Modern Biopolymer Science: Bridging the Divide between Fundamental Treatise and Industrial Application

Cover Page
......Page 1
Copyright 
......Page 2
Contributors
......Page 3
Preface
......Page 5
1.1.1.2 
What is a Gel?......Page 7
1.1.1.3 
‘Viscosifiers’......Page 8
1.1.2.2 
Structural Implications......Page 9
1.2.1.3 
U-tube Rheometer......Page 10
1.2.2.1 
Mechanical Spectroscopy......Page 11
1.2.2.1.1 
Controlled Strain Versus Controlled Stress......Page 12
1.2.2.2.2 
Biopolymer Gels......Page 13
1.2.2.4.1 
The Kinetic Gelation Experiment......Page 14
1.2.2.4.2 
Gelation Time Measurement......Page 15
1.2.2.4.4 
Chambon-Winter Method and Applicability in Biopolymer Self-Assembly......Page 16
1.2.2.4.6 
Ginf and the Equilibrium Modulus......Page 17
1.3.1 
Critical Gel Concentration......Page 18
1.3.3.1 
Flory-Stockmayer (FS) Model......Page 19
1.3.4 Random Branching in Solution......Page 20
1.3.4.1 Random Branching and Experiment......Page 24
1.3.5 Branching Models and Phase Separation......Page 27
1.3.6 Exponents and Critical Exponents......Page 28
1.3.7 Fractal Models......Page 29
1.4 Conclusions......Page 30
References......Page 31
2.1
Introduction......Page 34
2.2.1
Introduction......Page 35
2.2.2
Percolation Description of Gel Networks......Page 40
2.2.3
Linear Branch Description of Gel Networks......Page 44
2.2.4
Colloidal Cluster Description of Gel Networks......Page 45
2.2.5
Phase Separation and Structural Transitions in Relation to Percolation, Aggregation and Gelation......Page 47
2.2.6
Arrested States and Gelation......Page 55
2.2.7
Modeling Gel Networks and their Rheological Behavior: Conclusions......Page 56
2.3.1
Introduction......Page 63
2.3.2
Denaturation......Page 64
2.3.3
Refolding......Page 66
2.3.4
Enzymatic Hydrolysis......Page 67
2.3.6
General Model for Denaturation and Aggregation......Page 68
2.4
Gel structure type......Page 70
2.4.2
Fibers......Page 72
2.5.1
Introduction......Page 75
2.5.2
Oral Processing......Page 76
2.5.3
Large Strain and Fracture Properties......Page 77
2.5.4
Microstructure......Page 78
2.5.5
Sensory Analysis of Protein Gels......Page 79
2.6
Concluding remarks and future challenges......Page 83
References......Page 84
3.1.1
Discovery and Purpose......Page 97
3.1.3.1
AFGP......Page 98
3.1.3.2
AFP I......Page 99
3.1.3.5
Insect and Plant AFPs......Page 100
3.1.3.5.2
Daucus Carota (Worrall etnbspal., 1998)......Page 101
3.2.1
Thermal Hysteresis......Page 102
3.2.2
Recrystallization Inhibition......Page 103
3.2.3.1
Crystallographic Principles......Page 105
3.2.3.2
Antifreeze Protein-Binding Sites......Page 106
3.2.3.3
Native and Synthetic AFP I Ice Binding......Page 108
3.2.3.3.1
The AFP I Ice Binding Motif......Page 109
3.2.3.4
AFGP Ice Binding......Page 110
3.2.3.5
AFP III Ice Binding......Page 111
3.2.3.6
Plant AFPs......Page 112
3.2.4.1
Ice Crystal Growth: Principles......Page 113
3.2.4.3
Ice Crystal Growth in the Presence of AFPs......Page 115
3.2.4.4
The Nanoliter Osmometer Method......Page 116
3.2.4.5.1
 AFP Type I......Page 117
3.2.4.5.2
AFP Type III......Page 118
3.2.4.5.4
AFP II......Page 119
3.2.4.5.6
Plant AFP Ice Crystal Shapes......Page 120
3.2.4.5.7
Summary......Page 121
3.3.1
The Adsorption-Inhibition Models......Page 122
3.3.2
The Kelvin Effect......Page 123
3.3.4
Hall and Lips Model of AFP Action......Page 124
3.4
Applications of AFP......Page 125
References......Page 128
4.2
Emulsion Science And Technology Terminology......Page 133
4.3.2
Droplet Size Distribution......Page 135
4.3.4
Droplet Interfacial Properties......Page 136
4.3.5
Droplet-Droplet Interactions......Page 137
4.4.1.1
Pre-Homogenization......Page 138
4.4.1.3
Post-Homogenization......Page 139
4.4.2
Physical Principles of Homogenization......Page 140
4.5
Emulsion Stability......Page 141
Electrostatic Interactions......Page 142
Hydrophobic Interactions......Page 143
Overall Interaction Potential......Page 144
Gravitational Separation: Creaming and Sedimentation......Page 145
Flocculation and Coalescence......Page 146
Partial Coalescence......Page 147
Ostwald Ripening......Page 148
Chemical and Biochemical Stability......Page 149
4.6.2
Modeling Emulsion Rheology......Page 150
4.6.3.1
Continuous Phase Rheology......Page 151
4.6.3.4
Droplet Size......Page 152
4.6.5
Mathematical Modeling of Emulsion Color......Page 153
4.6.7
Flavor......Page 154
Flavor Partitioning......Page 155
4.7
Biopolymer Emulsifiers......Page 156
4.7.1
Interfacial Activity and Emulsion Stabilization......Page 157
4.7.3
Proteins......Page 159
4.7.3.4
Plant Proteins......Page 160
4.7.4.2
Modified Starches......Page 161
4.7.6
Selection of an Appropriate Emulsifier......Page 162
4.8
Biopolymer Texture Modifiers......Page 164
References......Page 167
5.1.1
Possible Outcomes of Mixing Two Different Biopolymers......Page 171
5.1.4
Phase Separation in Solutions and Gels......Page 172
5.1.5
Polymer Blending Laws......Page 173
5.2
Applicability of Polymer Blending Laws tonbspBiphasic Networks......Page 174
5.3.1
Segregation in the Solution State......Page 176
5.3.2
Partition of Polymers and Solvent in Biphasic Co-Gels......Page 177
5.4.1
 Experimental Procedure......Page 178
5.4.2
Phase Structure......Page 180
5.4.3
Analysis of Co-Gel Moduli by Polymer Blending Laws......Page 181
5.5.1
Experimental Procedure......Page 182
5.5.2
Starch Networks......Page 183
5.5.3
Phase Structure......Page 184
5.5.4
Blending Law Analysis......Page 185
5.6.1
Electrostatic Association in Mixtures of Gelatin with Pectin......Page 186
5.6.2
Ordered Association of Xanthan with Konjac Glucomannan (KGM)......Page 188
5.7.1
Effect of Soluble Biopolymers on Self-Association of Calcium Pectinate......Page 193
5.7.2
Effect of Guar Gum on Thermal Gelation of WPI......Page 195
5.7.4
Effect of Soluble Biopolymers on Gelation of Gelatin......Page 196
5.8.1
Effect of Soluble Biopolymers on Gelation From Single-Phase Mixtures......Page 197
References......Page 198
6.1.2
Gelation Processes (Time and Length Scales)......Page 203
6.1.4
General Considerations and Thermodynamic Aspects of Phase Separation......Page 204
6.1.5
Phase-Diagrams......Page 205
6.1.6
Mechanisms of Demixing......Page 206
6.2
Fluid/Sheared Gels......Page 207
6.3.1
Interfacial Tension......Page 214
6.3.3
Phase Inversion......Page 215
6.4 
Processing Inside People......Page 216
6.4.1
Processing in the Mouth......Page 217
6.4.2
Processing in the Stomach......Page 220
6.4.3
Processing in the Small Intestine......Page 223
6.5
The Future......Page 224
References......Page 225
7.1.1
Fat, Calories and Healthful Diet......Page 229
7.1.2
Textural and Mouthfeel Implications of Fat/Protein Reduction......Page 230
7.2.1
Kinetic Influences on the State of Phase Separation in Gels......Page 231
7.2.2
Tangible Evidence of Non-Interacting Phase-Separated Gels......Page 234
7.2.3
Mechanical Measurements as an Empirical Indicator of Phase-Separation Patterns in Binary Gels......Page 236
7.3 
Utilization Of Reaction Kinetics To Identify Phase-Separation Phenomena In Biopolymer Mixtures......Page 239
7.4.1
Blending Laws for Two-Phase, Synthetic Polymer Systems......Page 241
7.4.2 
Addressing the Issue of Dynamic Solvent Partition Between Phases in Biological Mixtures......Page 242
7.4.3
Refining the Blending-Law Analysis: Effect of the  Shape of the Filler......Page 244
7.5.1
Experimental Observations  Across the Range of Solids for Industrial Formulations......Page 246
7.5.2
Structural Basis for the Mechanistic Understanding of the Transformation from Low- to High-Solid Biomaterials......Page 247
7.5.3
Changing Viscoelasticity as a Function of Increasing Levels of Co-Solute in Biopolymer Mixtures......Page 248
7.5.4
Quantitative Explorations of the Structural Properties in Biopolymer Mixtures at High Levels of Co-Solute......Page 249
7.6
Molecular Dynamics Of Bioactive Compounds In A High-Solids Carbohydrate Matrix......Page 252
7.7
Structural Properties Of Non-Aqueous Systems Used In Controlled Topical Delivery......Page 255
7.8 
Concluding Remarks......Page 257
References......Page 258
8.2 
Glass transition......Page 265
8.3 
Glass formation......Page 269
8.4 
Determination of glass transition......Page 270
8.5 
Water plasticization and plasticizers......Page 271
8.7 
Mechanical properties and relaxations......Page 273
8.10 
Stickiness and caking......Page 275
8.11 
Glass transitions innbspfrozen foods......Page 276
8.13 
State diagrams and stability......Page 277
References......Page 279
9.1 Carbohydrate Phase Behavior in the Prediction of Food and Pharmaceutical Stability......Page 281
9.2 Effects of Water on the Structure of Carbohydrate Glasses......Page 283
9.3 Molecular Packing in Glassy Carbohydrates......Page 285
9.4 Structural Aspects ofnbspthe Aging of Carbohydrate Glasses......Page 288
9.5 Dynamic Properties Close to the Glass Transition......Page 289
9.6 Technological Implications......Page 291
References......Page 296
10.2 Mechanisms of Film Formation......Page 298
10.3 Obtaining a Well-Matched Coating......Page 301
10.4 Film-Application Stages and Methods for Testing Films......Page 302
10.5 Selecting Biopolymers for Specific Applications......Page 303
10.6.1 Packaging Materials Fit for Human Consumption......Page 304
10.6.2 Inclusion of Food Additives within Edible Coatings......Page 306
10.6.3 Meat, Seafood and Fish Coatings......Page 308
10.6.4 Edible Coatings for Fruits and Vegetables......Page 311
10.6.5 Coatings for Fried Products......Page 314
10.6.6 Miscellaneous Coatings......Page 315
10.7 Novel Products......Page 317
10.9 Next Generation of Edible Films......Page 319
References......Page 321
11.1 Introduction......Page 330
11.2 Historical Background......Page 331
11.3 Structures formed during protein + polysaccharide associative phase separation......Page 332
11.4 Protein + Polysaccharide Associative Phase Separation Kinetics......Page 333
11.5 Internal structure of coacervates and interpolymeric complexes......Page 337
11.5.2 Complexes......Page 338
11.5.4 Coacervation vs. Complexation......Page 340
11.6.2 pH, Ionic Strength and Macromolecular Charge Density......Page 342
11.6.3 Molecular Conformation, Molecular Weight and ChargenbspDistribution......Page 343
11.6.4 Other Interactions: Hydrogen and Hydrophobic Bonding......Page 344
11.6.5.2 Acidification Rate......Page 345
11.7 Functional properties and potential applications of protein + polysaccharide complexes and coacervates......Page 346
Rheology of Soluble Complexes......Page 347
Rheology of Interpolymeric Insoluble Complexes......Page 348
Gelation of Proteins + Polysaccharides Under Associative Conditions......Page 349
Protein + Polysaccharide Complexes As Texturing Agents......Page 350
Foaming Properties......Page 351
Mixed Emulsions......Page 353
Mixed Emulsions for Encapsulation......Page 354
Bilayer Emulsions......Page 355
11.8 Main limitations for the use of coacervates and complexes in food applications and encapsulation......Page 356
References......Page 358
12.1.1 Image Formation......Page 367
12.1.2 Imaging Modes......Page 368
12.1.4 Macromolecules......Page 371
12.1.5 Polysaccharides......Page 372
12.1.7 Protein-Polysaccharide Complexes......Page 373
12.1.8 Bulk Gels and Networks......Page 375
12.1.9 Polysaccharide Gels......Page 376
12.1.10 Protein Gels......Page 378
12.1.12 Protein-Surfactant Interactions......Page 379
12.1.14 Starch......Page 382
12.1.15 Plant Cell Walls......Page 387
12.2 Surface forces......Page 388
12.2.2 Molecular Force Measurements......Page 389
12.2.3 Colloidal Forces......Page 391
12.2.5 Modes of Operation......Page 393
12.2.6 Applications......Page 394
References......Page 395
13.1.1 Definitions and Analytical Methods......Page 400
The Southgate Method......Page 402
The Crude Fiber Method......Page 403
13.1.2 Physiological Effects of Dietary Fiber......Page 404
Dietary Fiber in Food: Influence in Diabetes Mellitus......Page 405
Dietary Fiber in Food: Influence in CVD......Page 408
Regulatory Issues......Page 410
New Challenges......Page 411
13.2.2 Viscosity, Gel-Forming Capacity and Texturizing......Page 412
13.2.5 Soluble and Insoluble Dietary Fibre......Page 413
Structures......Page 414
Molecular Weight and Confor	mational Properties......Page 415
Functional Properties of beta-Glucan and Arabinoxylans: Flow Behavior, Viscoelastic and Gelation Properties......Page 417
Physiological properties......Page 418
Organoleptic Properties......Page 420
Psyllium......Page 421
Structural Features and Molecular Characteristics of Psyllium Polysaccharides......Page 422
Hydration, Viscoelastic and Gelling Properties......Page 423
Calcium-Ion-Binding Capacity of Psyllium Polysaccharides......Page 424
Physiological and Organoleptic Properties of Psyllium......Page 425
Process and Preparation of Inulins......Page 427
Chemical properties......Page 428
Functional Properties......Page 429
Applications of Inulins......Page 431
Digestion of Inulins......Page 432
Effect on Lipid Metabolism......Page 433
Immunomodulation and Anticancer Effects of Inulins......Page 434
13.3.3 Insoluble Dietary Fiber......Page 436
Wheat Bran......Page 437
Rice Bran......Page 439
Resistant Starch (RS)......Page 440
13.4 Concluding remarks......Page 441
References......Page 442
14.1 Introduction......Page 450
14.2 Measurement of resistant starch......Page 451
14.2.1 In Vivo Methods......Page 452
14.2.2 In Vitro Methods......Page 455
14.3 Health benefits of RS......Page 457
14.3.1 Energy Intake, Weight Management and Obesity......Page 458
14.3.3 Blood Lipids and Heart Health......Page 459
14.3.4 Bowel Health......Page 460
14.4 Effect of processing on resistant starch formation in foods......Page 462
14.4.2 Extrusion Cooking......Page 463
14.4.3 Boiling and High-Pressure Cooking......Page 473
14.4.4 Baking......Page 476
14.4.5 Effects of Non-Starch Materials on Resistant Starch Formation......Page 477
14.4.6 Effects of Acid or Enzyme Hydrolysis......Page 479
14.4.7 Fermentation......Page 480
14.5.1 X-ray Diffraction Studies......Page 481
14.5.3 Chain Length Distribution......Page 482
14.6.1 Chain Length and Branching Characteristics of Resistant Fractions......Page 485
14.6.2 Characterization Techniques......Page 487
14.6.3 Mechanisms of Resistance to Enzymic Digestion of Starch Granules......Page 491
14.6.4 Mechanisms of Resistance to Enzymic Digestion of Processed Starches......Page 494
14.7 Concluding remarks......Page 497
References......Page 501
15.2 Processing and carbohydrate digestibility......Page 512
15.3 The effect of extrusion parameters and processing on foodnbspquality......Page 513
15.4 Manipulating the glycemic impact of extruded snack products......Page 514
15.5 The link between slowly digestible and rapidly digestible carbohydrates and the glycemic impact of processed foods......Page 515
15.6 Use of dietary fiber in manipulating starch digestibility......Page 517
References......Page 518
16.1 Introduction......Page 520
16.2 Drug loading and release......Page 522
16.3 Modeling diffusion......Page 523
16.3.2 Fick’s Second Law......Page 524
16.4 Higuchian model......Page 525
16.5 Swelling......Page 526
16.6.1 pHhyphensensitive Hydrogels......Page 527
16.7 Equilibrium swelling and the Flory-Rehner theory......Page 528
16.9 Glutaraldehyde......Page 530
16.10 Genipin......Page 531
16.11 Quinones and phenols......Page 532
16.12 Polyelectrolyte crosshyphenlinking and complexes......Page 533
16.13 Polymer-drug interactions......Page 534
16.14.1 Crosshyphenlinked Collagen in Controlled Drug Delivery......Page 535
16.14.4 Collagenhyphenbased Formulations in Oral Delivery Systems......Page 536
16.15.1 Gelatin in Peptide Delivery......Page 537
16.15.4 Gelatin Microhyphen and Nanoparticles as Delivery Systems......Page 539
16.15.5 Gelatin as a Matrix for Biologically Active Agents......Page 540
16.16.1 Chitin/Chitosan as a Matrix for Biologically Active Agents......Page 541
16.16.4 Chemically Modified Chitin/Chitosan for Drug Delivery......Page 542
16.17 Celluloses......Page 543
16.17.2 Cellulose Esters......Page 544
16.18 Alginates......Page 545
16.18.1 Alginates in Diffusion-Controlled Delivery Systems......Page 546
16.18.4 Alginates as Encapsulating Agents......Page 547
Summary......Page 548
References......Page 549
17.1 Introduction to protein misfolding and fibril formation......Page 559
17.2 Amyloid formation, nature and disease......Page 560
17.3.1 Disease......Page 561
17.4 Amyloid fibrils innbspnature......Page 563
17.6.2 Biotechnology......Page 564
17.7.3 Off Pathway Model......Page 565
17.8.1 Fluorescence......Page 566
17.8.5  NMR Spectroscopy......Page 567
Soluble Intermediates: Protein Denaturation, Folding and Partially Folded Intermediates (Molten Globule State)......Page 568
17.9.2 Protein Aggregation - Protofilaments and Oligomers......Page 572
17.9.2.2Quasielastic Light Scattering......Page 573
17.10 Detection of amyloid fibrils......Page 574
17.13 Conditions that promote fibril formation......Page 579
17.13.2 Chemical......Page 581
17.14.4 Shear......Page 582
17.13.5 Interfaces......Page 583
17.14.1 Strength and Stability......Page 584
17.15 Nanotubes and nanowires......Page 585
17.16 Fibrillar gels......Page 586
17.18 Conclusions......Page 588
References......Page 589
18.1.1 Oral Delivery......Page 595
Tablets......Page 596
Pharmaceutical Capsules......Page 597
Alternative Oral Delivery Systems......Page 598
18.1.2 Ocular Delivery......Page 600
18.1.3 Mucoadhesion......Page 601
18.1.4.1 The Development of Biopharmaceuticals......Page 602
18.2 Tissue engineering......Page 604
18.2.2 Cell-Adhesive Hydrogels......Page 605
18.2.2.1 Collagen......Page 606
18.2.2.2 Fibrin......Page 607
18.2.3 Non-cell Adhesive Hydrogels......Page 608
18.2.4 Mechanical Conditioning......Page 610
18.2.4.2 Cell Migration......Page 612
18.2.5.2 Microfluidic Scaffolds......Page 613
References......Page 614
Index
......Page 619