Textile dyeing with a flavonoid dye Textile Textile dyeing with a flavonoid dye: photo-stability and analytical Alexandre Villela was chemistry methods born in Rio de Janeiro, Brazil in 1975. He studied chemistry in Brazil and the Netherlands: BSc at the Federal University of Rio de Janeiro, MSc at 2020 Alexandre Villela the Federal University of Santa Catarina, and PhD at Wageningen University. Alexandre is member of the International Society for Ethnopharmacology, and can be reached through alexandre.villela@ naturalproductschemistry. com. Alexandre Villela Propositions 1. There are limitations to the yellow colour of wool dyed with weld. (this thesis) 2. Using short UHPLC columns on conventional HPLC systems is an economical way of modernising HPLC-based analyses. (this thesis) 3. People and planet are better taken care of through organic agriculture than through conventional agriculture. (based on Reganold JP, Wachter JM. Nat. Plants 2016) 4. The release of genetically engineered organisms in natural, rural and urban areas is an ecocide. 5. The pursuit of excellence as human being must precede that of professional excellence. 6. Pride is fruit of short-sightedness. Propositions belonging to the thesis entitled Textile dyeing with a flavonoid dye: photo-stability and analytical chemistry methods Alexandre Villela Wageningen, 15 April 2020 Textile dyeing with a flavonoid dye: photo-stability and analytical chemistry methods Alexandre Villela Textile dyeing with a flavonoid dye: photo-stability and analytical chemistry methods Alexandre Villela Thesis committee Promotor Prof. Dr J.T. Zuilhof Professor of Organic Chemistry Wageningen University & Research Co-promotor Dr T.A. van Beek Assistant professor, Laboratory of Organic Chemistry Wageningen University & Research Other members Thesis Prof. Dr J.H. Bitter, Wageningen University & Research submitted in fulfilment of the requirements for the degree of doctor Prof. Dr R. Verpoorte, Leiden University at Wageningen University Prof. Dr P.J. Schoenmakers, University of Amsterdam by the authority of the Rector Magnificus, Prof. Dr M.H.M. Eppink, Wageningen University & Research Prof. Dr A.P.J. Mol, in the presence of the Thesis Committee appointed by the Academic Board This research was conducted under the auspices of the graduate school VLAG to be defended in public (Advanced studies in Food Technology, Agrobiotechnology, Nutrition and Health on Wednesday 15 April 2020 Sciences). at 1:30 p.m. in the Aula. Textile dyeing with a flavonoid dye: photo-stability and analytical chemistry methods Alexandre Villela Thesis committee Promotor Prof. Dr J.T. Zuilhof Professor of Organic Chemistry Wageningen University & Research Co-promotor Dr T.A. van Beek Assistant professor, Laboratory of Organic Chemistry Wageningen University & Research Other members Thesis Prof. Dr J.H. Bitter, Wageningen University & Research submitted in fulfilment of the requirements for the degree of doctor Prof. Dr R. Verpoorte, Leiden University at Wageningen University Prof. Dr P.J. Schoenmakers, University of Amsterdam by the authority of the Rector Magnificus, Prof. Dr M.H.M. Eppink, Wageningen University & Research Prof. Dr A.P.J. Mol, in the presence of the Thesis Committee appointed by the Academic Board This research was conducted under the auspices of the graduate school VLAG to be defended in public (Advanced studies in Food Technology, Agrobiotechnology, Nutrition and Health on Wednesday 15 April 2020 Sciences). at 1:30 p.m. in the Aula. In memory of my grandmother Pérola (Voca) Alexandre Villela Textile dyeing with a flavonoid dye: photo-stability and analytical chemistry methods, 168 pages. PhD thesis, Wageningen University, Wageningen, the Netherlands (2020) With references, with summary in English ISBN 978-94-6395-334-4 DOI-link https://doi.org/10.18174/516631 In memory of my grandmother Pérola (Voca) Alexandre Villela Textile dyeing with a flavonoid dye: photo-stability and analytical chemistry methods, 168 pages. PhD thesis, Wageningen University, Wageningen, the Netherlands (2020) With references, with summary in English ISBN 978-94-6395-334-4 DOI-link https://doi.org/10.18174/516631 Table of contents Chapter 1. General introduction 9 Chapter 2. LC–UV method for the quantitation of the main flavonoids of weld 17 Chapter 3. Spectrophotometric comparison of the content of chlorophylls in weld 33 Chapter 4. Photo-stability of the dye of weld in presence of aluminium ions 43 Chapter 5. Analysis of a natural dye: an experiment for analytical organic chemistry 69 Chapter 6. General discussion 77 Summary 87 Acknowledgements 91 Publications and training activities 95 Appendix A. Chapter 2: Supplementary information 99 Appendix B. Chapter 3: Supplementary information 103 Appendix C. Chapter 4: Supplementary information 109 Appendix D. Chapter 5: Supplementary information 147 Table of contents Chapter 1. General introduction 9 Chapter 2. LC–UV method for the quantitation of the main flavonoids of weld 17 Chapter 3. Spectrophotometric comparison of the content of chlorophylls in weld 33 Chapter 4. Photo-stability of the dye of weld in presence of aluminium ions 43 Chapter 5. Analysis of a natural dye: an experiment for analytical organic chemistry 69 Chapter 6. General discussion 77 Summary 87 Acknowledgements 91 Publications and training activities 95 Appendix A. Chapter 2: Supplementary information 99 Appendix B. Chapter 3: Supplementary information 103 Appendix C. Chapter 4: Supplementary information 109 Appendix D. Chapter 5: Supplementary information 147 Chapter 1 General introduction Chapter 1 General introduction 1.1. Introduction Coloured textiles have been used by mankind throughout times [1]. Dyes have been obtained from different natural sources, including plants, molluscs and insects [1] and were valuable in the past [2]. Although the use of natural dyes experienced a fast decline from the 1850s with the first synthetic dyes entering the market [3, 4], there has been a renewed interest. Currently, this is due to innovation-related, economical, personal, and ethical reasons [5]. Figure 1.1 depicts yarns dyed with natural dyes in various colours. The contents of this chapter are, to a large extent, part of the following papers: Villela A, van der Klift EJC, Mattheussens ESGM, Derksen GCH, Zuilhof H, van Beek TA. Fast chromatographic separation for the quantitation of the main flavone dyes in Reseda luteola (weld). J Chromatogr A 2011; 1218(47): 8544–50 Villela A, Derksen GCH, Zuilhof H, van Beek TA. Spectrophotometric comparison of the content of chlorophylls in weld (Reseda luteola). Anal Methods 2011; 3(6): 1424–7 Villela A, van Vuuren MSA, Willemen HM, Derksen GCH, van Beek TA. Photo-stability of a flavonoid dye in presence of aluminium ions. Dyes Pigments 2019; 162: 222–31 Villela A, Derksen GCH, van Beek TA. Analysis of a natural yellow dye: an experiment for analytical organic chemistry. J Chem Educ 2014; 91(4): 566–9 Figure 1.1. Yarns of wool dyed with natural dyes.1 In addition, identification of dyestuff of historical textiles is of historical and conservational interest [2]. Figure 1.2 depicts a live mannequin wearing a costume dyed with a natural dye. 1 Dyed by Judy Hardman (United Kingdom); picture taken in La Rochelle/France (2011). 10 11 1.1. Introduction Coloured textiles have been used by mankind throughout times [1]. Dyes have been obtained from different natural sources, including plants, molluscs and insects [1] and were valuable in the past [2]. Although the use of natural dyes experienced a fast decline from the 1850s with the first synthetic dyes entering the market [3, 4], there has been a renewed interest. Currently, this is due to innovation-related, economical, personal, and ethical reasons [5]. Figure 1.1 depicts yarns dyed with natural dyes in various colours. Chapter 1 The contents of this chapter are, to a large extent, part of the following papers: Villela A, van der Klift EJC, Mattheussens ESGM, Derksen GCH, Zuilhof H, van Beek TA. Fast chromatographic separation for the quantitation of the main flavone dyes in Reseda luteola (weld). J Chromatogr A 2011; 1218(47): 8544–50 Villela A, Derksen GCH, Zuilhof H, van Beek TA. Spectrophotometric comparison of the content of chlorophylls in weld (Reseda luteola). Anal Methods 2011; 3(6): 1424–7 Villela A, van Vuuren MSA, Willemen HM, Derksen GCH, van Beek TA. Photo-stability of a flavonoid dye in presence of aluminium ions. Dyes Pigments 2019; 162: 222–31 Villela A, Derksen GCH, van Beek TA. Analysis of a natural yellow dye: an experiment for analytical organic chemistry. J Chem Educ 2014; 91(4): 566–9 Figure 1.1. Yarns of wool dyed with natural dyes.1 In addition, identification of dyestuff of historical textiles is of historical and conservational interest [2]. Figure 1.2 depicts a live mannequin wearing a costume dyed with a natural dye. 1 Dyed by Judy Hardman (United Kingdom); picture taken in La Rochelle/France (2011). 10 11 Figure 1.2. Valérie Fischbach acting as a live mannequin OH 3' wearing a costume in Incroyables et Merveilleuses style 2' OH 2 4' dyed with weld (Reseda luteola L.). 8 1 8a 1' HO O 5' 7 2 6' 6 4a 3 5 4 OH O Figure 1.3. Structure of the flavone luteolin (lut), the aglycone of the main flavonoids of weld (Reseda luteola L.). RP-HPLC–UV (reversed phase high-performance liquid chromatography with spectrophotometric detection in the ultraviolet range of the electromagnetic spectrum) is a very suitable technique for the separation and detection of these non-volatile moderately polar UV- active analytes, and is available in most laboratories. Various assays have been published for the quantitation of flavonoids in weld, by different analytical techniques. RP-HPLC–DAD (RP- HPLC–diode-array detector) has been used to quantify the aglycones quercetin, luteolin, and apigenin in weld after simultaneous extraction-hydrolysis of the glycosides [10]. Other groups used RP-HPLC–UV to quantify only luteolin [11, 12]. Cristea et al. [13] extracted weld with methanol–water 8:2 at room temperature and under reflux and, afterwards, analysed the three main flavones by the same technique with external standardisation.