4.2.3
Non-ionic Amphipols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 165
4.2.3.1 THAM-Based Non-ionic Amphipols . . . . . . . . . . . . . . . . . . . 165
4.2.3.2 Glucose-Based Non-ionic Amphipols (NAPols) . . . . . . . . . . . 167
4.2.3.3 NVoy ¼ NV10 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 169
4.3
Self-Association Behavior of Amphipols in Aqueous Solutions . . . . . . . . . . . . . 169
4.3.1
Formation, Structure, and Dynamics of A8-35 Particles . . . . . . . . . . . . . 170
4.3.1.1 Critical Association Concentration . . . . . . . . . . . . . . . . . . . . 170
4.3.1.2 The Size, Shape, and Organization of A8-35 Particles . . . . . . . 176
4.3.1.2.1 Mass and Dispersity of Individual A8-35
Molecules . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 176
4.3.1.2.2 Homogeneity, Mass, and Size of A8-35
Particles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 178
4.3.1.2.3 Shape and Internal Organization of A8-35
Particles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 183
4.3.1.2.4 Dynamics of A8-35 Particles . . . . . . . . . . . . . . . . . 187
4.3.1.2.5 Data Pertaining to the Phase Diagram
of A8-35 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 191
4.3.2
Solution Properties of Other Amphipols . . . . . . . . . . . . . . . . . . . . . . . . 192
4.4
Labeled and Functionalized Amphipols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 198
4.4.1
Synthesis of Labeled or Tagged Derivatives of A8-35 and A8-75 . . . . . 198
4.4.2
Solution Behavior of Labeled or Tagged Derivatives of A8-35
and A8-75 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 203
4.5
Protocol 4.1: Synthesis of A8-35 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 205
4.5.1
Preparation and Characterization of the PAA Precursor . . . . . . . . . . . . . 205
4.5.2
Hydrophobic Modification of the PAA Precursor . . . . . . . . . . . . . . . . . 207
4.5.3
Purification of A8-35 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 208
4.5.4
Determination of the Chemical Composition of the Final Product . . . . . 208
4.6
Annexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 210
4.6.1
Annex 4.1. Determining and Expressing the Average Mass
and Dispersity of Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 210
4.6.1.1 The Origin of Dispersity . . . . . . . . . . . . . . . . . . . . . . . . . . . . 210
4.6.1.2 How Can Size Dispersity Be Limited? . . . . . . . . . . . . . . . . . . 211
4.6.1.3 Expressing the Average Mass and Dispersity of Polymers . . . . 213
4.6.1.4 Determining the Average Mass and Dispersity of Polymers . . . 214
4.6.1.5 Calibration of Size Exclusion Chromatography Columns . . . . . 214
4.6.2
Annex 4.2. Kinetics of Conventional Radical Polymerization
and Origin of Size Dispersity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 216
4.6.3
Annex 4.3. Expression of the Instantaneous and Cumulative
Average Degree of Polymerization in Conventional Radical
Polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 217
4.6.4
Annex 4.4. How to Control the Size of Polymers Obtained
by Radical Polymerization? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 218
4.6.4.1 Telomerization (Chain Transfer) . . . . . . . . . . . . . . . . . . . . . . 218
4.6.4.2 Controlled/Living Radical Polymerization (CRP) . . . . . . . . . . 219
4.6.5
Annex 4.5. Polymer Topology and How to Control It . . . . . . . . . . . . . . 222
4.6.5.1 Polymer Topology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 222
4.6.5.2 Polymer Composition (Microstructure) . . . . . . . . . . . . . . . . . . 223
Contents
xix
Non-ionic Amphipols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 165
4.2.3.1 THAM-Based Non-ionic Amphipols . . . . . . . . . . . . . . . . . . . 165
4.2.3.2 Glucose-Based Non-ionic Amphipols (NAPols) . . . . . . . . . . . 167
4.2.3.3 NVoy ¼ NV10 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 169
4.3
Self-Association Behavior of Amphipols in Aqueous Solutions . . . . . . . . . . . . . 169
4.3.1
Formation, Structure, and Dynamics of A8-35 Particles . . . . . . . . . . . . . 170
4.3.1.1 Critical Association Concentration . . . . . . . . . . . . . . . . . . . . 170
4.3.1.2 The Size, Shape, and Organization of A8-35 Particles . . . . . . . 176
4.3.1.2.1 Mass and Dispersity of Individual A8-35
Molecules . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 176
4.3.1.2.2 Homogeneity, Mass, and Size of A8-35
Particles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 178
4.3.1.2.3 Shape and Internal Organization of A8-35
Particles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 183
4.3.1.2.4 Dynamics of A8-35 Particles . . . . . . . . . . . . . . . . . 187
4.3.1.2.5 Data Pertaining to the Phase Diagram
of A8-35 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 191
4.3.2
Solution Properties of Other Amphipols . . . . . . . . . . . . . . . . . . . . . . . . 192
4.4
Labeled and Functionalized Amphipols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 198
4.4.1
Synthesis of Labeled or Tagged Derivatives of A8-35 and A8-75 . . . . . 198
4.4.2
Solution Behavior of Labeled or Tagged Derivatives of A8-35
and A8-75 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 203
4.5
Protocol 4.1: Synthesis of A8-35 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 205
4.5.1
Preparation and Characterization of the PAA Precursor . . . . . . . . . . . . . 205
4.5.2
Hydrophobic Modification of the PAA Precursor . . . . . . . . . . . . . . . . . 207
4.5.3
Purification of A8-35 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 208
4.5.4
Determination of the Chemical Composition of the Final Product . . . . . 208
4.6
Annexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 210
4.6.1
Annex 4.1. Determining and Expressing the Average Mass
and Dispersity of Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 210
4.6.1.1 The Origin of Dispersity . . . . . . . . . . . . . . . . . . . . . . . . . . . . 210
4.6.1.2 How Can Size Dispersity Be Limited? . . . . . . . . . . . . . . . . . . 211
4.6.1.3 Expressing the Average Mass and Dispersity of Polymers . . . . 213
4.6.1.4 Determining the Average Mass and Dispersity of Polymers . . . 214
4.6.1.5 Calibration of Size Exclusion Chromatography Columns . . . . . 214
4.6.2
Annex 4.2. Kinetics of Conventional Radical Polymerization
and Origin of Size Dispersity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 216
4.6.3
Annex 4.3. Expression of the Instantaneous and Cumulative
Average Degree of Polymerization in Conventional Radical
Polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 217
4.6.4
Annex 4.4. How to Control the Size of Polymers Obtained
by Radical Polymerization? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 218
4.6.4.1 Telomerization (Chain Transfer) . . . . . . . . . . . . . . . . . . . . . . 218
4.6.4.2 Controlled/Living Radical Polymerization (CRP) . . . . . . . . . . 219
4.6.5
Annex 4.5. Polymer Topology and How to Control It . . . . . . . . . . . . . . 222
4.6.5.1 Polymer Topology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 222
4.6.5.2 Polymer Composition (Microstructure) . . . . . . . . . . . . . . . . . . 223
Contents
xix