Preface ........................................................ xv
List of Contributors .......................................... xix
1 Antioxidants: Introduction 1
Chunhuan He, Yingming Pan, Xiaowen Ji and Hengshan Wang
1.1 The Meaning of Antioxidant .............................. 1
1.2 The Category of Antioxidants and Introduction
of often Used Antioxidants .............................. 2
1.2.1 BHT .............................................. 4
1.2.2 Quercetin ........................................ 5
1.2.3 BHA .............................................. 5
1.2.4 2-terf-Butylhydroquinone (TBHQ) .................. 6
1.2.5 Gallic Acid ...................................... 6
1.2.6 Resveratrol ...................................... 6
1.2.7 Luteolin ......................................... 7
1.2.8 CaffeicAcid ...................................... 7
1.2.9 Catechin ......................................... 7
1.3 Antioxidant Evaluation Methods .......................... 8
1.3.1 DPPH Radical Scavenging Assay .................... 8
1.3.2 ABTS Radical Scavenging Activity ................. 8
1.3.3 Phosphomolybdenum Assay .......................... 9
1.3.4 Reducing Power Assay ............................. 9
1.3.5 Total Phenols Assay by Folin-Ciocalteu Reagent .. 10
1.3.6 Hydroxyl Radical Scavenging Assay ............... 10
1.3.7 ß-carotene-linoleic Acid Assay .................. 11
1.3.8 Superoxide Radical Scavenging Assay ............. 11
1.3.9 Metal Ion Chelating Assay ....................... 12
1.3.10 Determination of Total Flavonoid Content ........ 12
1.4 Antioxidant and its Mechanisms ......................... 13
1.4.1 Mechanism of Scavenging Free Radicals ........... 13
1.4.2 Mechanism of Metal Chelating Properties ......... 14
1.5 Adverse Effects of Antioxidants ........................ 15
References .................................................. 16
2 Natural Polyphenol and Flavonoid Polymers ................... 23
Kelly C. Heim
2.1 Introduction ........................................... 23
2.2 Structural Classification of Polyphenols ............... 24
2.2.1 Simple Phenolics ................................ 24
2.2.2 Stilbenes ....................................... 26
2.2.3 Lignin .......................................... 27
2.2.4 Flavonoids ...................................... 28
2.2.5 Tannins ......................................... 29
2.3 Polyphenol Biosynthesis and Function in Plants ......... 34
2.3.1 Biosynthesis .................................... 34
2.3.2 Protective Roles ................................ 36
2.4 Tannins in Human Nutrition ............................. 36
2.4.1 Dietary Sources and Intake ...................... 36
2.4.2 Absorption and Metabolism ....................... 37
2.5 Antioxidant Activity of Tannins ........................ 41
2.5.1 Mechanisms ...................................... 41
2.5.2 Structure-activity Relationships ................ 44
2.6 Protective Effects of Proanthocyanidins in Human
Health ................................................. 45
2.7 Conclusion ............................................. 46
Acknowledgements ............................................ 46
References .................................................. 47
3 Synthesis and Applications of Polymeric Flavonoids .......... 55
Hiroshi Uyama and Young-Jin Kim
3.1 Introduction ........................................... 55
3.2 Polycondensates of Catechin with Aldehydes ............. 57
3.3 Enzymatically Polymerized Flavonoids ................... 69
3.4 Biopolymer-flavonoid Conjugates ........................ 76
3.5 Conclusion ............................................. 84
References .................................................. 84
4 Antioxidant Polymers: Metal Chelating Agents ................ 87
Hiba M. Zalloum and Mohammad S. Mubarak
4.1 Introduction ........................................... 87
4.1.1 Antioxidants .................................... 87
4.1.2 Natural Polymers as Antioxidants ................ 88
4.1.3 Chelating Polymers and Heavy Metal Ions ......... 90
4.2 Chitin and Chitosan .................................... 91
4.2.1 Chitin and Chitosan Derivatives ................. 94
4.2.2 Chitin and Chitosan as Chelating Agents ......... 95
4.3 Alginates .............................................. 96
4.4 Chelation Studies ...................................... 97
4.4.1 Chitosan Derivatives as Chelating Agents ....... 101
4.4.2 Alginates as Chelating Agents .................. 103
4.5 Conclusions ........................................... 106
References ................................................. 107
5 Antioxidant Polymers by Chitosan Modification .............. 115
Jarmila Vinšová and Eva Vavříková
5.1 Introduction .......................................... 115
5.2 Chitosan Characteristics .............................. 117
5.3 Reactive Oxygen Species and Chitosan as Antioxidant ... 117
5.4 Structure Modifications ............................... 120
5.4.1 N-Carboxymethyl Chitosan Derivatives ........... 120
5.4.2 Quaternary Salts ............................... 121
5.4.3 Sulphur Derivatives ............................ 122
5.4.4 Chitosan Containing Phenolic Compounds ......... 124
5.4.5 Schiff Bases of Chitosan ....................... 127
5.5 Conclusion ............................................ 129
References ................................................. 129
6 Cellulose and Dextran Antioxidant Polymers for Biomedical
Applications ............................................... 133
Sonia Trombino, Roberta Cassano and Teresa Ferrarelli
6.1 Introduction .......................................... 133
6.2 Antioxidant Polymers Cellulose-based .................. 134
6.2.1 Cellulose ...................................... 134
6.2.2 Antioxidant Biomaterials
Carboxymethylcellulose-based ................... 135
6.2.3 Ferulate Lipoate and Tocopherulate Cellulose ... 136
6.2.4 Cellulose Hydrogel Containing Tnms-ferulic
Acid ........................................... 138
6.2.5 Polymeric Antioxidant Membranes Based on
Modified Cellulose and PVDF/cellulose Blends ... 139
6.2.6 Synthesis of Antioxidant Novel Broom and
Cotton Fibers Derivatives ...................... 140
6.3 Antioxidant Polymers Dextran-based .................... 142
6.3.1 Dextran ........................................ 142
6.3.2 Biocompatible Dextran-coated Nanoceria with
pH-dependent Antioxidant Properties ............ 143
6.3.3 Coniugates of Dextran with Antioxidant
Properties ..................................... 145
6.3.4 Dextran Hydrogel Linking Trans-ferulic Acid
for the Stabilization and Transdermal
Delivery of Vitamin E .......................... 146
References ................................................. 149
7 Antioxidant Polymers by Free Radical Grafting on Natural
Polymers ................................................... 153
Manuela Curcio, Ortensia Ilaria Parisi, Francesco Puoci,
Ilaria Altimari, Untile Gianfranco Spizzirri and Nevio
Picci
7.1 Introduction .......................................... 153
7.2 Grafting of Antioxidant Molecules on Natural
Polymers .............................................. 156
7.3 Proteins-based Antioxidant Polymers ................... 157
7.4 Polysaccharides-based Antioxidant Polymers ............ 164
7.4.1 Chitosan ....................................... 164
7.4.2 Starch ......................................... 166
7.4.3 Inulin and Alginate ............................ 170
7.5 Conclusions ........................................... 175
Acknowledgements ........................................... 176
References ................................................. 176
8 Natural Polymers with Antioxidant Properties: Poly-/
oligosaccharides of Marine Origin .......................... 179
Guangling Jiao, Guangli Yu, Xiaoliang Zhao, Junzeng
Zhang and H. Stephen Ewart
8.1 Introduction to Polysaccharides from Marine Sources ... 180
8.1.1 Polysaccharides from Marine Algae .............. 180
8.1.2 Polysaccharides from Marine Invertebrates ...... 181
8.1.3 Marine Bacteria Polysaccharides ................ 182
8.2 Antioxidant Activities of Marine Polysaccharides
and their Derivatives ................................. 183
8.2.1 Antioxidant Evaluation Methods ................. 183
8.2.2 Marine Sulfated Polysaccharides ................ 187
8.2.3 Marine Uronic Acid-containing Polysaccharides .. 188
8.2.4 Marine Non-acidic Polysaccharides and their
Oligomers ...................................... 189
8.2.5 Marine Glycoconjugates ......................... 189
8.3 Applications of Marine Antioxidant Polysaccharides
and their Derivatives ................................. 191
8.3.1 Applications in Food Industry .................. 191
8.3.2 Applications as Medicinal Materials ............ 191
8.3.3 Applications as Cosmetic Ingredients ........... 192
8.3.4 Applications in Other Fields ................... 193
8.4 Structure-antioxidant Relationships of Marine
Poly-/oligosaccharides ................................ 193
8.5 Conclusions ........................................... 195
Acknowledgements ........................................... 195
References ................................................. 195
9 Antioxidant Peptides from Marine Origin: Sources,
Properties and Potential Applications ...................... 203
Begoña Giménez, M. Elvira López-Caballero, M. Pilar
Montero and M. Carmen Gómez-Guillén
9.1 Introduction .......................................... 204
9.2 Whole Fish Hydrolysates ............................... 207
9.3 Marine Invertebrate Hydrolysates ...................... 223
9.4 Fish Frames Hydrolysates .............................. 227
9.5 Viscera Hydrolysates .................................. 228
9.6 Muscle Hydrolysates ................................... 232
9.7 Collagen and Gelatin Hydrolysates ..................... 240
9.8 Seaweeds Hydrolysates ................................. 243
9.9 Potential Applications ................................ 245
9.10 Conclusions ........................................... 249
Acknowledgements ........................................... 250
References ................................................. 250
10 Synthetic Antioxidant Polymers: Enzyme Mimics .............. 259
Cheng Wang, Gang-lin Yan and Gui-min Luo
10.1 Introduction .......................................... 260
10.2 Organo-selenium/tellurium Compound Mimics ............. 261
10.2.1 Chemistry of Organo-selenium/tellurium ......... 261
10.2.2 Synthetic Organo-selenium/tellurium
Compounds as GPX Mimics ........................ 263
10.2.3 Cyclodextrin-based Mimics ...................... 272
10.3 Metal Complex Mimics .................................. 281
10.3.1 The Role of Metal Ions in Complexes ............ 282
10.3.2 Manganese Complexes Mimics ..................... 283
10.3.3 Other Metal Complex Mimics ..................... 293
10.4 Selenoprotein Mimics .................................. 295
10.4.1 Strategies of Selenoprotein Synthesis .......... 295
10.4.2 Synthetic Selenoproteins ....................... 305
10.5 Supramolecular Nanoenzyme Mimics ...................... 312
10.5.1 Advantages of Supramolecular Nanoenzyme
Mimics ......................................... 313
10.5.2 Supramolecular Nanoenzyme Mimics with
Antioxidant Acitivity .......................... 314
10.6 Conclusion ............................................ 325
References ................................................. 325
11 Synthetic Polymers with Antioxidant Properties ............. 333
Ashveen V. Nand and Paul A. Kilmartin
11.1 Introduction .......................................... 334
11.2 Intrinsically Conducting Polymers ..................... 335
11.3 Intrinsically Conducting Polymers with Antioxidant
Properties ............................................ 336
11.4 Synthesis of Antioxidant Intrinsically Conducting
Polymers .............................................. 337
11.4.1 Chemical Synthesis ............................. 337
11.4.2 Electrochemical Synthesis ...................... 338
11.4.3 Other Polymerization Techniques ................ 339
11.5 Polymer Morphologies .................................. 340
11.5.1 Polyaniline .................................... 340
11.5.2 Polypyrrole .................................... 342
11.5.3 Poly(3,4-ethylenedioxythiophene) ............... 343
11.6 Mechanism of Radical Scavenging ....................... 344
11.7 Assessment of Free Radical Scavenging Capacity ........ 346
11.7.1 DPPH Assay ..................................... 347
11.7.2 ABTS Assay ..................................... 347
11.8 Factors Affecting the Radical Scavenging Activity ..... 348
11.9 Polymer Blends and Practical Applications ............. 350
References ................................................. 351
12 Synthesis of Antioxidant Monomers Based on Sterically
Hindered Phenols, a-Tocopherols, Phosphites and Hindered
Amine Light Stabilizers (HALS) and their Copolymerization
with Ethylene, Propylene or Styrene ........................ 355
Carl-Eric Wilén
12.1 Introduction .......................................... 356
12.2 Synthesis of Antioxidant Monomers to Enhance
Physical Persistence and Performance of Stabilizers ... 361
12.2.1 Copolymerization of Antioxidants with
α-Olefins Using Coordination Catalysts ......... 363
12.2.2 Synthesis of Antioxidant Monomers .............. 364
12.3 Phenolic Antioxidant Monomers and their
Copolymerization with Coordination Catalysts .......... 369
12.3.1 Copolymerization of Antioxidant Monomers
with Ethylene or Propylene using Traditional
Ziegler-Natta Catalysts ....................... 369
12.4 Copolymerization of Antioxidant Monomers with
Ethylene, Propylene, Styrene and Carbon Monoxide
Using Single Site Catalysts ........................... 372
12.4.1 Copolymerization of Phenolic Antioxidant
Monomers ....................................... 372
12.4.2 Copolymerization of HALS Monomers using
Single Site Catalysts .......................... 376
12.5 Conclusions ........................................... 379
Acknowledgements ........................................... 380
References ................................................. 380
13 Novel Polymeric Antioxidants for Materials ................. 385
Ashish Dhawan, Vijayendra Kumar, Virinder S. Parmarand and
Ashok L. Cholli
13.1 Industrial Antioxidants ............................... 386
13.2 Antioxidants Used in Plastics (Polymer) Industry ...... 386
13.2.1 Primary Antioxidants ........................... 388
13.2.2 Secondary Antioxidants ......................... 389
13.3 Antioxidants Used in Lubricant Industry ............... 389
13.4 Antioxidants Used in Elastomer (Rubber) Industry ...... 390
13.5 Antioxidants Used in Fuel Industry .................... 392
13.6 Antioxidants Used in Food Industry .................... 393
13.6.1 Natural Food Antioxidants ...................... 393
13.6.2 Synthetic Food Antioxidants .................... 394
13.7 Limitations of Conventional Antioxidants .............. 395
13.7.1 Performance Issues because of Antioxidant
Efficiency Loss ................................ 395
13.7.2 Environmental Issues and Safety Concerns ....... 395
13.7.3 Compatibility Issues ........................... 396
13.7.4 Poor Thermal Stability ......................... 396
13.8 Trends towards High Molecular Weight Antioxidants ..... 396
13.8.1 Functionalization of Conventional
Antioxidants with Hydrocarbon Chains ........... 397
13.8.2 Macromolecular Antioxidants .................... 397
13.8.3 Polymer-bound Antioxidants ..................... 398
13.8.4 Polymeric Antioxidants ......................... 401
13.9 Motivation, Design and Methodology for Synthesis of
Novel Polymeric Antioxidant Motivation ................ 407
13.9.1 Design of the Polymeric Antioxidants ........... 408
13.9.2 Methodology .................................... 408
13.10 Biocatalytic Synthesis of Polymeric Antioxidants ..... 409
13.11 General Procedure for Enzymatic Polymerization ....... 410
13.11.1 Synthesis and Characterization of Polymeric
Antioxidants .................................. 411
13.11.2 Antioxidant Activity of Polymeric
Antioxidants .................................. 417
13.11.3 Evaluation of Polymeric Antioxidants in
Vegetable Oils by Accelerated Oxidation ....... 420
13.12 Conclusions .......................................... 421
Acknowledgement ............................................ 422
References ................................................. 422
14 Biopolymeric Colloidal Particles Loaded with Polyphenolic
Antioxidants ............................................... 427
Ashok R. Patel and Krassimir P. Velikov
14.1 Introduction .......................................... 427
14.2 Polyphenols: Antioxidant Properties and Health
Benefits .............................................. 428
14.3 Polyphenols: Formulation and Delivery Challenges ...... 429
14.3.1 Solubility ..................................... 430
14.3.2 Chemical Reactivity and Degradation ............ 430
14.3.3 Stability in Physiological Conditions .......... 430
14.3.4 First Pass Metabolism and Pharmacokinetics ..... 431
14.3.5 Organoleptic Properties and Aesthetic Appeal ... 431
14.4 Polyphenols Loaded Biopolymeric Colloidal Particles ... 431
14.4.1 Curcumin Loaded Biopolymeric Colloidal
Particles ...................................... 433
14.4.2 Silibinin Loaded Biopolymeric Colloidal
Particles ...................................... 441
14.4.3 Quercetin Loaded Biopolymeric Colloidal
Particles ...................................... 447
14.5 Conclusion ............................................ 454
References ................................................. 455
15 Antioxidant Polymers for Tuning Biomaterial
Biocompatibility: From Drug Delivery to Tissue
Engineering ................................................ 459
David Cochran and Thomas D. Dziubla
15.1 Introduction .......................................... 459
15.2 Oxidative Stress in Relation to Biocompatibility ...... 460
15.2.1 Mechanism of Immune Response ................... 460
15.2.2 Examples in Practice ........................... 464
15.3 Antioxidant Polymers in Drug Delivery ................. 467
15.3.1 Uses as Active Pharmaceutical Ingredients ...... 467
15.3.2 Uses as Pharmaceutical Excipients .............. 468
15.4 Antioxidant Polymers in Anti-cancer Therapies ......... 470
15.5 Antioxidant Polymers in Wound Healing and Tissue
Engineering ........................................... 472
15.5.1 Antioxidant Polymers Incorporated into
Biomaterials .................................. 472
15.6 Conclusions and Perspectives .......................... 476
References ................................................. 479
Index ......................................................... 485
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