Macromolecules in solution:
Gespeichert in:
| 1. Verfasser: | |
|---|---|
| Format: | Buch |
| Sprache: | English |
| Veröffentlicht: |
New York
Wiley
1975
|
| Ausgabe: | 2. ed. |
| Schriftenreihe: | High polymers.
21. |
| Schlagworte: | |
| Online-Zugang: | Inhaltsverzeichnis |
| Beschreibung: | XVII, 749 S. Ill. u. graph. Darst. |
Internformat
MARC
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Datensatz im Suchindex
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| adam_text | MACROMOLECULES
IN SOLUTION
Second Edition
HERBERT IMORAWETZL
Polytechnic Institute of New York
Brooklyn, New York
A WILEY-INTERSCIENCE PUBLICATION
JOHN WILEY amp; SONS, INC
New York • London • Sydney • Toronto
CONTENTS
Glossary of Symbols xv
I General Considerations 1
A Comparison of Methods Used for the Study of Small and Large
Molecules 2
1 Methods More Applicable to Small than to Large Molecules 3
2 Methods Specifically Suited to Macromolecules 5
3 Motivation Characteristic of the Study of Macromolecules 7
B Distribution Functions of Chain Lengths and Composition 11
1 The “Most Probable Distribution” of Chain Lengths 12
2 Chain Length Distribution in Vinyl Polymerization Terminated
by Radical Recombination 15
3 The Poisson Distribution 16
4 Molecular Weight Averages 19
5 Real Distributions and Generalized Molecular Weight
Distribution Functions 21
6 The Distribution of Copolymer Composition 23
C Relation of the Study of Macromolecules in Solution and in Bulk 24
1 Molecular Weight and Polydispersity 25
2 The Shape of Macromolecules 27
3 Relation of Solution Properties to Technologically Important
Characteristics 30
II The Solubility of Marcomolecules 33
A rormation of Solutions from Species of Low Molecular Weight 33
1 Thermodynamic Considerations 33
2 The Ideal Solution 37
3 Regular Solutions 38
4 Estimation of the Heat of Mixing from Cohesive Energy Densities 39^
5 Deviation from Ideality in Real Solutions of Small Molecules 42
6 The Solvent Properties of Water 46
7 Phase Equilibria 50
8 Solubility of Crystalline Solids 53
IX
X
B Binary Systems Containing Macromolecules 54
1 Deviation of Polymer Solutions from Ideal Solution Behavior 54
2 Phase Equilibrium in Systems of a Polymer and Poor Solvents 61
3 The Consolute Point 62
4 Anisotropic Solutions of Macromolecules 67
5 Some Typical Examples of Polymer-Solvent Interaction 69
6 The Solubility of Crystalline Chain Polymers 75
7 Thermally Reversible Gelation 78
8 Application of the Concept of “Solution” to Extremely
Large Molecules 81
C Three-Component and Multicomponent Systems Containing
Macromolecules 82
1 The Effect of Polydispersity on Polymer Solubility 82
2 Solubility of Polymers in Mixed Organic Solvents 83
3 Solubility in Aqueous Electrolyte Solutions 85
4 Incompatibility of Polymer Solutions 90
5 Emulsions of Systems Containing Two Polymeric Solutes 91
6 Ternary Systems with Strongly Interacting Polymers 93
III Configuration and Conformation of Chain Molecules 96
A The Stereoisomerism of Chain Molecules 97
B Geometry of Flexible Chains 104
1 The Flexibility of Molecular Chains 104
2 Statistics of Random Flight Chains 119
3 Model Chains with Restricted Flexibility 124
4 Random Flight Models of Branched Chain Molecules 126
5 The “Unperturbed Chain Dimensions” 128
6 Effect of Long-Range Interactions on the Shape of Flexible
Chains 133
7 Conformation of Copolymers 140
C Specific Conformations 141
1 Ordered Conformations of Polypeptide Chains 141
2 The Coiled-Coil Structure of Collagen and Myosin 153
3 Ordered Structures in Solutions of Nucleic Acids and Synthetic
Polynucleotides 155
4 Polyisocyanates 166
5 Theoretical Treatments of Helix-Coil Transitions 167
6 The Conformation of Globular Protein Molecules 170
IV Equilibrium Properties of Dilute Solutions 182
A The Colligative Properties 182
1 Raoult’s Law as a Limiting Law 182
2 Relation of Solvent Activity to Measurable Quantities 183
3 The Scope of the Methods 185
4 Deviations from Raoult’s Law in Dilute Solutions 187
5 Osmometry with Semipermeable and with Partially Selective v
Membranes 194
XI
6 Surfaces of Macromolecular Solutions 197
7 Distribution of Macromolecules between a Solution and a Gel
Phase 200
B Equilibrium Centrifugation 201
1 Methods for Determining Solute Distribution in the
Ultracentrifuge Cell 202
2 Ultracentrifuge Equilibrium in a Two-Component System 203
3 Equilibrium Centrifugation of a Polydisperse Polymer Solution 205
4 Time Required for Approach to Equilibrium 208
5 Equilibrium Sedimentation in a Density Gradient 209
V Spectroscopy, Optical Activity, and the Scattering of Light
and X-Rays 217
A Absorption Spectroscopy 219
1 Ultraviolet Spectra 219
2 Infrared Spectra 226
3 Raman Spectra 228
4 NMR Spectra 229
5 Fluorescence Spectra 239
B Optical Activity and Circular Dichroism 242
1 General Considerations 242
2 Synthetic Polypeptides and Proteins 249
3 Polynucleotides 260
4 Vinyl Polymers and Polyethers 260
C Light Scattering 265
1 Scattering by Gases 265
2 Scattering from Solutions of Molecules Much Smaller than the
Wavelength of Light 267
3 Estimation of the Size and Shape of Macromolecules from the
Angular Dependence of the Scattered Light Intensity 271
4 Light Scattering from Solutions in Mixed Solvent Media 280
5 Light Scattering from Solutions of Polymers with a Variable
Chemical Composition 282
D X-Ray Scattering 283
VI Frictional Properties of Dissolved Macromolecules 290
A Linear Translation 129
1 The Frictional Coefficient of Rigid Particles 291
2 Frictional Coefficients of Chain Molecules 293
3 Diffusion 295
4 Sedimentation Velocity 299
5 Mobility of Small Molecules and Ions in Polymer Solutions 305
B Rotary Diffusion 306
1 Rotary Diffusion Coefficient of Rigid Particles 306
2 Rotary Diffusion of Chain Molecules 308
3 Flow Birefringence 308
4 Disorientation of Oriented Solutions 316
5 Depolarization of Fluorescence 318
l
Xll CONTENTS
C Solution Viscosity 321
1 Viscosity of Solutions of Rigid Molecules 321
2 Viscosity of Solutions of Flexible Chain Molecules 324
3 Interpretation of Intrinsic Viscosity in Conjunction with Other
Solution Properties 335
4 Viscoelasticity of Dilute Solutions 338
5 Drag Reduction in Turbulent Flow 340
D Shear Degradation 342
VII Polyelectrolytes 344
A The Expansion of Flexible Polyions 348
1 Theories of Poly ion Expansion 350
2 Experimental Evidence for Polyion Expansion 358
B The Distribution of Counterions 363
C Thermodynamic Properties 369
1 Ionic Activity Coefficients 369
2 Ionization Equilibria 375
D Transport Properties 387
1 Electrophoresis 387
2 Conductance and Dielectric Increment 391
3 Diffusion and Sedimentation 393
VIII Molecular Association 397
A Association of Macromolecules with Low Molecular Weight Species 399
1 Association of Small Molecules and Ions with Flexible Chain
Molecules 399
2 Binding of Small Molecules and Ions to Globular Proteins 407
B Molecular Aggregation of Macromolecules 414
1 Aggregation of Flexible Chain Molecules 414
2 Association of Globular Proteins 418
3 The Antigen-Antibody Reaction 428
4 Nucleoproteins and Their Analogs 434
IX Chemical Kinetics in Macromolecular Solutions 439
A Rates of Conformational Transitions in Dissolved Macromolecules ___440
1 Rates of Conformational Transitions in Randomly Coiled Chains 440
2 Kinetics of Transformations Involving Helical Conformations ___ 442
3 Rates of Conformational Transitions in Globular Proteins 447
B Reactions of Polymers with Small Molecules and Ions 449
1 Isotope Exchange 449
2 Effects of Conformation of Globular Proteins on Their
Reactivity 453
3 Reactions of Flexible Chain Molecules with Low Molecular
Weight Species 457
C Intramolecular Interaction Effects on Polymer Reactivity 466
1 Neighboring Group Effects on the Reactivity of Chain
Molecules 466
CONTENTS Xlll
2 Statistical Analysis of the Kinetic Pattern 472
3 Effects of Non-neighboring Groups 475
D Reactions of Two Low Molecular Weight Species in the Presence of
Polyions 478
E Chemical Interaction between Groups Attached to Different Flexible
Chain Molecules 485
References 489
Index 537
i
MACROMOLECULES
IN SOLUTION
Second Edition
HERBERT MORA WETZ
Polytechnic Institute of New York
Brooklyn, New York
A WILEY-INTERSCIENCE PUBLICATION
JOHN WILEY amp; SONS, INC
New York • London • Sydney • Toronto
CONTENTS
Glossary of Symbols xv
I General Considerations 1
A Comparison of Methods Used for the Study of Small and Large
Molecules 2
1 Methods More Applicable to Small than to Large Molecules 3
2 Methods Specifically Suited to Macromolecules 5
3 Motivation Characteristic of the Study of Macromolecules 7
B Distribution Functions of Chain Lengths and Composition 11
1 The “Most Probable Distribution” of Chain Lengths 12
2 Chain Length Distribution in Vinyl Polymerization Terminated
by Radical Recombination 15
3 The Poisson Distribution 16
4 Molecular Weight Averages 19
5 Real Distributions and Generalized Molecular Weight
Distribution Functions 21
6 The Distribution of Copolymer Composition 23
C Relation of the Study of Macromolecules in Solution and in Bulk 24
1 Molecular Weight and Polydispersity 25
2 The Shape of Macromolecules 27
3 Relation of Solution Properties to Technologically Important
Characteristics 30
II The Solubility of Marcomolecules 33
A formation of Solutions from Species of Low Molecular Weight 33
1 Thermodynamic Considerations 33
2 The Ideal Solution 37
3 Regular Solutions 38
4 Estimation of the Heat of Mixing from Cohesive Energy Densities 39
5 Deviation from Ideality in Real Solutions of Small Molecules 42
6 The Solvent Properties of Water 46
7 Phase Equilibria 50
8 Solubility of Crystalline Solids 53
IX
X
B Binary Systems Containing Macromolecules 54
1 Deviation of Polymer Solutions from Ideal Solution Behavior 54
2 Phase Equilibrium in Systems of a Polymer and Poor Solvents 61
3 The Consolute Point 62
4 Anisotropic Solutions of Macromolecules 67
5 Some Typical Examples of Polymer-Solvent Interaction 69
6 The Solubility of Crystalline Chain Polymers 75
7 Thermally Reversible Gelation 78
8 Application of the Concept of “Solution” to Extremely
Large Molecules 81
C Three-Component and Multicomponent Systems Containing
Macromolecules 82
1 The Effect of Polydispersity on Polymer Solubility 82
2 Solubility of Polymers in Mixed Organic Solvents 83
3 Solubility in Aqueous Electrolyte Solutions 85
4 Incompatibility of Polymer Solutions 90
5 Emulsions of Systems Containing Two Polymeric Solutes 91
6 Ternary Systems with Strongly Interacting Polymers 93
III Configuration and Conformation of Chain Molecules 96
A The Stereoisomerism of Chain Molecules 97
B Geometry of Flexible Chains 104
1 The Flexibility of Molecular Chains 104
2 Statistics of Random Flight Chains 119
3 Model Chains with Restricted Flexibility 124
4 Random Flight Models of Branched Chain Molecules 126
5 The “Unperturbed Chain Dimensions” 128
6 Effect of Long-Range Interactions on the Shape of Flexible
Chains 133
7 Conformation of Copolymers 140
C Specific Conformations 141
1 Ordered Conformations of Polypeptide Chains 141
2 The Coiled-Coil Structure of Collagen and Myosin 153
3 Ordered Structures in Solutions of Nucleic Acids and Synthetic
Polynucleotides 155
4 Polyisocyanates 166
5 Theoretical Treatments of Helix-Coil Transitions 167
6 The Conformation of Globular Protein Molecules 170
IV Equilibrium Properties of Dilute Solutions 182
A The Colligative Properties 182
1 Raoult’s Law as a Limiting Law 182
2 Relation of Solvent Activity to Measurable Quantities 183
3 The Scope of the Methods 185
4 Deviations from Raoult’s Law in Dilute Solutions 187
5 Osmometry with Semipermeable and with Partially Selective
Membranes 194
XI
6 Surfaces of Macromolecular Solutions 197
7 Distribution of Macromolecules between a Solution and a Gel
Phase 200
B Equilibrium Centrifugation 201
1 Methods for Determining Solute Distribution in the
Ultracentrifuge Cell 202
2 Ultracentrifuge Equilibrium in a Two-Component System 203
3 Equilibrium Centrifugation of a Polydisperse Polymer Solution 205
4 Time Required for Approach to Equilibrium 208
5 Equilibrium Sedimentation in a Density Gradient 209
V Spectroscopy, Optical Activity, and the Scattering of Light
and X-Rays 217
A Absorption Spectroscopy 219
1 Ultraviolet Spectra 219
2 Infrared Spectra 226
3 Raman Spectra 228
4 NMR Spectra 229
5 Fluorescence Spectra 239
B Optical Activity and Circular Dichroism 242
1 General Considerations 242
2 Synthetic Polypeptides and Proteins 249
3 Polynucleotides 260
4 Vinyl Polymers and Polyethers 260
C Light Scattering 265
1 Scattering by Gases 265
2 Scattering from Solutions of Molecules Much Smaller than the
Wavelength of Light 267
3 Estimation of the Size and Shape of Macromolecules from the
Angular Dependence of the Scattered Light Intensity 271
4 Light Scattering from Solutions in Mixed Solvent Media 280
5 Light Scattering from Solutions of Polymers with a Variable
Chemical Composition 282
D X-Ray Scattering 283
VI Frictional Properties of Dissolved Macromolecules 290
A Linear Translation 129
1 The Frictional Coefficient of Rigid Particles 291
2 Frictional Coefficients of Chain Molecules 293
3 Diffusion 295
4 Sedimentation Velocity 299
5 Mobility of Small Molecules and Ions in Polymer Solutions 305
B Rotary Diffusion 306
1 Rotary Diffusion Coefficient of Rigid Particles 306
2 Rotary Diffusion of Chain Molecules 308
3 Flow Birefringence 308
4 Disorientation of Oriented Solutions 316
5 Depolarization of Fluorescence 318
Xll CONTENTS
C Solution Viscosity 321
1 Viscosity of Solutions of Rigid Molecules 321
2 Viscosity of Solutions of Flexible Chain Molecules 324
3 Interpretation of Intrinsic Viscosity in Conjunction with Other
Solution Properties 335
4 Viscoelasticity of Dilute Solutions 338
5 Drag Reduction in Turbulent Flow 340
D Shear Degradation 342
VII Polyelectrolytes 344
A The Expansion of Flexible Polyions 348
1 Theories of Poly ion Expansion 350
2 Experimental Evidence for Polyion Expansion 358
B The Distribution of Counterions 363
C Thermodynamic Properties 369
1 Ionic Activity Coefficients 369
2 Ionization Equilibria 375
D Transport Properties 387
1 Electrophoresis 387
2 Conductance and Dielectric Increment 391
3 Diffusion and Sedimentation 393
VIII Molecular Association 397
A Association of Macromolecules with Low Molecular Weight Species___399
1 Association of Small Molecules and Ions with Flexible Chain
Molecules 399
2 Binding of Small Molecules and Ions to Globular Proteins 407
B Molecular Aggregation of Macromolecules 414
1 Aggregation of Flexible Chain Molecules 414
2 Association of Globular Proteins 418
3 The Antigen-Antibody Reaction 428
4 Nucleoproteins and Their Analogs 434
IX Chemical Kinetics in Macromolecular Solutions 439
A Rates of Conformational Transitions in Dissolved Macromolecules 440
1 Rates of Conformational Transitions in Randomly Coiled Chains 440
2 Kinetics of Transformations Involving Helical Conformations 442
3 Rates of Conformational Transitions in Globular Proteins 447
B Reactions of Polymers with Small Molecules and Ions 449
1 Isotope Exchange 449
2 Effects of Conformation of Globular Proteins on Their
Reactivity 453
3 Reactions of Flexible Chain Molecules with Low Molecular
Weight Species 457
C Intramolecular Interaction Effects on Polymer Reactivity 466
1 Neighboring Group Effects on the Reactivity of Chain
Molecules 466
|
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| id | DE-604.BV001971731 |
| illustrated | Illustrated |
| indexdate | 2024-07-09T15:38:09Z |
| institution | BVB |
| language | English |
| oai_aleph_id | oai:aleph.bib-bvb.de:BVB01-001285998 |
| oclc_num | 630800918 |
| open_access_boolean | |
| owner | DE-91G DE-BY-TUM DE-355 DE-BY-UBR DE-83 DE-188 |
| owner_facet | DE-91G DE-BY-TUM DE-355 DE-BY-UBR DE-83 DE-188 |
| physical | XVII, 749 S. Ill. u. graph. Darst. |
| psigel | TUB-nvmb |
| publishDate | 1975 |
| publishDateSearch | 1975 |
| publishDateSort | 1975 |
| publisher | Wiley |
| record_format | marc |
| series | High polymers. |
| series2 | High polymers. A Wiley-Interscience publ. |
| spelling | Morawetz, Herbert Verfasser aut Macromolecules in solution 2. ed. New York Wiley 1975 XVII, 749 S. Ill. u. graph. Darst. txt rdacontent n rdamedia nc rdacarrier High polymers. 21. A Wiley-Interscience publ. Lösung Chemie (DE-588)4036159-7 gnd rswk-swf Polymerlösung (DE-588)4175242-9 gnd rswk-swf Makromolekül (DE-588)4037172-4 gnd rswk-swf Makromolekül (DE-588)4037172-4 s Lösung Chemie (DE-588)4036159-7 s DE-604 Polymerlösung (DE-588)4175242-9 s High polymers. 21. (DE-604)BV001888976 21. HEBIS Datenaustausch application/pdf http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=001285998&sequence=000001&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA Inhaltsverzeichnis |
| spellingShingle | Morawetz, Herbert Macromolecules in solution High polymers. Lösung Chemie (DE-588)4036159-7 gnd Polymerlösung (DE-588)4175242-9 gnd Makromolekül (DE-588)4037172-4 gnd |
| subject_GND | (DE-588)4036159-7 (DE-588)4175242-9 (DE-588)4037172-4 |
| title | Macromolecules in solution |
| title_auth | Macromolecules in solution |
| title_exact_search | Macromolecules in solution |
| title_full | Macromolecules in solution |
| title_fullStr | Macromolecules in solution |
| title_full_unstemmed | Macromolecules in solution |
| title_short | Macromolecules in solution |
| title_sort | macromolecules in solution |
| topic | Lösung Chemie (DE-588)4036159-7 gnd Polymerlösung (DE-588)4175242-9 gnd Makromolekül (DE-588)4037172-4 gnd |
| topic_facet | Lösung Chemie Polymerlösung Makromolekül |
| url | http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=001285998&sequence=000001&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA |
| volume_link | (DE-604)BV001888976 |
| work_keys_str_mv | AT morawetzherbert macromoleculesinsolution |