The Porphyrins V3

Physical Chemistry, Part A

1st Edition - December 28, 1978
Editor: David Dolphin
Language: English
eBook ISBN:
9 7 8 - 0 - 3 2 3 - 1 4 3 9 0 - 5

The Porphyrins, Volume III: Physical Chemistry, Part A deals with the physical chemistry of porphyrins, their precursors, catabolic derivatives, and related systems. The book… Read more

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The Porphyrins, Volume III: Physical Chemistry, Part A deals with the physical chemistry of porphyrins, their precursors, catabolic derivatives, and related systems. The book covers electronic structure and spectroscopy including circular dichroism and magnetic circular dichroism as well as electronic, infrared, resonance Raman, and Zeeman spectroscopy. Porphyrin stereochemistry, X-ray crystallography, and mass spectroscopy are also included. This volume is organized into 12 chapters and begins with an overview of the optical absorption and emission spectra of porphyrins and the theory by which these facts are understood. The discussion then shifts to the electronic states of the iron porphyrin complex in various heme proteins as displayed by the light absorption properties in the visible region of the electromagnetic spectrum. The reader is methodically introduced to the electronic absorption spectra and molecular orbital theory of chlorophylls, the magnetic optical activity of porphyrins and hemoproteins, and circular dichroism studies of hemoproteins. The book also examines the mass spectra and infrared spectroscopy of porphyrins, resonance Raman scattering from metalloporphyrins and hemoproteins, and photographic essay of porphyrins and related macrocycles. It then concludes with a chapter on high-resolution Zeeman spectroscopy of metalloporphyrins. This book should be useful to inorganic, organic, physical, and biochemists interested in the physical chemistry of porphyrins.

List of Contributors

General Preface

Preface

Contents of Other Volumes

1 Optical Spectra and Electronic Structure of Porphyrins and Related Rings

I. Scope of Chapter

II. Regular Porphyrins [Groups I-V—Valence I-V, respectively;Th(IV); U(VI)]

III. Irregular Porphyrins

IV. Theory

References

2 Electronic Absorption Spectra of Hemes and Hemoproteins

I. Introduction

II. Description of Porphyrin Spectra

III. Theoretical Description of Porphyrin Spectra

IV. Theoretical Description of Iron Porphyrins

V. Heme Proteins

VI. Summary

References

3 Electronic Absorption Spectra of Chlorophylls

I. Molecular Orbital Theory of Chlorophylls

II. Phenomenology and Comparison with Theory

III. Further Applications of Molecular Orbital Theory of Chlorophylls

References

4 The Magnetic Optical Activity of Porphyrins

I. Introduction

II. The Phenomena

III. Classification of Porphyrins by Spectral Type

IV. Zero Field Splitting

V. Instrumentation

References

5 The Magnetic Optical Activity of Hemoproteins

I. Introduction

II. Magnetic Optical Activity: The Faraday Effect

III. Sensitivity to the Chemistry of Iron

IV. Effects of Protein Environment

V. Microparticulate Heme Proteins

VI. Lanthanide-Substituted Porphyrins

References

6 Circular Dichroism Studies of Hemoproteins and Heme Models

I. Introduction

II. Definitions

III. Electronic Configuration and Absorption Properties of Heme Systems

IV. Protein Optical Activity: Theory and Analysis

V. Heme Optical Activity: Origin and Analysis

VI. CD Spectra of Selected Examples

References

7 Infrared Spectroscopy of Porphyrins

I. Introduction

II. Sampling Considerations

III. Band Assignments

IV. Trans-Ligand Structure of Heme Protein Complexes

V. Polarizability of Metal-Porphyrin Complexes

VI. Cis and Trans Effects

VII. Nonpolar Interactions and Molecular Pairs in Heme Proteins

References

8 Resonance Raman Scattering from Metalloporphyrins and Hemoproteins

I. Introduction

II. Experimental Techniques

III. Theory

IV. Metalloporphyrin Resonance Raman Spectra

References

9 Mass Spectra of Porphyrins and Related Compounds

I. General Remarks

II. Porphine Derivatives

III. Corrins

IV. Homoporphyrins

V. Heteraporphine and Heteracorrin Derivatives

VI. Concluding Remarks

References

10 Porphyrin Stereochemistry

I. Introduction

II. Metalloporphyrin Stereochemistry

III. Stereochemistry of Metal-Free Porphyrins

IV. Addendum

References

11 A Photographic Essay of Porphyrins and Related Macrocycles

Text

References

12 High-Resolution Zeeman Spectroscopy of Metalloporphyrins

I. Introduction

II. Zeeman Effect in Metalloporphyrins

References

Author Index

Subject Index