Editors

Thomas Bechtold, PhD, is a Professor at the Research Institute for Textile Chemistry and Textile Physics at the University of Innsbruck, Austria

Avinash P. Manian, PhD, is an Assistant Professor at the Research Institute for Textile Chemistry and Textile Physics, University of Innsbruck, Austria

Tung Pham, PhD, is the Head of Institute and BMK Endowed Professor at the Research Institute for Textile Chemistry and Textile Physics at the University of Innsbruck, Austria

Series Editor

Christian V. Stevens, Faculty of Bioscience Engineering, Ghent University, Belgium

List of Contributors xxi Series Preface xxv Preface xxvii I Historical Development 1 1 History of Natural Dyes in the Ancient Mediterranean Civilization 3Maria J. Melo 1.1 Introduction 3 1.1.1 Ancient Mediterranean World 3 1.1.2 Dyes from Antiquity 4 1.1.3 Unveiling the Secrets of Ancient Dyes with Modern Science 7 1.2 Ancient Reds 7 1.2.1 Anthraquinone Reds 7 1.2.2 Redwoods 10 1.2.3 Flavylium/Anthocyanin Reds 12 1.2.3.1 Equilibria in solution 13 1.3 Ancient Blues 14 1.3.1 Indigo Blues 14 1.3.2 Anthocyanin Blues 15 1.4 Ancient Purples 16 1.4.1 Tyrian Purple: Real Purple from Sea Snails 16 1.4.2 Orchil Purples 18 1.4.3 Folium 18 1.5 Ancient Yellows 20 1.5.1 Flavonoid Yellows 20 1.5.2 Carotenoid Yellows 21 1.5.3 Chalcone and Aurone Yellows 22 Acknowledgements 22 References 22 2 Colors in Civilizations of the World and Natural Colorants: History under Tension 27Dominique Cardon 2.1 Introduction 27 2.2 The Triumph of Mauveine: Synthetic Fulfillment of the Antique Purplemania 28 2.3 Blue: From Kingly Regional to Globally Democratic 29 2.4 Red and Yellow: From Micro to Macro Scales 29 2.5 What Is the Future for Natural Colorants in the Dawning Era of Renewable Resources? 30 Acknowledgement 31 References 31 3 History of Natural Dyes in North Africa_Egypt 33Harby Ezzeldeen Ahmed 3.1 Introduction 33 3.2 Natural Dyes in Pharaonic Textiles 34 3.3 Dyeing Techniques 34 3.4 Dye Sources 34 3.4.1 Woad 35 3.4.2 Indigo 35 3.4.3 Red 35 3.4.4 Yellow 36 3.4.5 Black 36 3.4.6 Brown 36 3.4.7 Green 36 3.4.8 Purple 36 3.5 Dyeing in Coptic Textiles 36 3.6 Wool- Dyed Fabric with Natural Dye 38 3.7 Dyes in Islamic Textiles 38 3.8 Mordants 40 References 40 II Natural Colorants in Different Regions of the World 43 4 Sources for Natural Colorants in Europe 45Thomas Bechtold, Tung Pham and Avinash P. Manian 4.1 Introduction 45 4.2 Cultivation 46 4.2.1 Potential European Dye Plants Yesterday and Now 46 4.2.2 Modern Cultivation Methods- General Facts 47 4.2.3 Blue- Dye Plants 48 4.2.4 Red- Dye 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 63Veridiana 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) 75Tung 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 89Ren-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 103Prof. (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 161Wendy 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 183María 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 195Philip 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 251Maria 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 271Goverdina 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 317Riikka 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 333Riitta 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 351U. 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...