, New York, New York, USA

Werner Kaminsky, Department of Chemistry, University of Washington, Seattle, Washington, USA

David S. Kliger, Department of Chemistry and Biochemistry, University of California, Santa Cruz, California, USA

Holger Kruse, Institute of Theoretical Organic Chemistry and Organic Chemistry, University of Muenster, Muenster, Germany

Hans-Georg Kuball, Department of Chemistry—Physical Chemistry, Technical University of Kaiserslautern, Kaiserslautern, Germany

Reiko Kuroda, Department of Life Sciences, Graduate School of Arts and Sciences, The University of Tokyo, Tokyo, Japan

Giovanna Longhi, Department of Biomedical Sciences and Biotechnologies, University of Brescia, Brescia, Italy and CNISM Consorzio Nazionale Interuniversitario per le Scienze Fisiche della Materia, Rome, Italy

Gilles Muller, Department of Chemistry, San José State University, San José, California, USA

Laurence A. Nafie, Department of Chemistry, Syracuse University, Syracuse, New York, USA

Koji Nakanishi, Department of Chemistry, Columbia University, New York, New York, USA

Valentin Paul Nicu, Division of Theoretical Chemistry, Faculty FEW/Chemistry, VU University, Amsterdam, The Netherlands

Magdalena Pecul, Faculty of Chemistry, University of Warsaw, Warszawa, Poland

Prasad L. Polavarapu, Department of Chemistry, Vanderbilt University, Nashville, Tennessee, USA

Ivan Powis, School of Chemistry, University of Nottingham, Nottingham, United Kingdom

Gerhard Raabe, Institute of Organic Chemistry, RWTH Aachen University, Aachen, Germany

Hanju Rhee, Seoul Center, Korea Basic Science Institute, Seoul, South Korea

James P. Riehl, Department of Chemistry, University of Minnesota, Duluth, Minnesota, USA

G. L. J. A. Rikken, National Laboratory of Intense Magnetic Fields, Toulouse, France

Alison Rodger, Warwick Centre for Analytical Science and Department of Chemistry, University of Warwick, Coventry, United Kingdom

Andrei Rogalev, European Synchrotron Radiation Laboratory, Grenoble, France

Kenneth Ruud, Centre for Theoretical and Computational Chemistry, Department of Chemistry, University of Tromsø, Tromsø, Norway

Piero Salvadori, Department of Chemistry and Industrial Chemistry, University of Pisa, Pisa, Italy

Matthias Stolte, Institute of Organic Chemistry, University of Würzburg, Würzburg, Germany

John C. Sutherland, Department of Physics, East Carolina University, Greenville, North Carolina, USA and Biology Department, Brookhaven National Laboratory, Upton, New York, USA

Patrick H. Vaccaro, Department of Chemistry, Yale University, New Haven, Connecticut, USA

Georges H. Wagnière, Institute of Physical Chemistry, University of Zürich, Zürich, Switzerland

Hong-fei Wang, Environmental Molecular Science Laboratory, Pacific Northwest National Laboratory, Richland, Washington, USA

Robert W. Woody, Department of Biochemistry and Molecular Biology, Colorado State University, Fort Collins, Colorado, USA

Part I

INTRODUCTION