Handbook of Natural Colorants

Plants 49 4.2.5 Yellow- Dye Plants 49 4.2.6 Brown- Dye Plants 52 4.2.7 Production of Dye Extracts 54 4.3 Natural Colorants from Agro- Food Residues 55 4.4 Natural Colorants from Forestry and Timber Industry 56 4.5 Relevant Examples for the Application 57 4.6 Conclusions, Discussion, and Summary 58 Acknowledgement 58 References 59 5 Dyes in South America 63 Veridiana Vera de Rosso and Adriana Zerlotti Mercadante 5.1 Introduction 63 5.2 Annatto 65 5.3 Turmeric 67 5.4 Marigold 68 5.5 Cochineal and Carmine 69 Acknowledgements 71 References 71 6 Natural Dyes in Eastern Asia (Vietnam and Neighboring Countries) 75 Tung Pham and Thomas Bechtold 6.1 Introduction 75 6.2 Annatto (Bixa orellana L., Family Bixaceae) 75 6.3 Tea (Camellia sinensis (L.) Kuntze, Family Theaceae) 77 6.4 Umbrella Tree (Terminalia catappa L., Family Combretaceae) 77 6.5 Mackloeur (Diospyros mollis L. Griff, Family Ebenaceae) 78 6.6 Indigo (Indigofera L., Family Fabaceae) 79 6.6.1 Indigofera tinctoria L. 79 6.6.2 Indigofera galegoides dc 80 6.6.3 Strobilanthes cusia (Baphicacanthus) 80 6.7 Henna (Kok Khan or Khao Youak in Laos) (Lawsonia spinosa L., Family Lythraceae) 80 6.8 Nacre (African Mahogany, Khaya senegalensis, Family Meliaceae) 81 6.9 Sappan Wood (Caesalpinia sappan L., Family Fabaceae) 81 6.10 Japanese Pagoda Tree Flowers (Sophora japonica L., Family Leguminosae) 82 6.11 Turmeric (Curcuma longa L., Family Zingiberaceae) 82 6.12 Sapodilla (Manilkara zapota L. or Achras zapota, Family Sapotaceae) 82 6.13 Betel (Piper betel L., Family Piperaceae) 83 6.14 Eucalyptus (Eucalyptus, Family Myrtaceae) 83 6.15 Caesalpinia Yellow (Caesalpinia pulcherrima L., Family Fabaceae) 83 6.16 Brow- Tuber; Yam (Dioscorea cirrhosa Lour, Family Dioscoreaceae) 83 6.17 Others 84 Acknowledgement 84 References 84 7 Sources for Natural Colorants in China 89 Ren-Cheng Tang 7.1 Introduction 89 7.2 Sophora japonica Yellow 92 7.3 Turmeric 93 7.4 Gardenia Yellow 93 7.5 Emodin 93 7.6 Baicalin 94 7.7 Berberine 94 7.8 Henna 94 7.9 Monascus Red 95 7.10 Madder 95 7.11 Sorghum Red 95 7.12 Mulberry Red 96 7.13 Shikonin 96 7.14 Indigo 96 7.15 Condensed Tannins 97 7.16 Tea Polyphenols 98 7.17 Gallnut 99 References 99 8 Sources, Application, and Analysis of Natural Colorants: An Indian Perspective 103 Prof. (Dr.) Ashis Kumar Samanta and Prof. (Dr.) Deepali Singhee 8.1 Introduction 103 8.2 Natural Dyes in India 104 8.2.1 History 104 8.2.2 Traditional Processes of Dyeing with Natural Dyes in Different Parts of India 105 8.2.3 Sources of Natural Dyes in India 106 8.2.4 Use of Some Natural Dyes in Traditional Textiles of India 107 8.3 Details of Some Dye Sources and Their Application in India 109 8.3.1 Turmeric 109 8.3.2 Pomegranate 111 8.3.3 Flame of Forest 114 8.3.4 Marigold 116 8.3.5 Safflower 118 8.3.6 Annatto 120 8.3.7 Madder 123 8.3.8 Indian Mulberry 125 8.3.9 Arjuna 127 8.3.10 Sappanwood 130 8.3.11 Eucalyptus 132 8.3.12 Catechu 134 8.3.13 Gallnut 137 8.3.14 Myrobolan 140 8.3.15 Lac 142 8.3.16 Indigo 145 References 147 9 Natural Dye Gardens in North America 161 Wendy Weiss and Thomas Bechtold 9.1 Introduction 161 9.2 Participants 162 9.3 Education 163 9.4 Motivation to Work with Natural Dye 166 9.5 Plant List-- Cultivated Plants 166 9.6 Chemical Background of Most Relevant Plants 168 9.7 Plant List-- Foraged Plants 172 9.8 Plants with Indigotin 172 9.9 Importance of the Fibershed Movement 173 9.10 Educational and Community Gardens 174 9.11 Mexico 177 9.12 Canada 177 9.13 Future Research 178 References 178 Notes 179 III Colorant Production and Properties 181 10 Chlorophylls 183 María Roca 10.1 Introduction 183 10.2 Chemical Structures and Physicochemical Properties 184 10.3 Chlorophylls as Colorants 187 10.4 New Trends in the Use of Chlorophylls as Colorants 189 10.5 Stability and Analysis 190 10.6 Toxicological and Safety Aspects 191 References 192 11 Indigo-- Production and Properties 195 Philip John and Luciana Gabriella Angelini 11.1 Introduction 195 11.2 Agronomy 196 11.2.1 Isatis 196 11.2.1.1 Developmental Stages and Climate and Soil Crop Requirements 197 11.2.1.2 Rotation 201 11.2.1.3 Soil Tillage and Seed Sowing 202 11.2.1.4 Weeds, Pests, and Diseases 203 11.2.1.5 Fertilizers and Irrigation 204 11.2.1.6 Harvesting and Yields 205 11.2.1.7 Seed Production 207 11.2.1.8 Isatis indigotica Compared with Isatis tinctoria 208 11.2.2 Persicaria 209 11.2.2.1 Introduction 209 11.2.2.2 Developmental Stages 211 11.2.2.3 Sowing, Harvesting, and Yield 211 11.2.2.4 Weeds, Pests, and Diseases 216 11.2.2.5 Fertilizer and Irrigation Requirement 216 11.2.2.6 Seed Production 217 11.2.3 Indigofera 217 11.3 Methods of Determining Indigo 219 11.4 Precursors in the Plants 222 11.5 Direct Dyeing with Indican 227 11.6 Indigo Formation 227 11.7 Extraction Procedures 229 11.7.1 Traditional Process Using Crushed Leaf Material 229 11.7.1.1 Isatis 229 11.7.1.2 Persicaria 230 11.7.2 Steeping in Water 231 11.7.2.1 Indigofera 232 11.7.2.2 Isatis 234 11.7.2.3 Persicaria 239 11.8 Purity of Natural Indigo 240 11.8.1 Purification by Sublimation 241 11.8.2 Impurities in Natural Indigo 242 Acknowledgements 245 References 245 12 Anthocyanins: Revisiting Nature's Glamorous Palette 251 Maria J. Melo, Fernando Pina, Natércia Teixeira and Claude Andary 12.1 Chemical Basis 251 12.1.1 Chemical Structures 251 12.1.2 Equilibria in Solution 253 12.1.3 Kinetics 254 12.1.4 Color and Color Stability 254 12.1.5 Anthocyanins as Antioxidants 258 12.2 Natural Sources and Applications for Anthocyanins 259 12.2.1 Plants Sources, Content, Influencing Parameters 259 12.2.2 Food Colorants 260 12.2.3 Other Uses 261 12.2.4 Examples of Commercial Products and Processing 262 References 263 Appendix 1 267 A1.1 Multi-Equilibria in Acidic and Basic Media 267 A1.2 Measuring the Equilibria Constants 269 13 Natural Colorants-- Quinoid, Naphthoquinoid, and Anthraquinoid Dyes 271 Goverdina C. H. Derksen and Thomas Bechtold 13.1 Introduction 271 13.2 Benzoquinone Dyes 271 13.3 Diaryloylmethane Dyes 273 13.4 Naphthoquinone Dyes 273 13.4.1 Lawson (2- hydroxy- 1,4- naphthoquinone, CI Natural Orange 6) 274 13.4.1.1 Properties and Use 274 13.4.1.2 Agricultural Aspects 276 13.4.2 Juglone (5- hydroxy- 1,4- naphthoquinone, CI Natural Brown 7) 278 13.5 Anthraquinone Dyes 279 13.5.1 Main Components Emodin and Chrysophanol-- Rheum and Rumex Species 279 13.5.2 Main Components Alizarin and/or Pseudopurpurin/Purpurin 281 13.5.2.1 Plant Sources 281 13.5.2.2 Madder CI Natural Red 8 282 References 294 14 Natural Colorants from Lichens and Mushrooms 317 Riikka Räisänen 14.1 Use of Lichen and Mushroom Colorants in History 317 14.2 Cultivation of Lichens and Mushrooms 318 14.3 Colorant Structures in Lichens and Mushrooms 319 14.3.1 Lichen Dyes: Orchils and Litmus 321 14.3.2 Yellowish, Brownish, and Reddish Colorants from Lichen 322 14.3.3 Blue Terphenylquinones from Mushrooms 322 14.3.4 Anthraquinones 324 14.3.4.1 Bloodred Webcap (Cortinarius sanguineus) 324 14.3.5 Other Colorants of Fungi 326 14.3.5.1 Yellows from Grevillines 326 14.3.5.2 Yellow and Orange Colors from Pulvinic Acid Derivatives 326 14.3.5.3 Brown from Badiones 326 14.4 Stability of Lichen and Mushroom Colorants 326 14.5 New Approaches to Lichen and Fungal Colorants 327 References 328 15 Focus on Tannins 333 Riitta Julkunen-Tiitto and Hely Häggman 15.1 Introduction 333 15.2 Chemical Structure, Biosynthesis, and Degradation 335 15.3 Properties of Tannins 338 15.4 Chemical Activities of Tannins 340 15.5 Analysis of Tannins 340 15.5.1 Sample Preservation 340 15.5.2 Extraction and Purification 340 15.5.3 Quantification of Tannins 341 15.6 Use, Toxicology, and Safety Aspects of Tannins 342 References 345 16 Carotenoid Dyes-- Properties and Production 351 U. Gamage Chandrika 16.1 Introduction 351 16.1.1 Occurrence of Carotenoids 351 16.1.2 Chemistry of Carotenoids 351 16.1.3 Chemical Characteristics of Natural Carotenoids 352 16.2 Properties and Functions of Carotenoids 354 16.2.1 Carotenoids' Role as Pro- vitamin A 354 16.2.2 Use of Carotenoids as Markers of Dietary Practices 356 16.2.3 Carotenoids as Antioxidants 356 16.2.4 Carotenoids in the Macular Region of the Retina 357 16.2.5 Carotenoids as Anticancer Agents 357 16.2.6 Carotenoids as Natural Colorants 357 16.3 General Procedure for Carotenoid Analysis 357 16.3.1 Sampling 359 16.3.2 Extraction 359 16.3.3 Saponification of Carotenoids 359 16.3.4 Chromatographic Separation 359 16.3.5 Chemical Tests 361 16.3.6 Detection and Identification of Carotenoids 361 16.3.7 Quantification of Carotenoids 362 16.4 Problems in Carotenoid Analysis 362 16.5 Factors Influencing Carotenoid Composition in Plant Sources 363 16.5.1 Stage of Maturity 363 16.5.2 Cultivar or Varietal Differences 363 16.5.3 Climatic or Geographic Effects 364 16.5.4 Post- Harvest Storage and Packing 364 16.5.5 Changes in Processing/Cooking 364 16.5.6 Effect of Agrochemicals 366 References 366 17 Flavonoids as Natural Pigments 371 M. Monica Giusti, Gonzalo Miyagusuku-Cruzado and Taylor C. Wallace 17.1 Introduction 371 17.2 Role of Localized Flavonoids in the Plant 372 17.3 General Flavonoid Chemical Structure 372 17.4 Biosynthesis of Flavonoids 373 17.5 Anthocyanins as Natural Colorants 373 17.5.1 Structure 375 17.5.2 Structural Transformation and pH 376 17.5.3 Temperature 377 17.5.4 Oxygen and Ascorbic Acid 377 17.5.5 Light 378 17.5.6 Enzymes and Sugars 379 17.5.7 Sulfur Dioxide 379 17.5.8 Co- Pigmentation and Metal Complexation 380 17.6 Other Flavonoids as Natural Colorants 381 17.6.1 Yellow Flavonoid Pigments 381 17.6.2 Tannins 381 17.6.3 Anthocyanin- Derived Pigments: Pyranoanthocyanins 382 17.7 Therapeutic Effects of Flavonoids in the Diet 382 17.8 The Use of Flavonoids as Food Colors in the US and EU 383 References 384 18 Natural Colorants from Fungi 391 Cassamo U. Mussagy, Fernanda de Oliveira and Valeria C. Santos-Ebinuma 18.1 Introduction 391 18.2 Types of Fungi Colorants 392 18.3 Fungal Producer of Colorants 394 18.4 Bioprocess 395 18.4.1 Biosynthesis Pathway 395 18.4.2 Production and Extraction Process 400 18.5 Toxicity 404 18.6 Industrial Application of Fungi Colorants 406 18.7 Conclusion 407 References 407 19 Natural Colorants from Cyanobacteria and Algae 417 Laurent Dufossé 19.1 Introduction 417 19.2 Phycobiliproteins from Cyanobacteria 418 19.2.1 Structural Characteristics of Phycobiliproteins 420 19.2.2 Food Grade Phycobiliproteins 422 19.2.3 Future Trends 422 19.3 Pigments from Microalgae 422 19.3.1 ß- Carotene from the Microalga Dunaliella, Salty but Effective! 423 19.3.1.1 ß- Carotene from Microalgae 423 19.3.1.2 Dunaliella Species for Carotenoids 424 19.3.2 Why Carotenoids from Dunaliella? 424 19.3.2.1 Natural vs. Synthetic ß- Carotene 424 19.3.2.2 Applications of ß- Carotene 424 19.3.2.3 Advantages of Carotenoids Production from Dunaliella 425 19.3.2.4 Process for Production of ß- Carotene from Dunaliella 425 19.3.2.5 Companies Producing Dunaliella 425 19.3.2.6 Marketed Products of ß- Carotene 426 19.3.3 Haematococcus for Astaxanthin, the Red Gold Rush 426 19.3.3.1 Advantages of Astaxanthin over Other Carotenoids 427 19.3.3.2 Astaxanthin as Nutraceutical 427 19.3.3.3 Astaxanthin as Antioxidant 427 19.3.3.4 Astaxanthin for Health 428 19.3.3.5 Astaxanthin for Salmon and Trout Feeds 428 19.3.3.6 Astaxanthin for Humans 429 19.3.3.7 Production System for Haematococcus 429 19.3.3.8 Companies Producing Astaxanthin from Haematococcus 430 19.3.3.9 Astaxanthin- Containing Formulations 431 19.4 Natural Colorants from Macroalgae (e.g., Seaweeds) 431 19.4.1 Biodiversity of Seaweeds 431 19.4.2 Seasonal Variations and Environmental Threats 432 19.4.3 Major Classes of Seaweed Pigments 433 19.4.3.1 Chlorophylls 433 19.4.3.2 Carotenoids 433 19.4.3.3 Phycobiliproteins 434 19.5 Conclusion 434 References 434 20 Biotechnological Production of Microbial Pigments: Recent Findings 439 Vivian Katherine Colorado Gómez, Juan Pablo Ruiz-Sánchez, Alejandro Méndez-Zavala, Lourdes Morales-Oyervides and Julio Montañez 20.1 Introduction 439 20.2 Microbial Pigments Market 440 20.3 Production Strategies 440 20.4 Novel Extraction Technologies for Pigments Recovery 441 20.5 Regulation and Biosynthesis of Microbial Pigments 443 20.6 Strain Engineering Strategies for Pigment Production 446 20.7 Trends in New Microbial Sources of Pigments 448 20.8 Microbial Pigments Applications 449 20.8.1 Solar Cells 449 20.8.2 Therapeutic Application 450 20.8.3 Other Applications 450 20.9 Regulations on Microbial Pigments Use 451 20.10 Conclusions and Future Perspectives 452 References 452 21 Analytical Methods for Characterization and Standardization of Natural Dyes and Pigments 459 Tung Pham, Avinash Manian and Thomas Bechtold 21.1 Introduction 459 21.2 Chemical Analysis-- Identification 460 21.3 Quantification by Sum Parameters 463 21.4 Applicatory Tests 464 21.5 Product Performance 465 References 466 22 Wood-- From Natural Color Patterns Toward Naturally Altered Color Impressions 469 Martin Weigl-Kuska, Andreas Kandelbauer, Christian Hansmann and Ulrich Müller 22.1 The Color of Wood 469 22.1.1 Wood Chemical Composition 470 22.1.2 Wood Anatomical Appearance 471 22.1.3 Physical Properties of the Wood Surface 472 22.2 Coatings 473 22.3 Dyes 477 22.3.1 Impregnation 477 22.3.1.1 Technology 477 22.3.1.2 Color 479 22.3.1.3 Products 480 22.4 Color Modification 481 22.4.1 Drying 482 22.4.1.1 Basics 482 22.4.1.2 Technology 483 22.4.1.3 Color 484 22.4.2 Steaming 485 22.4.2.1 Basics 485 22.4.2.2 Technology 485 22.4.2.3 Color 486 22.4.3 Thermal Treatment 487 22.4.3.1 Technology 487 22.4.3.2 Color 487 22.4.4 Ammoniation 488 22.4.4.1 Basics 488 22.4.4.2 Color 489 22.4.5 Bleaching 491 22.4.5.1 Basics 491 22.4.5.2 Color 491 22.4.6 Enzymatic Treatment 492 22.4.6.1 Basics 492 22.4.6.2 Laccases 493 22.4.7 Radiation 495 22.4.7.1 Basics 495 22.4.7.2 Color 495 22.4.7.3 Technology 497 22.5 Outlook 498 References 498 23 The Role of Mordants in Fixation of Natural Dyes 507 Avinash P. Manian 23.1 Introduction 507 23.2 Metal Salts 508 23.3 Biomordants 508 23.4 Substrate Pretreatments 508 23.5 No Mordant 509 References 509 24 Textile Coloration with Natural Dyes and Pigments 517 Thomas Bechtold, Tung Pham and Avinash P. Manian 24.1 Introduction 517 24.2 Reasons for Natural Coloration 518 24.3 The Dyestuff-Fiber Interaction 520 24.4 Design of a Dyeing Process 521 24.5 Transfer of a Dyeing Process into Technical Scale 523 24.6 Processes and Resources 524 24.7 Technical Requirements for a Natural Dyestuff 526 24.7.1 Gamut and Color Shade 526 24.7.2 Fastness Criteria 528 24.8 Handling of Natural Dyes in a Technical Dyehouse 530 24.9 Mordanting 531 24.10 Natural Dyes on an Industrial Scale 533 24.10.1 Dyeing Technology-- Exhaust Process 533 24.10.2 Hank Dyeing of Woolen Yarn and Production of Woolen Caps 534 24.10.3 Dyeing of Cones in a Yarn Dyeing Machine 534 24.10.4 Dyeing of Cotton Fabric on a Jet Dyeing Machine 535 24.10.5 Fabric Dyeing on a Garment Dyeing Machine 536 24.10.6 Dyeing of Polyamide Tights in a Paddle Dyeing Machine 536 24.10.7 Dyeing Technology-- Continuous Dyeing 536 24.11 Conclusion 537 Acknowledgement 538 References 538 25 Hair Coloration with Natural Dyes and Pigments 543 Thomas Bechtold 25.1 Introduction 543 25.2 Human Hair 544 25.3 General Requirements on Hair Dyeing Concepts 544 25.4 Chemical Principles of Dyestuff Binding 546 25.5 Relevant Natural Dyes for Hair Dyeing 546 25.5.1 Naphthoquinone Dyes-- Henna and Walnut 546 25.5.1.1 Henna, CI (Color Index) Natural Orange 6 546 25.5.1.2 Juglon, CI Natural Brown 7 547 25.5.2 Indigo 548 25.5.3 Metal Complexes 548 25.5.4 Metal Reaction Dyes 550 25.5.5 Anthraquinoid Dyes 551 25.6 Specialties 551 25.7 Regulations 552 References 552 26 Natural Colorants in the Mass Coloration of Plastics 557 Thomas Bechtold and Tung Pham 26.1 Introduction 557 26.2 Representative Examples 559 Acknowledgement 561 References 561 27 Natural Colorants in Printing/Packaging 563 Thomas Bechtold and Tung Pham 27.1 Introduction 563 27.2 Packaging Films 564 27.3 Film Coloration 567 27.4 Paper Dyeing 568 27.5 Paints 568 Acknowledgement 569 References 569 28 Technical Aspects and Requirements to Produce Natural Colorants-- Processes and Product Standardization 573 Thomas Bechtold and Avinash Manian 28.1 Introduction 573 28.2 Sources of Plant Material-- Product I 576 28.2.1 Organic Farming 576 28.2.2 Sustainable Farming 576 28.2.3 Native Species 577 28.2.4 Farming for Food or/and Natural Colorants 577 28.2.5 Residual Materials and By- Products 577 28.3 Processing to Dyestuff-- Product II 579 28.4 Quality Control and Standardization of a Dye (Product II) 583 28.4.1 Anthocyanins 584 28.4.2 Flavonoids 584 28.4.3 Dye Lakes 585 28.5 Challenges for the Industrial Use of Natural Colorants 585 28.6 Dealing with Sustainability 586 28.7 Conclusions 587 References 587 29 Environmental and Economic Position of Natural Colorants-- Energy and Resources Balances, Sustainability, Ecology, and Costs 591 Susanne Geissler and Thomas Bechtold 29.1 Introduction 591 29.2 Dye Plant Production 592 29.3 Dye Extraction and Dyestuff Production 595 29.4 Transportation 596 29.5 Textile Dyeing 596 29.6 Commercial Aspects-- Costs 597 29.6.1 Basic Requirements for the Industrial Use of Natural Colorants 598 29.6.1.1 Precondition 1: acceptable costs of natural colorants and dyeing processes 599 29.6.1.2 Precondition 2: feasible cost of process engineering 599 29.6.1.3 Precondition 3: compliance with requested colorfastness properties 599 29.6.1.4 Precondition 4: competitive cost of naturally dyed products 600 29.6.1.5 Precondition 5: security of natural colorant supply 600 29.6.2 Consumer Expectations 600 29.6.3 Market Research for Naturally Dyed Products 601 29.7 Production Costs of Natural Colorant Products 602 29.7.1 Cost Categories 603 29.7.2 Aspects Influencing Production Costs 603 29.8 Prices of Synthetic Dyes-- How Much Are Textile Companies Prepared to Pay for Dyes? 605 29.9 Acceptable Production Costs through a Mixed Portfolio (Agricultural Primary Production and Residues from Other Production Processes) 606 29.10 Closed- Loop Economy: Toward a Zero- Emission and Zero- Waste Society 607 29.11 Considerations Concerning the Life Cycle 609 29.12 Conclusion: Aspects Influencing Market Development for Natural Colorants 609 References 610 30 Aspects of Human Toxicology and Consumer Safety 613 Judith Büttler, Thomas Bechtold and Tung Pham 30.1 Introduction 613 30.2 Basic Aspects of Xenobiotic- Induced Toxicity 614 30.3 Toxicological Aspects of Natural Colorants in Food and Medical Applications 615 30.3.1 Risk Assessment 617 30.3.2 Therapeutic Effects (= Risk) 618 30.4 Toxicological Aspects of Natural Colorants in Cosmetics 618 30.4.1 Risk Assessment 619 30.5 Toxicological Aspects of Natural Colorants in Textile Dyeing 619 30.5.1 Plant Extracts 620 30.5.2 Pretreatment Agents and Mordants 621 30.5.3 Wastewater and Antimicrobial Compounds 621 30.5.4 Dyed Products 622 30.6 Test Methods for Toxicity Screening 622 30.6.1 Extract Preparation 624 30.6.2 Cytotoxicity 624 30.6.3 Mutagenicity and Carcinogenicity 625 30.6.4 Antimicrobial Activity 625 30.6.5 Metabolism and In Vivo Animal Bioassays 626 Acknowledgement 626 References 626 Index 629