WILEY-VCH A JOHN WILEY & SONS, INC., PUBLICATION New York Chichester Weinheim Brisbane Singapore Toronto

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1 CIRCULAR DICHROISM Principles and Applications SECOND EDITION Edited by NINA BEROVA KOJI NAKANISHI ROBERT W. WOODY WILEY-VCH A JOHN WILEY & SONS, INC., PUBLICATION New York Chichester Weinheim Brisbane Singapore Toronto

2 Preface Contributors xv xvii 1 Circular Dichroism: An Introduction 1 Günther Snatzke (edited by Robert W. Woody) 1.1 Introduction Principles of UV Spectroscopy Principles of CD Spectroscopy 28 2 From Pasteur to Parity Nonconservation: Theories of the Origin of Molecular Chirality 37 Stephen F. Mason 2.1 Introduction Pasteur on Molecular and Cosmic Dissymmetry Stereoselective Chiral Synthesis Symmetry Principles and Chiral Fields Chance and Necessity in the Evolution of Biochemical Homochirality Parity and Its Nonconservation Summary and Conclusion 50 3 Theoretical Approach To Electronic Optical Activity 55 Axel Koslowski, Narasimha Sreerama, and Robert W. Woody 3.1 Introduction Theory of Optical Activity Quantum-Chemical versus Classical Methods for Calculation of Optical Activity Calculation of Optical Properties of Proteins Calculation of Optical Properties of Nucleic Acids Perspectives 86 4 Vibrational Optical Activity Theory 97 Laurence A. Nafie and Teresa B. Freedman 4.1 Introduction Theory of Vibrational Circular Dichroism Theory of Raman Optical Activity 111 vii

3 4.4 Spectral Simulation of VOA Using Ab Initio Methods Recent Technological Advances 124 Circular Dichroism of Oriented Molecules 133 Hans-Georg Kuball and Tatiana Höfer 5.1 Introduction Molecular Chirality and Chiral Anisotropie Phases ACD Spectroscopy in Chiral Anisotropie Phases without Suprastructural Chirality Description of ACD and Polarized UV Spectroscopy Results and Discussion of ACD Spectroscopy of Phases without Superstructural Chirality ACD Spectroscopy in Chiral Anisotropie Phases with Suprastructural Chirality Summary and Outlook 156 Solid-State CD: Application to Inorganic and Organic Chemistry 159 Reiko Kuroda 6.1 Introduction Uniaxial Single Crystals Decomposition of CD Bands into the E and A 2 Components Microcrystalline CD CD Intrinsic to the Solid State Following a Solid-State Reaction by Solid-State CD Interpretation of CD Spectra Comments and New Developments in Experimental Procedures Conclusion 183 Circularly Polarized Luminescence: A Probe for Chirality in the Excited State 185 Harry P. J. M. Dekkers 7.1 Introduction Scope of the CPL Technique Principles of Measurement and Instrumentation Relationship between Experimental and Theoretical Quantities Applications of CPL Spectroscopy: Organic Carbonyl Compounds Conclusion 211 Chiroptical Luminescence Spectroscopy as a Probe of the Chirality-Dependent Electronic State Structure, Stereochemical Dynamics, and Intermolecular Interaction Properties of Dissymmetric Metal Complexes in Solution 217 F. S. Richardson and David H. Metcalf 8.1 Introduction Chiroptical Luminescence Measurements 218

4 ix 8.3 Decay Kinetics of Chiral Luminophores Emitting-State Populations of Luminophores under Steady-State Excitation/Emission Conditions Circularly Polarized Excitation Examples of Applications and Experimental Results Conclusion Fast Time-Resolved Circular Dichroism Measurements 243 David S. Kliger and James W. Lewis 9.1 Introduction Ellipsometric CD Measurements Ellipsometric Magnetic CD Measurements Extension of Ellipsometric Approach to Other Polanzation Spectroscopies Potential Artifacts in Ellipsometric Polarization Spectroscopies Applications The Octant Rule 261 David A. Lightner 10.1 Introduction Description of the Octant Rule Defining the Boundaries of the Octant Rule Theory and Analysis Applications of the Octant Rule Concluding Comments Circular Dichroism and Chirality of Dienes 305 J. K. Gawronski 11.1 Introduction UV Spectra Skewed s-cis Dienes The 1,3-Cyclohexadiene Chirality Model Endocyclic s-trans Dienes Exocyclic s-trans Dienes Strained Dienes Interactions with Other Chromophores Exciton Chirality Method: Principles and Applications 337 Nina Berova and Koji Nakanishi 12.1 Exciton Chirality Method: Basic Principles Additivity Relations in Exciton-Coupled CD Curves Unique UV-VIS Absorption and CD Exciton-Split Spectra of Chiral Biscyanine Dye CD Chromophores with Favorable Properties for Exciton Coupling and Other Practical Aspects of Exciton Chirality Method Application of Exciton Chirality Method to Acyclic Compounds 364

5 x CONTENTS 12.6 Sensitivity Enhancement of Exciton-Coupled CD by Fluorescence Detection is-substituted Aromatics and Exciton Chiraiity 383 Chantal Andraud, Chantal Garcia, and Andre Collet 13.1 Introduction Synthesis, Resolution, and Absolute Configuration of Sulfur-Substituted Cyclotriveratrylenes The Exciton Mechanism in C 3 -Cyclotriveratrylenes Sulfur-Substituted Cyclotriveratrylenes and Exciton Chiraiity Conclusion Applications of the Benzene Sector and Benzene Chiraiity Rules 397 Howard E. Smith 14.1 Introduction Benzene Sector Rule Benzene Chiraiity Rule Applications to Compounds Related to Phenylcarbinamine and Carbinol Applications to Compounds Related to Benzylcarbinamine and Benzylcarbinol Benzocycloalkenes Circular Dichroism of Twisted ir-electron Systems: Theoretical Determination of the Absolute Stereochemistry of Natural Products and Chiral Synthetic Organic Compounds 431 Nobuyuki Harada 15.1 Theoretical Calculation of CD and UV Spectra by the 7t-Electron SCF-CI-DV MO Method Absolute Stereochemistry of (+)-l,8a-dihydro-3,8-dimethylazulene, a Labile Biosynthetic Intermediate for 1,4-Dimethylazulene Circular Dichorism and Absolute Stereochemistry of Chiral Troponoid Spiro Compounds Absolute Stereochemistry of the Halenaquinol Family: Marine Natural Products with a Novel Pentacyclic Skeleton, as Determined by Theoretical Calculation of CD Spectra Chiral Spiromatics of 9,9'-Spirobifluorene Skeleton Atropisomerism of Natural Products: CD and Absolute Stereochemistry of the Biflavone, 4,4'",7,7"-Tetra-0-methylcupressuflavone Conclusion Determination of Conformations and Absolute Configurations by Semiempirical Calculation of CD Spectra 459 Jan Sandström 16.1 Introduction Spectroscopic and Computational Methods Studies of Rigid Molecules 467

6 xi 16.4 Flexible Molecules: Planar Groups with Attached Chiral Rotors Concluding Remarks A Model for How Polymers Amplify Chirality 491 Mark M. Green 17.1 Introduction The Uniform Chiral Field The Quenched Random Chiral Field Final Remarks Induced CD or Polymers 521 Eiji Yashima and Yoshio Okamoto 18.1 Introduction Helix Formation and Induced CD of Polyacetylenes Induced CD of Polyisocyanates Induced CD of Other 7t-Conjugated Polymers: Polyaniline and Polypyrrole Application of CD to the Study of Some Cholesteric Mesophase 547 Giovanni Gottarelli and Gian Piero Spada 19.1 Introduction Validity of CD Measurements on Cholesteric Samples CD Study of Some Lyotropic Cholesterics Circular Dichroism of Inorganic Complexes: Interpretation and Applications 563 Reiko Kuroda and Yoshihiko Saito 20.1 Introduction Trisbidentate Complexes Complexes Involving Multidentate Ligands Chiral Tetrahedral Coordination Investigation of Formation Reaction and Thermodynamic Stability Lanthanide Complexes Application to Life Sciences Concluding Remarks Circular Dichroism of Peptides and Proteins 601 Narasimha Sreerama and Robert W. Woody 21.1 Introduction Peptide Backbone and Far-UV CD CD of Model Polypeptides Structural Analysis of Proteins Aromatic Side Chains and Disulfides Extrinsic Chromophores 615

7 xü CONTENTS 22 Peptide and Protein Conformational Studies with Vibrational Circular Dichroism and Related Spectroscopies 621 Timothy A. Keiderling 22.1 Introduction Experimental Techniques Peptide VCD Studies Protein VCD Spectral Results Quantitative Protein VCD Studies in Terms of Structure Conclusions Vibrational Raman Optical Activity: From Fundamentals to Biochemical Applications 667 Laurence D. Barron and Lutz Hecht 23.1 Introduction Basic Theory of ROA ROA Instrumentation Some Experimental ROA Results Concluding Remarks CD of Nucleic Acids 703 W. Curtis Johnson 24.1 Introduction Right-Handed Nucleic Acids Left-Handed DNA Applications of CD to Study Secondary Structure Circular Dichroism of Nucleic Acids: Nonclassical Conformations and Modified Oligonucleotides 719 Jean Claude Maurizot 25.1 Introduction Nonclassical Nucleic Acid Structures CD of Chemically Modified Oligonucleotides Concluding Remarks DNA-Drug Interactions 741 Malin Ardhammar, Tomas Kurucsev, and Bengt Norden 26.1 Introduction Background Intercalation Groove Binding Illustrative Examples Additional Systems Studied Triplex and Z-Form DNA Metal Complexes 757

8 xiü 26.9 Peptide Nucleic Acid Drugs Other Nucleic Acid Complexes CD of Protein-Nucleic Acid Interactions 769 Donald M. Gray 27.1 Introduction Complexes Dominated by CD Changes of Protein Secondary Structure Complexes that Involve CD Changes of Nucleic Acids Complexes with Nucleotides , Summary HPLC-CD: Stereochemical Analysis at Work 797 Piero Salvadori, Lorenzo Di Bari, and Gennaro Pescitelli 28.1 Introduction HPLC-CD Device Applications and Interpretation Methods Related Techniques and Perspectives Conclusions Applications of Chiroptical Spectroscopy in the Characterization of Compounds Having Pharmaceutical Importance 819 Harry G. Brittain 29.1 Introduction Applications of Circular Birefringence (Polarimetry) Applications of Circular Dichroism Concluding Remarks 841 Index 845