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  • Cover Page

  • Title Page

  • ISBN 0471281387

  • CONTENTS

    • Preface to the Second Edition

    • Preface to the First Edition

    • 1 Introduction

    • 2 Syntheses of Macromolecular Compounds

    • 3 Distribution of Molecular Weight

    • 4 Macromolecular Thermodynamics

    • 5 Chain Configurations

    • 6 Liquid Crystals

    • 7 Rubber Elasticity

    • 8 Viscosity and Viscoelasticity

    • 9 Osmotic Pressure

    • 10 Diffusion

    • 11 Sedimentation

    • 12 Optical Rotatory Dispersion and Circular Dichroism

    • 13 High-Performance Liquid Chromatography and Electrophoresis

    • 14 Light Scattering

    • 15 Fourier Series

    • 16 Small-Angle X-Ray Scattering, Neutron Scattering, and Laser Light Scattering

    • 17 Electronic and Infrared Spectroscopy

    • 18 Protein Molecules

    • 19 Nuclear Magnetic Resonance

    • 20 X-Ray Crystallography

    • Author Index

    • Subject Index

  • 1 INTRODUCTION

    • 1.1 COLLOIDS

    • 1.2 MACROMOLECULES

      • 1.2.1 Synthetic Polymers

      • 1.2.2 Biological Polymers

    • 1.3 MACROMOLECULAR SCIENCE

    • REFERENCES

  • 2 SYNTHESES OF MACROMOLECULAR COMPOUNDS

    • 2.1 RADICAL POLYMERIZATION

      • 2.1.1 Complications

      • 2.1.2 Methods of Free-Radical Polymerization

      • 2.1.3 Some Well-Known Overall Reactions of Addition Polymersy

    • 2.2 IONIC POLYMERIZATION

      • 2.2.1 Anionic Polymerization

      • 2.2.2 Cationic Polymerization

      • 2.2.3 Living Polymers

    • 2.3 COORDINATION POLYMERIZATION

    • 2.4 STEPWISE POLYMERIZATION

    • 2.5 KINETICS OF THE SYNTHESES OF POLYMERS

      • 2.5.1 Condensation Reactions

      • 2.5.2 Chain Reactions

    • 2.6 POLYPEPTIDE SYNTHESIS

      • 2.6.1 Synthesis of Insulin

      • 2.6.2 Synthesis of Ribonucleus

    • 2.7 DNA SYNTHESIS

    • REFERENCES

    • PROBLEMS

  • 3 DISTRIBUTION OF MOLECULAR WEIGHT

    • 3.1 REVIEW OF MATHEMATICAL STATISTICS

      • 3.1.1 Binomial Distribution

      • 3.1.2 Poisson Distribution

      • 3.1.3 Gaussian Distribution

    • 3.2 ONE-PARAMETER EQUATION

      • 3.2.1 Condensation Polymers

      • 3.2.2 Addition Polymers

    • 3.3 TWO-PARAMETER EQUATIONS

      • 3.3.1 Normal Distribution

      • 3.3.2 Logarithm Normal Distribution

    • 3.4 TYPES OF MOLECULAR WEIGHT

    • 3.5 EXPERIMENTAL METHODS FOR DETERMINING MOLECULAR WEIGHT AND MOLECULAR WEIGHT DISTRIBUTION

    • REFERENCES

    • PROBLEMS

  • 4 MACROMOLECULAR THERMODYNAMICS

    • 4.1 REVIEW OF THERMODYNAMICS

    • 4.2 DS OF MIXING: FLORY THEORY

    • 4.3 DH OF MIXING

      • 4.3.1 Cohesive Energy Density

      • 4.3.2 Contact Energy (First-Neighbor Interaction or Energy Due to Contact)

    • 4.4 DG OF MIXING

    • 4.5 PARTIAL MOLAR QUANTITIES

      • 4.5.1 Partial Specific Volume

      • 4.5.2 Chemical Potential

    • 4.6 THERMODYNAMICS OF DILUTE POLYMER SOLUTIONS

      • 4.6.1 Vapor Pressure

      • 4.6.2 Phase Equilibrium

    • APPENDIX: THERMODYNAMICS AND CRITICAL PHENOMENA

    • REFERENCES

    • PROBLEMS

  • 5 CHAIN CONFIGURATIONS

    • 5.1 PRELIMINARY DESCRIPTIONS OF A POLYMER CHAIN

    • 5.2 RANDOM WALK AND THE MARKOV PROCESS

      • 5.2.1 Random Walk

      • 5.2.2 Markov Chain

    • 5.3 RANDOM-FLIGHT CHAINS

    • 5.4 WORMLIKE CHAINS

    • 5.5 FLORY’S MEAN-FIELD THEORY

    • 5.6 PERTURBATION THEORY

      • 5.6.1 First-Order Perturbation Theory

      • 5.6.2 Cluster Expansion Method

    • 5.7 CHAIN CROSSOVER AND CHAIN ENTANGLEMENT

      • 5.7.1 Concentration Effect

      • 5.7.2 Temperature Effect

      • 5.7.3 Tube Theory (Reptation Theory)

      • 5.7.4 Images of Individual Polymer Chains

    • 5.8 SCALING AND UNIVERSALITY

    • APPENDIX A SCALING CONCEPTS

    • APPENDIX B CORRELATION FUNCTION

    • REFERENCES

    • PROBLEMS

  • 6 LIQUID CRYSTALS

    • 6.1 MESOGENS

    • 6.2 POLYMERIC LIQUID CRYSTALS

      • 6.2.1 Low-Molecular-Weight Liquid Crystals

      • 6.2.2 Main-Chain Liquid-Crystalline Polymers

      • 6.2.3 Side-Chain Liquid-Crystalline Polymers

      • 6.2.4 Segmented-Chain Liquid-Crystalline Polymers

    • 6.3 SHAPES OF MESOGENS

    • 6.4 LIQUID-CRYSTAL PHASES

      • 6.4.1 Mesophases in General

      • 6.4.2 Nematic Phase

      • 6.4.3 Smectic Phase

      • 6.4.4 Compounds Representing Some Mesophases

      • 6.4.5 Shape and Phase

      • 6.4.6 Decreasing Order and DH of Phase Transition

    • 6.5 THERMOTROPIC AND LYOTROPIC LIQUID CRYSTALS

    • 6.6 KERR EFFECT

    • 6.7 THEORIES OF LIQUID-CRYSTALLINE ORDERING

      • 6.7.1 Rigid-Rod Model

      • 6.7.2 Lattice Model

      • 6.7.3 De Genne’s Fluctuation Theory

    • 6.8 CURRENT INDUSTRIAL APPLICATIONS OF LIQUID CRYSTALS

      • 6.8.1 Liquid-Crystal Displays

      • 6.8.2 Electronic Devices

    • REFERENCES

  • 7 RUBBER ELASTICITY

    • 7.1 RUBBER AND RUBBERLIKE MATERIALS

    • 7.2 NETWORK STRUCTURE

    • 7.3 NATURAL RUBBER AND SYNTHETIC RUBBER

    • 7.4 THERMODYNAMICS OF RUBBER

    • 7.5 STATISTICAL THEORY OF RUBBER ELASTICITY

    • 7.6 GELS

    • REFERENCES

    • PROBLEMS

  • 8 VISCOSITY AND VISCOELASTICITY

    • 8.1 VISCOSITY

      • 8.1.1 Capillary Viscometers

      • 8.1.2 Intrinsic Viscosity

      • 8.1.3 Treatment of Intrinsic Viscosity Data

      • 8.1.4 Stokes’ Law

      • 8.1.5 Theories in Relation to Intrinsic Viscosity of Flexible Chains

      • 8.1.6 Chain Entanglement

      • 8.1.7 Biological Polymers (Rigid Polymers, Inflexible Chains)

    • 8.2 VISCOELASTICITY

      • 8.2.1 Rouse Theory

      • 8.2.2 Zimm Theory

    • REFERENCES

    • PROBLEMS

  • 9 OSMOTIC PRESSURE

    • 9.1 OSMOMETERS

    • 9.2 DETERMINATION OF MOLECULAR WEIGHT AND SECOND VIRIAL COEFFICIENT

    • 9.3 THEORIES OF OSMOTIC PRESSURE AND OSMOTIC SECOND VIRIAL COEFFICIENT

      • 9.3.1 McMillan–Mayer Theory

      • 9.3.2 Flory Theory

      • 9.3.3 Flory–Krigbaum Theory

      • 9.3.4 Kurata–Yamakawa Theory

      • 9.3.5 des Cloizeaux–de Gennes Scaling Theory

      • 9.3.6 Scatchard’s Equation for Macro Ions

    • APPENDIX A ENSEMBLES

    • APPENDIX B PARTITION FUNCTIONS

    • APPENDIX C MEAN-FIELD THEORY AND RENORMALIZATION GROUP THEORY

    • APPENDIX D LAGRANGIAN THEORY

    • APPENDIX E GREEN’S FUNCTION

    • REFERENCES

    • PROBLEMS

  • 10 DIFFUSION

    • 10.1 TRANSLATIONAL DIFFUSION

      • 10.1.1 Fick’s First and Second Laws

      • 10.1.2 Solution to Continuity Equation

    • 10.2 PHYSICAL INTERPRETATION OF DIFFUSION: EINSTEIN’S EQUATION OF DIFFUSION

    • 10.3 SIZE, SHAPE, AND MOLECULAR WEIGHT DETERMINATIONS

      • 10.3.1 Size

      • 10.3.2 Shape

      • 10.3.3 Molecular Weight

    • 10.4 CONCENTRATION DEPENDENCE OF DIFFUSION COEFFICIENT

    • 10.5 SCALING RELATION FOR TRANSLATIONAL DIFFUSION COEFFICIENT

    • 10.6 MEASUREMENTS OF TRANSLATIONAL DIFFUSION COEFFICIENT

      • 10.6.1 Measurement Based on Fick’s First Law

      • 10.6.2 Measurement Based on Fick’s Second Law

    • 10.7 ROTATIONAL DIFFUSION

      • 10.7.1 Flow Birefringence

      • 10.7.2 Fluorescence Depolarization

    • REFERENCES

    • PROBLEMS

  • 11 SEDIMENTATION

    • 11.1 APPARATUS

    • 11.2 SEDIMENTATION VELOCITY

      • 11.2.1 Measurement of Sedimentation Coefficients: Moving-Boundary Methods

      • 11.2.2 Svedberg Equation

      • 11.2.3 Application of Sedimentation Coefficient

    • 11.3 SEDIMENTATION EQUILIBRIUM

      • 11.3.1 Archibald Method

      • 11.3.2 Van Holde–Baldwin (Low-Speed) Method (Rotor Velocity 10,000–14,000 rpm)

      • 11.3.3 Yphantis (High-Speed) Method (Rotor Velocity 28,000–32,000 rpm)

      • 11.3.4 Absorption System

    • 11.4 DENSITY GRADIENT SEDIMENTATION EQUILIBRIUM

    • 11.5 SCALING THEORY

    • REFERENCES

    • PROBLEMS

  • 12 OPTICAL ROTATORY DISPERSION AND CIRCULAR DICHROISM

    • 12.1 POLARIZED LIGHT

    • 12.2 OPTICAL ROTATORY DISPERSION

    • 12.3 CIRCULAR DICHROISM

    • 12.4 COTTON EFFECT

    • 12.5 CORRELATION BETWEEN ORD AND CD

    • 12.6 COMPARISON OF ORD AND CD

    • REFERENCES

    • PROBLEMS

  • 13 HIGH-PERFORMANCE LIQUID CHROMATOGRAPHY AND ELECTROPHORESIS

    • 13.1 HIGH-PERFORMANCE LIQUID CHROMATOGRAPHY

      • 13.1.1 Chromatographic Terms and Parameters

      • 13.1.2 Theory of Chromatography

      • 13.1.3 Types of HPLC

    • 13.2 ELECTROPHORESIS

      • 13.2.1 Basic Theory

      • 13.2.2 General Techniques of Modern Electrophoresis

      • 13.2.3 Agarose Gel Electrophoresis and Polyacrylamide Gel Electrophoresis

      • 13.2.4 Southern Blot, Northern Blot, and Western Blot

      • 13.2.5 Sequencing DNA Fragments

      • 13.2.6 Isoelectric Focusing and Isotachophoresis

    • 13.3 FIELD-FLOW FRACTIONATION

    • REFERENCES

    • PROBLEMS

  • 14 LIGHT SCATTERING

    • 14.1 RAYLEIGH SCATTERING

    • 14.2 FLUCTUATION THEORY (DEBYE)

    • 14.3 DETERMINATION OF MOLECULAR WEIGHT AND MOLECULAR INTERACTION

      • 14.3.1 Two-Component Systems

      • 14.3.2 Multicomponent Systems

      • 14.3.3 Copolymers

      • 14.3.4 Correction of Anisotropy and Deporalization of Scattered Light

    • 14.4 INTERNAL INTERFERENCE

    • 14.5 DETERMINATION OF MOLECULAR WEIGHT AND RADIUS OF GYRATION BY THE ZIMM PLOT

    • APPENDIX EXPERIMENTAL TECHNIQUES OF THE ZIMM PLOT

    • REFERENCES

    • PROBLEMS

  • 15 FOURIER SERIES

    • 15.1 PRELIMINARIES

    • 15.2 FOURIER SERIES

      • 15.2.1 Basic Fourier Series

      • 15.2.2 Fourier Sine Series

      • 15.2.3 Fourier Cosine Series

      • 15.2.4 Complex Fouries Series

      • 15.2.5 Other Forms of Fourier Series

    • 15.3 CONVERSION OF INFINITE SERIES INTO INTEGRALS

    • 15.4 FOURIER INTEGRALS

    • 15.5 FOURIER TRANSFORMS

      • 15.5.1 Fourier Transform Pairs

    • 15.6 CONVOLUTION

      • 15.6.1 Definition

      • 15.6.2 Convolution Theorem

      • 15.6.3 Convolution and Fourier Theory: Power Theorem

    • 15.7 EXTENSION OF FOURIER SERIES AND FOURIER TRANSFORM

      • 15.7.1 Lorentz Line Shape

      • 15.7.2 Correlation Function

    • 15.8 DISCRETE FOURIER TRANSFORM

      • 15.8.1 Discrete and Inverse Discrete Fourier Transform

      • 15.8.2 Application of DFT

      • 15.8.3 Fast Fourier Transform

    • APPENDIX

    • REFERENCES

    • PROBLEMS

  • 16 SMALL-ANGLE X-RAY SCATTERING, NEUTRON SCATTERING, AND LASER LIGHT SCATTERING

    • 16.1 SMALL-ANGLE X-RAY SCATTERING

      • 16.1.1 Apparatus

      • 16.1.2 Guinier Plot

      • 16.1.3 Correlation Function

      • 16.1.4 On Size and Shape of Proteins

    • 16.2 SMALL-ANGLE NEUTRON SCATTERING

      • 16.2.1 Six Types of Neutron Scattering

      • 16.2.2 Theory

      • 16.2.3 Dynamics of a Polymer Solution

      • 16.2.4 Coherently Elastic Neutron Scattering

      • 16.2.5 Comparison of Small-Angle Neutron Scattering with Light Scattering

      • 16.2.6 Contrast Factor

      • 16.2.7 Lorentzian Shape

      • 16.2.8 Neutron Spectroscopy

    • 16.3 LASER LIGHT SCATTERING

      • 16.3.1 Laser Light-Scattering Experiment

      • 16.3.2 Autocorrelation and Power Spectrum

      • 16.3.3 Measurement of Diffusion Coefficient in General

      • 16.3.4 Application to Study of Polymers in Semidilute Solutions

    • REFERENCES

    • PROBLEMS

  • 17 ELECTRONIC AND INFRARED SPECTROSCOPY

    • 17.1 ULTRAVIOLET (AND VISIBLE) ABSORPTION SPECTRA

      • 17.1.1 Lambert–Beer Law

      • 17.1.2 Terminology

      • 17.1.3 Synthetic Polymers

      • 17.1.4 Proteins

      • 17.1.5 Nucleic Acids

    • 17.2 FLUORESCENCE SPECTROSCOPY

      • 17.2.1 Fluorescence Phenomena

      • 17.2.2 Emission and Excitation Spectra

      • 17.2.3 Quenching

      • 17.2.4 Energy Transfer

      • 17.2.5 Polarization and Depolarization

    • 17.3 INFRARED SPECTROSCOPY

      • 17.3.1 Basic Theory

      • 17.3.2 Absorption Bands: Stretching and Bending

      • 17.3.3 Infrared Spectroscopy of Synthetic Polymers

      • 17.3.4 Biological Polymers

      • 17.3.5 Fourier Transform Infrared Spectroscopy

    • REFERENCES

    • PROBLEMS

  • 18 PROTEIN MOLECULES

    • 18.1 PROTEIN SEQUENCE AND STRUCTURE

      • 18.1.1 Sequence

      • 18.1.2 Secondary Structure

      • 18.1.3 Tertiary Structure

      • 18.1.4 Quaternary Structure

    • 18.2 PROTEIN STRUCTURE REPRESENTATIONS

      • 18.2.1 Representation Symbols

      • 18.2.2 Representations of Whole Molecule

    • 18.3 PROTEIN FOLDING AND REFOLDING

      • 18.3.1 Computer Simulation

      • 18.3.2 Homolog Modeling

      • 18.3.3 De Novo Prediction

    • 18.4 PROTEIN MISFOLDING

      • 18.4.1 Biological Factor: Chaperones

      • 18.4.2 Chemical Factor: Intra- and Intermolecular Interactions

      • 18.4.3 Brain Diseases

    • 18.5 GENOMICS, PROTEOMICS, AND BIOINFORMATICS

    • 18.6 RIBOSOMES: SITE AND FUNCTION OF PROTEIN SYNTHESIS

    • REFERENCES

  • 19 NUCLEAR MAGNETIC RESONANCE

    • 19.1 GENERAL PRINCIPLES

      • 19.1.1 Magnetic Field and Magnetic Moment

      • 19.1.2 Magnetic Properties of Nuclei

      • 19.1.3 Resonance

      • 19.1.4 Nuclear Magnetic Resonance

    • 19.2 CHEMICAL SHIFT (d) AND SPIN–SPIN COUPLING CONSTANT (J)

    • 19.3 RELAXATION PROCESSES

      • 19.3.1 Spin–Lattice Relaxation and Spin–Spin Relaxation

      • 19.3.2 Nuclear Quadrupole Relaxation and Overhauser Effect

    • 19.4 NMR SPECTROSCOPY

      • 19.4.1 Pulsed Fourier Transform Method

      • 19.4.2 One-Dimensional NMR

      • 19.4.3 Two-Dimensional NMR

    • 19.5 MAGNETIC RESONANCE IMAGING

    • 19.6 NMR SPECTRA OF MACROMOLECULES

      • 19.6.1 Poly(methyl methacrylate)

      • 19.6.2 Polypropylene

      • 19.6.3 Deuterium NMR Spectra of Chain Mobility in Polyethylene

      • 19.6.4 Two-Dimensional NMR Spectra of Poly-c-benzyl-L-glutamate

    • 19.7 ADVANCES IN NMR SINCE 1994

      • 19.7.1 Apparatus

      • 19.7.2 Techniques

    • 19.8 TWO EXAMPLES OF PROTEIN NMR

      • 19.8.1 Membrane Protein

      • 19.8.2 A Brain Protein: Prion

    • REFERENCES

    • PROBLEMS

  • 20 X-RAY CRYSTALLOGRAPHY

    • 20.1 X-RAY DIFFRACTION

    • 20.2 CRYSTALS

      • 20.2.1 Miller Indices, hkl

      • 20.2.2 Unit Cells or Crystal Systems

      • 20.2.3 Crystal Drawing

    • 20.3 SYMMETRY IN CRYSTALS

      • 20.3.1 Bravais Lattices

      • 20.3.2 Point Group and Space Group

    • 20.4 FOURIER SYNTHESIS

      • 20.4.1 Atomic Scattering Factor

      • 20.4.2 Structure Factor

      • 20.4.3 Fourier Synthesis of Electron Density

    • 20.5 PHASE PROBLEM

      • 20.5.1 Patterson Synthesis

      • 20.5.2 Direct Method (Karle–Hauptmann Approach)

    • 20.6 REFINEMENT

    • 20.7 CRYSTAL STRUCTURE OF MACROMOLECULES

      • 20.7.1 Synthetic Polymers

      • 20.7.2 Proteins

      • 20.7.3 DNA

    • 20.8 ADVANCES IN X-RAY CRYSTALLOGRAPHY SINCE 1994

      • 20.8.1 X-Ray Sources

      • 20.8.2 New Instruments

      • 20.8.3 Structure of Proteins

      • 20.8.4 Protein Examples

    • APPENDIX NEUTRON DIFFRACTION

    • REFERENCES

    • PROBLEMS

  • AUTHOR INDEX

  • SUBJECT INDEX

  • COLOR PLATES

    • FIGURE 5.9

    • FIGURE 18.6

    • FIGURE 18.7

    • FIGURE 18.9

    • FIGURE 18.10

    • FIGURE 18.14 Pro

    • FIGURE 19.18

    • FIGURE 19.19

    • FIGURE 20.21

    • FIGURE 20.22A

    • FIGURE 20.22B

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Nội dung

[...]... FIRST EDITION Physical chemistry of macromolecules is a course that is frequently offered in the biochemistry curriculum of a college or university Occasionally, it is also offered in the chemistry curriculum When it is offered in the biochemistry curriculum, the subject matter is usually limited to biological topics and is identical to biophysical chemistry When it is offered in the chemistry curriculum,... which chapters belong to biophysical chemistry and which chapters belong to polymer chemistry Roughly speaking, unit 1 may be considered to consist of the core materials of polymer chemistry Unit 2 contains materials belonging both to polymer chemistry and biophysical chemistry Unit 3, which covers the structure of macromolecules and their separations, is relatively independent of units 1 and 2 These materials... of diffusion is often complementary to knowledge of sedimentation and vice versa It should be pointed out that all the chapters in unit 2 (Chapters 6 through 12) so far deal with methods for determining molecular weight and the configuration of macromolecules They are standard chapters for both a course of polymer chemistry and a course of biophysical chemistry Chapters 13 through 17 describe some of. .. electrophoresis In conclusion, the organization of this book covers the basic ideas and issues of the physical chemistry of macromolecules including molecular structure, physical properties, and modern experimental techniques Mathematical equations are used frequently in this book, because they are a part of physical chemistry We use mathematics as a language in a way that is not different from our other... and macromolecules are different entities, many of the same laws that govern colloids also govern macromolecules For this reason, the study of the physical chemistry of macromolecules often extends to the study of colloids Although the main topic of this book is macromolecules, we are also interested in colloids Since colloids were known first, we will describe them first 1.1 COLLOIDS When small molecules... mg) The surface of the micelle liposome is similar to that of membrane lipids; it does no harm to the body when administered 1.2 MACROMOLECULES The physical properties of macromolecules, such as sedimentation, diffusion, and light scattering, are very similar to those of colloids For generations macromolecules have been regarded as associated colloids or lyophilic colloidal systems But macromolecules. .. X-Ray Crystallography Since the completion of the first edition in 1994, important developments have been going on in many fields of physical chemistry of macromolecules As a result, two new disciplines have emerged: materials science and structural biology The traditional field of polymers, even though already enlarged, is to be included in the bigger field of materials science Together with glasses,... note of thanks goes to Mr Christopher Frank who drew the figures in chapter 11 and provided comments xxiv PREFACE TO THE FIRST EDITION on the appendix, and to Mr Anthony DeLuca and Professor Andrew Taslitz, for improving portions of this writing Most parts of the manuscript were painstakingly typed by Ms Terry Cognard For many years, students and faculty members of the Department of Chemistry of Liberal... polarization of a molecule, and so on The English letter c can represent the concentration of a solution (for example, g/ mL, mol/L), the unit of coordinates (such as a, b, c), and so on To avoid confusion, some authors use different symbols to represent different kinds of quantities and provide a glossary at the end of the book The advantage of changing standard notation is the maintenance of consistency... binding of small molecules to macromolecules The second part, electrophoresis, describes the classical theory of ionic mobility and various types of modern techniques used for the separation and characterization of biological materials Chapter 17 ends with an additional section, field-flow fractionation, which describes the combined methods of HPLC and electrophoresis In conclusion, the organization of this .

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