Optical Activity of Proteins and Other Macromolecules

I The Realm of Proteins. Structural Features. The Phenomenon of Optical Activity. Historical Highlights.- II The Phenomena of Optical Activity. Terms and Definitions. Theoretical Considerations. The Drude and Moffitt Equations.- 1. Refraction of Monochromatic Polarized Light.- 2. Optical Rotation.- 3. Specific Rotation.- 4. Corrected Mean Residual Specific Rotation.- 5. Optical Activity and Absorption of Light.- 6. Optical Rotatory Dispersion. The Drude Equation.- 7. The Moffitt Equation for the Rotatory Dispersion of Helical Structures.- 8. Configuration and Conformation.- 9. The Far Ultraviolet Absorption Maxima and Cotton Effects.- 10. Absorption and Refraction.- 11. Circular Dichroism.- 12. Magnetic Circular Dichroism.- III Polarimeters and Spectropolarimeters. The Measurement of Optical Activity.- 1. Visual Polarimetry.- 2. Photoelectric Spectropolarimetry.- 3. Optical Rotatory Dispersion Measurement. General Principles of Operation. Sources of Errors. Accuracy and Reproducibility.- 4. Cells and Solutions.- 5. Circularly Polarized Light.- 6. Circular Dichroism Measurement.- 7. Resolution of Circular Dichroism Curves.- 8. Circular Dichroism Measurement in the Vacuum Ultraviolet Region.- IV Optical Activity of Amino Acids, Peptides, and Proteins.- 1. Optical Rotation and Configuration of ?-Amino Acids.- 2. Optical Rotatory Dispersion of ?-Amino Acids.- 3. Rotatory Contribution of Amino Acid Residues in Peptides.- 4. Optical Rotation of Proteins at Various pH.- 5. Circular Dichroism of Amino Acids.- V The Optical Rotatory Dispersion of Polyamino Acids and Proteins. Measurements in the Visible and Near Ultraviolet Spectral Zones.- 1. Rotatory Dispersion of Polyamino Acids as Protein Models.- 2. Rotatory Dispersion of Proteins.- 3. Limitations of the Drude and MoffittMethods in the Elucidation of Protein Conformation.- 4. Amino Acid Composition and Conformation of Proteins.- VI The Far Ultraviolet Cotton Effects of Synthetic Polyamino Acids.- 1. The ?-Helical and Random Conformations of Poly-?-l-glutamic Acid and Poly-?-l-lysine.- 2. ORD of Other Structural Orders.- 3. Circular Dichroism of Polyamino Acids of Various Conformations.- VII The Cotton Effects and Conformation of Proteins.- 1. Attempts to Classify Proteins According to Their Conformation.- 2. Comments on Nomenclature.- 3. Cotton Effects of Proteins with a High ?-Helix Content.- 4. Rotatory Dispersion, Circular Dichroism, X-Ray Diffraction, and Conformation of Myoglobin, Lysozyme, and Other Proteins.- 5. Conformational Transitions and Cotton Effects in the Near Ultraviolet and Visible Spectrum.- 6. The Fine Structure of the Near Ultraviolet CD Bands and Conformational Features of the Aromatic Chromophores.- VIII Cotton Effects and Conformation of Nonhelical Proteins.- 1. Globular Proteins of Known and Unknown Conformation.- 2. Globular Proteins having a High Content of ? Conformation.- 3. Cotton Effects and Conformation of Bovine Pancreatic Ribonuclease.- 4. Other Rigid Nonhelical Proteins.- 5. Cotton Effects and Conformation of Flexible Nonhelical Proteins.- 6. Cotton Effects and Conformation of Immunoglobulins.- 7. Effect of Detergents on the Conformation of Nonhelical Proteins.- 8. Circular Dichroism of Small Polypeptide Hormones.- IX Optical Activity of Structural Proteins.- 1. Natural Variety of Structural Proteins and Difficulties Involved in Their Study.- 2. Structural Proteins with a High ?-Helix Content.- 3. Optical Activity of Structural Proteins with ? Conformation.- 4. Optical Activity and Conformation of Collagen.- X Optical Activity of Nucleoproteinsand Histones.- 1. Conformation of Histones.- 2. Optical Activity of Nucleic Acids and Nucleoproteins.- 3. Conformation of Proteins and Nucleic Acids in Ribosomes, Viruses, and Phages.- XI Optical Activity of Glycoproteins and Lipoproteins.- 1. Glycoproteins and Polysaccharides.- 2. Lipoproteins.- 3. Membranes and Other Particulate Suspensions.- XII Concluding Remarks.- References.