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Allan J K, Tyrian Purple: An Ancient Industry, Australian Museum Magazine, 1934, 5(5), 147-151 A brief historical survey with drawings of Murex brandaris, Purpura lapillus, Tethys norfolkensis, Violet snails and ladder shells (Epitonium australe). No refs Aloupi E, Maniatis Y, Paradellis T, Karali-Yannacopoulou, L, Analysis of a Purple Material Found at Akrotiri, in Hardy, D.A, Thera and the Aegean World III, Vol. I: Archaeology, Proceedings of the Third International Congress, Santorini, September 03-09, 1989, London, 1990 Purple dye was found on powdered material at Akrotiri. It was probably used for cosmetics Andreotti A, Bonaduce I, Colombini M P, Ribechini, E, Characterisation of natural indigo and shellfish purple by mass spectrometric techniques, Rapid Communications in Mass Spectrometry, 2004, 18(11), 1213-1220 Online pyrolysis GC in the presence of hexamethyldisilazane followed by MS analysis (Py-silylation/GC/MS), and direct exposure MS (DE-MS), were used for indigo (from Indigofera tinctoria) and shellfish purple (from Murex trunculus). The following molecular markers were found to useful: 1,2-dihydro-3H-indol-3-one for indigoid dyes, 1,3-dihydro-2H-indol-2-one for indirubine, and 6-bromo-1,2-dihydro-3H-indol-3-one for shellfish purple. DBI, MBI and IND were found in shellfish purple and the presence of tyriverdin indicated. Augusti S, Sui Colori degli Antichi: Il Purpurissum, Rendiconti della Accademia di Archeologia, Lettere e Belle Arti, nouv. ser., 1961, 36, 123-130 Baker J T, Tyrian purple. Ancient dye, a modern problem, Endeavour, 1974, 33(118), 11-17 A review with 23 references Baker J T, Duke C C, Chemistry of the indoleninones. II. Isolation from the hypobranchial glands of marine molluscs of 6-bromo-2,2-dimethylthioindolin-3-one and 6-bromo-2-methylthioindoleninone as alternative precursors to Tyrian Purple, Australian Journal of Chemistry, 1973, 26, 2153-2157 The title compounds were isolated from ether extracts of Dicathais orbita. Both compounds are derived from sodium tyrindoxyl sulfate. Baker J T, Duke C C, Precursors of Tyrian Purple, Food-Drugs Sea, Proc. [Conf.], 4th, Meeting Date 1974, 1976, 345-353 A review and discussion of the formation of Tyrian Purple from mollusks with 25 references Baker J T, Duke C C, Isolation of Choline and Choline ester salts of Tyrindoxyl Sulphate from the Marine Mollusks Dicathais Orbita and Mancinella Keineri, Tetrahedron Letters, 1976, 1233-1234 Baker J T, Sutherland M D, Pigments of marine animals VIII. Precursors of 6,6'-Dibromoindigotin (Tyrian Purple) from the mollusc Dicathais Orbita Gmelin, Tetrahedron Letters, 1968, (1), 43-46 Chromatography and reactions of tyrindoxyl sulfate and the photolysis of tyriverdin Becker C, Did the people in Ayios Mamas produce purple-dye during the Middle Bronze Age? Considerations on the prehistoric production of purple-dye in the Mediterranean, Animals and Man in the Past: ARC-Publicatie, Groningen, the Netherlands, 2001122-134 Archaeological investigations with 77 refs Benkendorff K, Bioactive molluscan resources and their conservation: Biological and chemical studies on the egg masses of marine molluscs, Thesis, University of Wollongong, 1999 http://www.library.uow.edu.au/adt-NWU/public/adt-NWU20011204.154039/ contains abstract for and links to the entire thesis Benkendorff K, Bremner J B, Davis A R, Tyrian purple precursors in the egg masses of the Australian muricid, Dicathais orbita: A possible defensive role, Journal of Chemical Ecology, 2000, 26(4), 1037-1050 The fresh egg masses of Dicathais orbita contain a high proportion of tyrindoleninone, which reacts to form tyriverdin and subsequently Tyrian purple and 6-bromoisatin as the eggs develop and the larvae hatch. Tyrindoleninone and especially tyriverdin have antimicrobial activity. Benkendorff K, Bremner J B, Davis A R, Indole derivatives from the egg masses of Muricid molluscs, Molecules, 2001, 6(2), 70-78 A range of brominated indole derivatives were found in the egg masses of six species of muricid molluscs. Several non-brominated indoles were also present in the eggs of two Mediterranean Muricidae, although these were not found in the Australian species Benkendorf K, Westley C B and Gallardo C S, Observations on the production of purple pigments in the egg capsules, hypobranchial and reproductive glands from seven species of Muricidae (Gastropoda: Mollusca), Invertebrate reproduction and development, 2004, 46(2-3), 93-102 Tyrian purple is a well-known colourant that can be obtained from the hypobranchial glands of muricids. Here we investigate the presence of purple and related pigments in the hypobranchial glands, reproductive glands and egg capsules of three Rapaninae, three Ocenebrinae and one Muricinae species. Observations on the dissected specimens revealed the presence of purple pigmentation in the hypobranchial glands of all species. All of the Rapaninae and the Muricinae, but only some species of Ocenebrinae, appear to transfer the pigment precursors to their egg capsules. This provides evidence that the precursors of Tyrian purple are not produced for the sole purpose of protecting the egg masses as has been previously suggested. In all the subfamilies, the hypobranchial and reproductive (capsule and prostate) glands lie adjacent to one another. Colour changes in the reproductive glands, indicating the presence of dye precursors, were observed in two species of Rapaninae. In Dicathais orbita, colour changes could be seen in both the capsule glands of females and prostrate glands of males. The final colour was more red in the reproductive glands than the purple observed in the hypobranchial glands. Preliminary observations of detached hypobranchial gland sections in both D. orbita and Pterynotus triformis indicate a different suite of colour reactions occur when compared to sections that are intact and attached to the reproductive glands. This demonstrates that the reproductive glands can influence the chemical conversions of dye precursors synthesized by these species. Further studies on the secondary metabolism occurring within the hypobranchial glands and reproductive organs of Muricidae are ongoing, including histological sectioning and confirmation of the chemistry behind the colours observed and functional analysis of Tyrian purple precursors. Biggam CP, Whelks and purple dye in Anglo-Saxon England, THE ARCHAEO+MALACOLOGY GROUP NEWSLETTER, (9), 2006 A brief summary of written records which are being investigated to provide evidence for the importation of Mediterranean shellfish purple fabrics and whether Britain produced its own purple cloth and parchment http://home.earthlink.net/~aydinslibrary/MalacGp09.pdf Biggam CP, Knowledge of whelk dyes and pigments in Anglo-Saxon England, Anglo-Saxon England, 2007, 35 23-55 Anglo-Saxon texts in Latin, as well as glosses and glossaries, are peppered with words such as purpura, purpureus, murex, ostrum and others, which are usually found to have dictionary definitions involving the word 'purple'. In addition, some of the surviving manuscripts from the period have purple pages, and the 'vast textile wealth' of Anglo-Saxon churches and monasteries, is known to have included fabrics called purpurae. It has often been assumed, therefore, that religious communities, and the wealthier strata of secular society, would have been familiar with the extremely expensive and prestigious pigment and dye suggested by these words. The purpose of this paper is to attempt to assess the likelihood and extent of this presumed familiarity with whelk-derived colouring in Anglo-Saxon England. Two possibilities will be explored: that whelk-dyed fabrics and garments were imported into England from the Mediterranean region, and, secondly, that whelk dyeing was carried out in Britain. The first step is to acquire some background information which will enable such assessments to be made. 135 refs. Bizio B, Scoperta del principio purpureo nei due Murex brandaris e trunculus Lina., e studio delle sue proprietà, Annali delle Scienze del regno Lombardo-Veneto, 1833, 346-364 Boekschoten G J, Note on Roman Purple Winning at Chersonnissos, Basteria, Tijdschrift van de Nederlandse Malacologische Vereenigung, 1962, 26, 59-60 Report on a find of shells of Hexaplex trunculus from the Roman period at Chersonissos, Crete Born W, Purpura Shell-Fish, Ciba Review, 1937, 1(4), 106-110 A brief description of the researches of Lacaze-Duthiers and others, and historic drawings of molluscs Born W, Purple in Classical Antiquity, Ciba Review, 1937, 1(4), 111-118 A survey of the surviving relics from the Mediterranean industry Born W, Purple in the Middle Ages, Ciba Review, 1937, 1(4), 119-123 A survey of the use of shell-fish purple from 200 AD to 1453 AD Born W, The Use of Purple among the Indians of Central America, Ciba Review, 1937, 1(4), 124-127 The use of shellfish purple for dyeing and body painting, derived from Purpura pansa / patula Bouchilloux S and Roche J, Contribution a l'etude biochimique de la pourpre des Murex, Bull. Inst. Oceanographique, 1955, 52(1054), 1-23 Bouchilloux S and Roche J, Sur la pourpre des Murex trunculus et ses précurseurs, Comptes rendus des seances de la Societe de Biologie: Societe de Biologie de Lyon, 1954, 148, 1583-1587 Glands were extracted with ethanol (+2 degrees C, 2 d). After evaporation at 35 degrees C, paper chromatography (butanol - acetic acid - water, 78:5:17) showed Rf 0.29, 0.46 for Murex trunculus and Rf 0.50 for Murex brandaris. Column chromatography (Amberlite IRC50) gave the trunculus products as pale green and pale yellow crystals resp. which with purpurase gave blue and purple pigments Bouchilloux S and Roche J, Sur les prochromogenes et les pigments purpuriques de Murex trunculus Linné, Comptes rendus des seances de la Societe de Biologie: Societe de Biologie de Lyon, 1954, 148, 1732-1734 The two prochromogens from Murex trunculus are indoxyl sulfates which on hydrolysis give indigo and dibromoindigo Briend J, Humbert, J B, Tell Keisan (1971-1976), une cité phenicienne en Galilee, Fribourg-Göttingen-Paris, 1980, 1980 Report on the excavations at Tell Keisan, suggesting the existence of a purple dyeing workshop about 1100 B. C. Bruin F, Royal Purple and the dye industries of the Mycenaeans and Phoenicians, Sociétés et Compagnies de Commerce en Orient et dans l'Océan Indien (Acts du huitième colloque international d'histoire maritime, Beyrouth - 5-10 Septembre 1966), 1966, 73-90 Historical review of early use, molluscs used, technique of dyeing, chemistry and with details of electron spin resonance experiments. 156 references. Bruin F, Heineken F W and Bruin M, Electron spin resonance spectra of the basic indigoid dye radicals, Journal of Organic Chemistry, 1963, 28, 562-564 The dibromoindigo radical anion was generated using sodium hydroxide and acetone and observed by electron spin resonance spectroscopy. The esr spectrum of the product from Murex trunculus, processed according to the instructions of Aristotle and Pliny, was identical to that of synthetic dibromoindigo Bruneau P, Documents sur l'industrie Délienne de la Pourpre, Bulletin de Correspondance Hellénique, 1969, 93, 759-761 Report on Purple Dyeing at Delos in Antiquity Cardon D, Natural Dyes : Sources, Tradition, Technology and Science, Archetype Publications, 2007, 551-606 A translation of Le monde des teintures naturelles (2003) updated with more than 201 references Cardon D, Le monde des teintures naturelles, Belin, Paris, 2003, 421-467 Detailed descriptions in Chapter 11, with illustrations and 81 refs Cardon D, Teinture Precieuses de la Mediterranee - Pourpre - Kermes - Pastel, Carcassonne et Terrassa, 1999/2000, Exhibition catalogue, 179 page exhibition catalogue with examples of purple dyeing and a description of purple dyeing in antiquity. Cardon D, du Chatenet G, Guide des Teintures Naturelles, Delachaux et Niestlé, Lausanne, 1990, 338-354 A history and description of 7 species of molluscs with 23 references Cheek G T, Barthel, R V, Electrochemical studies of indigoid systems, Proc. - Electrochem. Soc., 93-11(Proceedings of the Fifth International Symposium on Redox Mechanisms and Interfacial Properties of Molecules of Biological Importance, 1993), 1993, 165-74 Redox potentials for the dibromoindigotin system were determined in order to determine the most likely reducing agent in the ancient process. Results suggest tin rather than lead or iron was the reagent. Christophersen C, Waetjen F, Buchardt O, Anthoni U, On the formation of indigotins, Tetrahedron Lett., 1977, (20), 1747-1748 A dimethylthio compound derived from the addition of methanethiol to dehydroindigo, gave on heating or exposure to light indigo and a similar precursor is postulated in the mollusks which give dibromoindigotin Christophersen C, Watjen F, [Organic marine chemistry of] purple, (Den.). Naturen Verden, 1978, (10), 326-334 A review in Danish of the history, biology, chemistry and dye use of Tyrian purple with 4 references Christophersen C, Watjen F, Buchardt O, Anthoni U, A revised structure of tyriverdin. The precursor of Tyrian purple, Tetrahedron, 1978, 34(18), 2779-2781 The spectral data for natural and synthetic tyriverdin are compared; synthetic tyriverdin was prepared from dibromoindigotin by acetylation, elimination of acetic acid and addition of methanethiol and the photochemical transformation to dibromoindigotin is shown to be a radical process Clark R J H, Cooksey C J, Bromoindirubins: the synthesis and properties of minor components of Tyrian purple and the composition of the colorant from Nucella lapillus, Journal of the Society of Dyers and Colourists, 1997, 113(11), 316-321 The identification of 6,6'-dibromoindirubin as a component of Tyrian purple has been confirmed by a practical synthesis; the first investigation of the composition of Tyrian purple from Nucella lapillus is reported Clark R J H, Cooksey C J, Monobromoindigos: a new general synthesis, the characterization of all four isomers and an investigation into the purple colour of 6,6'-dibromoindigo, New Journal of Chemistry, 1999, 323-328 6-Bromoindigo is synthesised and characterised. The purple colour of wool dyed with 6,6'-dibromoindigo is thought to be due to the interaction of the p system of two parallel molecules Clark R J H, Cooksey C J, Daniels M A M, Withnall R, Indigo - red, white and blue, Education in Chemistry, 1996, 33(1), 16-19 A review with 24 references and details of UV/VIS, IR and mass spectra of indigo, dibromoindigo and indirubin, and a preparation of the latter Clark R J H, Cooksey C J, Daniels M A M, Withnall R, Indigo, woad, and Tyrian Purple: important vat dyes from antiquity to the present, Endeavour, 1993, 17(4), 191-199 A review with 35 references and illustrations of molluscs and the mosaic in San Vitale, Ravenna Cocaign J Y, Le pourpre (nucella lapillus) et son utilisation comme teinture en Armorique, Annales de Bretagne et des Pays De L'Ouest, 1997, 104(4), 7-22 Cockburn J, A Journey over Land, from the Gulf of Honduras to the great South-Sea, performed by John Cockburn, and five other Englishmen, London: C Rivington, 1735 ... the Method used to die the Thread is only this, they take the Shell off the Rock where it sticks very fast, and rub it gently on the Thread, and then lay it down again where they found it, with great Care, for they are very cautious of killing the Fish. Eds: Coldstream J N, Huxley G L, Kythera - Excavations and Studies, London: Faber, 1972 Report on the excavations of Kythera with reference to the early purple dyeing industry there Cole W, Purple Fish, Philosophical Transactions of the Royal Society of London, 1685, 15, 1278-1286 In a letter to the Philosophical Society of Oxford, William Cole describes the colouring of linen with hypobrachial extracts of purpura species (with line drawings) from Minehead, the colour changes and odours on exposure to light and refers to ancient literature on Tyrian purple Cooksey C J, Making Tyrian purple, Dyes in History and Archaeology, 1994, 13, 7-13 A convenient synthesis of 6,6'-dibromoindigo via a nitrone Cooksey C J, TLC of the Indigoid Colorants in Shellfish Purple, Dyes in History and Archaeology, 1995, 14, 70-77 N-trifluoroacetylation provides solubility and TLV mobility to distinguish indigo and bromoindigos Cooksey C J and Sinclair R S, Colour Variations in Tyrian Purple Dyeing, Dyes in History and Archaeology, 2005, 20, 127-135 Theoretical calculations on the intermediate tyriverdin molecule formed during the formation of Tyrian purple from molluscs suggest that tyriverdin absorbs light maximally below 450nm and therefore has a yellow colour, rather than the green normally attributed to it. However, experiments on the colour pathway during oxidation of the leuco dye from chemically synthesised 6,6'-dibromoindigotin (DBI), the main constituent of Tyrian purple dyeings, shows that a green colour is produced when, some of the yellow leuco dye is oxidised to form a small amount of the blue-purple final product DBI. Overexposure of the leuco dye solution to UV radiation causes debromination and a change of colour from the red-purple hue of dyed DBI on cotton cellulose to the pure blue of indigotin itself. Variations in the colour of Tyrian purple dyeings reported over the years can be attributed to variations in the chemical compositions of the mollusc prochromogens, as recent studies have shown the presence of brominated and unsubstituted indigotins and indirubins. However the variations in colour shown by chemically synthesised DBI on different textile substrates are attributed here to the varying strengths of the intermolecular forces between the dye molecules and the substrate molecules and also possibly on the extent of self-aggregation or crystallinity of the DBI species in the final dyed product. The colour variations are quite significant, have been measured spectrophotometrically, and are specified quantitatively in international (CIE, CIELAB and Munsell) colour coordinates. Cooksey C J, Marine indirubins, in Indirubin, the red shade of indigo, editors Meijer L, Guyard N, Skaltsounis LA and Eisenbrand G, France: Life in Progress Editions, ISBN 2-9518029-0-0, 2006, 23-30 This chapter covers analytical techniques which have been applied to the purple pigment from shellfish to disclose the presence of indirubins (indirubin and three brominated indirubins), published analytical data on indirubins in shellfish, the chemical synthesis of bromoindirubins for use as analytical standards and some suggestions about the chemistry of the generation of indirubins in shellfish. Cooksey C, The Synthesis and Properties of 6-Bromoindigo: Indigo Blue or Tyrian Purple? The Effect of Physical State on the Colours of Indigo and Bromoindigos, Dyes in History and Archaeology, 2001, 16/17, 97-104 The first synthesis of 6-bromoindigo is reported and the properties are described. The purple colour of Tyrian purple probably arises from the closer stacking of the molecules compared to those of indigo, the situation being caused by van der Waals interaction between the bromine atoms Cooksey C and Withnall R, Chemical studies on Nucella lapillus, Dyes in History and Archaeology, 2001, 16/17, 91-96 The first investigations into the chemical nature of the initial precursors of the purple dye in Nucella lapillus and the composition of the resulting dye suggest that it is very similar to those of the dyestuff from Dicathais orbita and Thais clavigera Cooksey C J, The Synthesis of minor Components of Shellfish Purple: Bromoisatin, Bromoindigotin and Bromoindirubins, from Dibromoindigotin, Beiträge zur Waidtagung, 1998, 7, 71-74 Chemical oxidation of dibromoindigo gives 6-bromoisatin which can serve as a precursor to other mollusc pigments Cooksey C J, Tyrian purple: 6,6'-Dibromoindigo and Related Compounds, Molecules, 2001, 6, 736-769 A review with 133 references; available from http://www.mdpi.org/molecules/papers/60900736.pdf Cooksey C J, Dronsfield A T and Edmonds J, First, catch your fish, Education in Chemistry, 2005, 24(1), 16-19 The synthesis of dibromoindigo based on the Pinkney and Chambers route is described with examples of dyeing of wool and cotton Daniels V, The light-fastness of textiles dyed with 6,6'-dibromoindigotin (Tyrian purple), Journal of Photochemistry and Photobiology A: Chemistry, 2006, 184(1-2), 73-77 Samples of cotton, linen, silk, wool, Nylon 6 and Nylon 66 were dyed with dibromoindigo, reflectance spectra were measured, showing wavelength maxima between 522 (wool) and 540, 594 nm (Nylon 66) and fading under daylight simulation illumination measured. Least fading was obtained with wool and most fading with cotton Daniels V, Further work on the dye analysis of textile fragments from Enkomi, Dyes in History and Archaeology, 1987, 6, 3-7 Purpurin is identified (by TLC) in addition to dibromoindigotin. Extraction with 1:1 aqueous dimethylformamide differentiated between indigotin (soluble) and dibromoindigotin (insoluble) Daniels V, Dye analysis of two fragments from Enkomi, Dyes in History and Archaeology, 1985, 4, 15-18 Dibromoindigotin and indigotin on its own were identified in two textiles from Enkomi. Analysis was by extraction with hot pyridine followed by spectroscopy when indigo showed maximum absorption at 611.5 nm (20 deg) and 606 nm (60 deg) and dibromoindigotin at 601 nm (20 deg and 60 deg) [Note: this textile later proved to be from Kertch, E. Crimea - ed] Desjacques J P, Koeberlé P, Mogador et les Iles Purpuraires, Hespéris, 1955, 42, 193-202 Investigation into the origin of Gaetulian Purple. The authors demonstrate the existence of purple dyeing on Mogador and the origin of Gaetulian purple from this island Desrosiers S, Textiles decouverts dans deux tombes du Bas-Empire à Naintré (Vienne), in Cardon, D. u. Feugere, M., Archéologie des Origines au Ve Siècle, Montagnac, 2000 Find of purple dyestuff on textile material from a children's grave dated 4 - 5 century AD Doumet J, Étude sur la couleur pourpre ancienne et tentative de reproduction du procédé de teinture de la ville de Tyr décrit par Pline l'Ancien, Imprimerie Catholique, Beirut, 1980 Doumet J, De la Teinture en Pourpre des Anciens par l'Extraction du Produit Colorant des Murex Tronculus, Brandaris et des Purpura Haemastoma, National Museum News, 1999, 9, 10-18 The recipe of Pliny is detailed with emphasis on the use of tin metal as a reductant. With pictures of the relevant mollusks. Doumet J, De la Teinture en Pourpre des Anciens, Teintures précieuses de la Méditerranée: Musée des Beaux-Arts, Carcassonne, 1999-2000, 1999, 46-57 The recipe of Pliny is detailed with emphasis on the use of tin metal as a reductant. With pictures of the relevant mollusks. Driessen L A, Über eine charakteristische Reaktion des antiken Purpurs auf der Faser, Melliand Textilberichte, 1944, 25, 66 Photodebromination of leuco-dibromoindigo by UV or sunlight is described Dubois R, Sur la formation de la pourpre de Purpura lapillus, Comptes rendus de l'academie des sciences, 1903, 136, 117-118 A note which refutes the assertion of Letellier that the mechanism of formation of the purple is different in Purpura lapillus and Murex brandaris: the precursor, purpurine, is acted on by an enzyme, purpurase Duhamel du Monceau H L, Quelques experiences sur la liqueur colorante que fournit la Pourpre, Mémoires de l'Académie Royale des Sciences, Paris, 1736, 49-63 Working with a Murex on the coast of Provence, he showed that light is necessary for the development of colour from purple producing mollusks Edmonds J, Tyrian or Imperial purple dye, Historic Dye Series No 7, ISBN 0 9534133 65, 2000, 41pp Historic Dye Series No 7; Ancient vat dyeing was performed using biochemical reduction analogous to that used in woad dyeing. 18 refs Elsner O, Solution of the enigmas of dyeing Tyrian purple and the biblical tekhlet, Dyes in History and Archaeology, 1991, 10, 11-16 The ratio of indigotin to dibromoindigotin in the purple dye derived from Phyllonotus (Murex) trunculus alters as this mollusc changes its sex. The dye must be vatted, although other shellfish such as Thais (Purpura) haemostoma may be used as direct dyes. A range of shades can be obtained, one of which may be the biblical 'tekhelet' Elsner O, Spanier E, Dyeing with Murex extracts, an unusual dyeing method of wool to the Biblical sky blue, Proceedings of the 7th International Wool Textile Research Conference, Tokyo, 1985, 1985, 5, 118-130 The dyeing of wool with Tyrian purple to give tekhlet by a mollusk sex segregation method and by the photochemical debromination method are discussed Elsner O, Spanier E, The dyeing with Purpura haemostoma, 7th International Symposium on Fiber Science & Technology, September 1985, Hakone, Japan, 1985 Experiments in dyeing with P. haemastoma, which gives a reddish purple and was considered in antiquity to be a poorer dye Fabius Columna, De Purpurea, Rome, 1616 Woodcuts of molluscs used for purple Forbes R J, , Studies in Ancient Technology: Leiden, 1964, 4, Purple dyeing is described in the context of the dyeing methods of Antiquity . The reports of Plinius and other authors of Antiquity on purple dyeing are rendered Fouquet H, Bielig H J, Biological Precursors and Genesis of Tyrian Purple, Angewandte Chemie (Int Edit), 1971, 10, 816-817 Four chromogens in Murex trunculus are identified; the major chromogen of Murex brandaris, M. erinaceus and Purpura haemastoma is 6-bromo-2-methylsulfonyl-indoxyl sulfate Fouquet H, Bielig H J, Biologische Vorstufen und Genese von antikem Purpur, Angewandte Chemie, 1971, 83, 856-857 Four chromogens in Murex trunculus are identified; the major chromogen of Murex brandaris, M. erinaceus and Purpura haemastoma is 6-bromo-2-methylsulfonyl-indoxyl sulfate Fouquet H, Bau und Reaktionen natürlicher Chromogene indigoider Farbstoffe bei Purpurschnecken., Ph.D. Thesis. University of Saarbrücken, Saarbrücken, 1970 A major study of the chromogens of Mediterranean molluscs and their subsequent reactions giving Tyrian purple Fox M R, Pierce J H, Indigo: Past and Present, Textile Chemist and Colorist, 1990, 22(4), 13-15 A brief history with no references Friedlander P, Uber die Farbstoffe aus Purpura aperta und Purpura lapillus, Berichte der Deutschen Chemische Gesellschaft, 1922, 55, 1656-1658 Extraction of Tyrian purple from Purpura aperta and Purpura lapillus is described and photographs of these molluscs as well as Murex brandaris and Murex trunculus shown Friedlander P, Uber den Farbstoff des antiken Purpurs aus murex brandaris, Berichte der Deutschen Chemische Gesellschaft, 1909, 42, 765-770 The first identification of 6,6'-dibromoindigo from Murex brandaris, when 1.4g of dye was isolated from 12,000 mollusks, determined the empirical formula, synthesised it by two different routes and the products shown to have identical light absorption Friedlander P, Bruckner, S and Deutsch G, Uber Brom- und Methoxyderivate des Indigos, Annalen, 1912, 388, 23-49 The syntheses of dibromo- and dimethoxy-indigos is described; 6,6'-dibromoindigo has an absorption maximum of 585 nm in tetrachloroethane Fujii H, Sakamoto K and Ichihashi M, Textiles from at-Tar Caves - Part II-(3): Cave 16, Hill C, al-Rafidan, 1993, 14, 109-133 Details of textiles dyed with Tyrian purple, kermes, indigo and an unidentified yellow dye Fujise Y, Chemistry of the Production of Tyrian Purple and Related Natural Products, Kagakushi, 1999, 26(1), 34-44 A summary of chemical investigations since 1909 with 24 references Fujise Y, Miwa K and Ito S, Structure of tyriverdin, the intermediate precursor of Tyrian purple, Chemistry Letters, 1980, (6), 631-632 Stereoisomeric tyriverdins were isolated from Thais clavigera and characterised by UV, NMR (1H and 13C) and IR spectroscopy Gage T, The English-American. A new survey of the West-Indies, George Routledge & Sons Ltd: London, 1928, 359 An edited reprint of the 1648 1st edition. At Chira, Golfo de Salinas and Nicoya, shellfish are used to dye pita (a thread) Gage T, A new survey of the West-India's: or, The English American his travail by sea and land; ..., J. Sweeting: London, 1655, 192-193 2nd edition. Dyeing of thread (Pita) and Segovia cloth with shellfish at Nicoja Garay L, Le coquillage a Pourpre, Archimède, l'école des loisirs. Paris. ISBN 2 211 03684 8, 1996 Text and pictures of purple dyeing with Purpura pansa Gerhard P, Emperors' Dye of the Mixtecs, Natural History, 1964, 73(1), 26-31 History of the use of Purpura patula in Mexico and the current use at Pinotepa de Don Luis for making the posahuanco Gerlach, H J, Verfahren zur Herstellung von 2-Nitrobrombenzaldehyden sowie von 6,6'-Dibromindigo, Ger. Offen. DE 3910648 A1 901004 (BASF AG), 1990 4-Bromo-2-nitrobenzaldehyde is prepared in 92% yield by selective lithiation of 1,4-dibromo-2-nitrobenzene followed by reaction with dimethylformamide, and converted into 6,6'-dibromoindigotin by reaction with nitromethane followed by reduction. Ghiretti F, Bizio, Bartolomeo and the rediscovery of Tyrian purple, Experientia, 1994, 50(9), 802-807 A review with 33 references, claiming that the origin and chemical properties of Tyrian purple were first described by Bartelmeo Bizio, a Venetian chemist, whose description of the nature and properties of the dye was not only accurate, but predate what were claimed as original discoveries by later authors Gibaja Oviedo S, Salazar de Cavero L, Production of Tyrian purple from the Concholepas mollusk "Chanque", Boletin de la Sociedad Quimica del Peru, 1977, 43(3), 139-40 A light green extract of the hypobranchial gland of the mollusk gave a single greenish-yellow band on paper chromatography which turned to purple when exposed to sunlight Glover B, Are natural colorants good for your health - are synthetic ones better, Textile Chemist and Colorist, 1995, 27(4), 17-20 The feasibility and/or desirability of using natural dyes is compared to the alternative use of synthetic products including Tyrian purple and cochineal Glover B, Pierce J H, Are natural colorants good for your health ?, Journal of the Society of Dyers and Colourists, 1993, 109(1), 5-7 The impractibility of using mollusc dyeing in the modern world is discussed Golding B T, Pierpoint C, Indigo Blue, Education in Chemistry, 1986, (3), 71-73 A brief history with biosynthetic details Grandmougin E, Seyder P, Uber Indigo. V:Uber halogenierte Indigo und Derivate, Berichte der Deutschen Chemische Gesellschaft, 1914, 47, 2365-2373 The synthesis of dibromoindigotin is described from 6,6'-diaminoindigo by diazotization and reaction with copper(I) bromide and absorption maxima in xylene (591.6, 536.5 nm) and methyl benzoate (593.3, 554.0 nm) determined Greenberg H S, An Improved synthesis of Tyrian purple, M.A. Thesis (Temple University), 1964, 49 A synthesis via a nitrone intermediate is described, see Cooksey (1994); 49 pages Greenspan A, Bromine, Chemical & Engineering News, 2003, 81(36), 96 A short article introducing the element bromine is presented. The use of bromine as a dye in ancient Rome times, the Talmud, and the bible is discussed. The author describes his interaction with the Murex trunculus snail that has the ability to take bromine from the sea and bind it to indigo, forming dibromoindigo - Tyrian purple Grosjean D, Sensharma, D K & Cass G R, Fading of colorants by atmospheric pollutants: mass spectrometry studies., The Science of the Total Environment, 1994, 152(2), 125-134 Chemical ionization mass spectra are reported for curcumin, indigos, alizarin derivatives and isatins, the products of ozone-induced fading of indigo pigments. Grosjean D, Whitmore P M, Cass G R, Druzik J R, Ozone fading of natural organic colorants: mechanisms and products of the reaction of ozone with indigos, Environ. Sci. Technol., 1988, 22(3), 292-298 Samples of dibromoindigotin exposed to 10 ppm of ozone for 4 days were entirely decomposed to bromoisatin and bromoisatoic anhydride, as revealed by MS Haubrichs R, L'etude de la pourpre: histoire d'une couleur, chimie et experimentations, Preistoria Alpina, 2005, Suppl. 1, v.40, 133-160 An illustrated bibliography of the ancient use of purple, the molluscs from which it is obtained, its archaeology, literature, chemistry and different dyeing techniques. About 224 refs Haubrichs R, Natural history and iconography of purple shells, in Indirubin, the red shade of indigo, editors Meijer L, Guyard N, Skaltsounis LA and Eisenbrand G, France: Life in Progress Editions, ISBN 2-9518029-0-0, 2006, 55-70 The descriptions of molluscs in ancient literature, both in text and in illustrations, are accurate enough from the sixteenth century on to enable identification of the species used to obtain the Tyrian purple so prized in the Mediterranean region. This study is completed by an overview of some descriptions of other purple molluscs from various parts of the world, dating from the seventeenth to the nineteenth centuries. A brief account of the many illustrations which adorn the works reviewed is also given. 18 illustrations, 65 refs. Herzog I, The dyeing of purple in anciant Israel, Proceedings of the Belfast Natural History and Philosophical Society, 1919-1920, 2, 21-33 A history of argaman and tekhelet Hidaka S, Chemistry of the purple coloring matter from shellfish, Sen'i Kako, 1984, 36(6), 279-283, 300 A review with 10 references Higa T, Scheuer P J, Bisindoxyl-derived blue marine pigments, Heterocycles, 1976, 4(2), 227-230 The marine invertebrate Ptychodera flava laysanica contained 3 blue pigments, 6,6'-dibromoindigotin, 5,5',7,7'-tetrabromo-6,6'-dimethoxyindigotin, and 5,6',7-tribromo-6-methoxyindigotin, in addition to a colorless companion, 5,7-dibromo-6-methoxyindole Hiyoshi Y, Chemical education with familiar material in our hometown -- Dyeing with Tyrian purple from Thais bronni, Kagaku to Kyoiku, 1989, 37, 654-655 Hiyoshi Y, Fujise Y, Tyrian purple. As a learning tool for natural product chemistry, Kagaku to Kyoiku, 1992, 40(6), 390-393 The isolation of Tyrian Purple from Thais clavigera and T. bronii, conversion of it to indigotin and dyeing of cotton or silk is described. Hoffmann R, Marginalia - Pigments from a Snail - Biblical Blue and the Royal Purple, American Scientist, 1990, 78(4), 308-309 An historical review with 5 references on the production and identification of dibromoindigotin and tekhelet Hoffmann R, The Royal Purple and the Biblical Blue - Argaman and Tekhelet - The Study of Chief Rabbi Herzog,Isaac on the Dye Industries in Ancient-Israel and recent Scientific Contributions - Spanier,E, TLS-the Times Literary Supplement, 1989, (4524), Book review Hoffmann R, The royal purple and the biblical blue, Abstracts of papers of the American Chemical Society, 1999, 217(2), 1 Horn P, Textilien in biblischer Zeit - Die Färberei, Ciba-Rundschau, 1968, (2), 17-23 Review on dyeing methods of the Jews with some remarks on purple dyeing particularly on old workshops Huxtable R J, The Mutability of Blue, Molecular Interventions, 2001, 1(3), 141-144 A brief summary with 10 references of the origin and history of indigo (dye, pigment, in urine) and Tyrian purple (tekhelet) Imming P, Zentgraf M and Imhof I, An improved synthetic procedure for 6,6'-dibromoindigo (Tyrian purple), Synthetic Communications, 2001, 31(23), 3721-3727 A simple synthetic procedure is described that yields 6,6'-dibromoindigo in considerably improved overall yield (10%), of analytical purity and also being amenable to scale-up Imming P, Zentgraf M and Imhof I, Welche Farbe hatte der antike Purpur?, Textilveredlung, 2000, 35(9 to 10), 22-24 A review Imming P, Purpur, die Farbe der Kaiser, Pharmazeutische Zeitung, 2000, 145(16), 1263-1266 History and chemistry with 13 references Jackson J W, The Geographical Distribution of the Shell-Purple Industry, London: Longmans, Green and Co, 1917, 1-29 A chapter in 'Shells as Evidence of the migrations of early culture' with 92 references Jannun R and Coe E L, Bromoperoxidase from the marine snail, Murex-trunculus, Comparative Biochemistry and Physiology B-Comparative Biochemistry, 1987, 88B(3), 917-922 Jensen L B, Royal Purple of Tyre, Journal of Near Eastern Studies, 1963, 22, 104-118 A review of purple dyeing in Antiquity with remarks on finds of shells of purple snails, on purple dyeing and on the importance of purple Jodin A, Les établissements du roi Juba II aux îles Purpuraires (Mogador), fouilles du Service des antiquités du Maroc, Tanger, 1967 Based on the report of Plinius on Gaetulian purple its nature is discussed. According to the conclusion of the author it was dyed by using purple snails on the island Mogador Juan, Don Jorge and de Ulloa, Don Antonio, Relacion Historica del viage a la America Meridional, Madrid, 1748, (book 4), 242-244 Observations in 1744 of the dyeing methods used in Guayaquil (Ecuador) and Nicoya (Costa Rica) where cotton thread is drawn through the shellfish secretion, when after drying it becomes green then purple. Kanold I B, The Purple Fermentation Vat: Dyeing or Painting Parchment with Murex trunculus, Dyes in History and Archaeology, 2005, 20, 150-154 In January 2001, Inge Boesken Kanold succeeded in reconstructing a fermentation vat using fresh Murex trunculus with the help of John Edmonds' book. This was done at the Conservatoire des Ocres et Pigments Appliqués in Roussillon, Provence, during a private workshop where several ancient purple specialists were present. The escargot de mer, as the French call it, is available at the local markets. It was then suggested that we should demonstrate the operation of a working vat of shellfish purple that was described by Pliny in ancient times, but has not been used since 1453, at the 20th DHA meeting in Amsterdam in November 2001. During the following months, while preparing for travelling with fresh molluscs, the idea came up to preserve cut-out murex glands in salt in order to be independent of markets and seasons. Experiments were carried out to prove the feasibility. In August 2001, the first fermentation vat using dried murex glands produced dark purple coloured wool. This led to more research on a purple related subject: the parchment. Besides using the method of dyeing parchment in a cold murex vat, she also managed to paint the surface with the coloured liquid. Finally she invented a recipe of staining parchment in an artistic way by dipping the material in cut-out fresh glands for several hours, even days. Karapanagiotis I, de Villemereuil V, Magiatis P, Polychronopoulos P, Vougogiannopoulou K, and Skaltsounis A-L, Identification of the Coloring Constituents of Four Natural Indigoid Dyes, Journal of Liquid Chromatography & Related Technologies, 2006, 29, 1491-1502 A high performance liquid chromatography (HPLC) method combined with spectrophotometric UV-Vis detection is developed for the separation and identification of seven indigoid coloring compounds: indigotin, which is commercially available, and indirubin, 6-bromoindigotin, 6'-bromoindirubin, 6-bromoindirubin, 6,6'-dibromoindigotin, and 6,6'-dibromoindirubin, which are synthesized to be used as reference compounds in the HPLC analysis. The chromatographic method is employed for the identification of the blue/purple coloring compounds in samples extracted from four mollusks, which have been used for the production of Tyrian Purple since antiquity: Hexaplex trunculus, Murex brandaris, Nucella lapillus, and Thais haemastoma. The composition of the analyzed samples, with respect to the reference materials, is compared and discussed. All seven indigoids are identified in Hexaplex trunculus and some of them are identified in the other three purple extracts. Karapanagiotis I, Identification of Indigoid Natural Dyestuffs Used in Art Objects by HPLC Coupled to APCI-MS, American Laboratory, 2006, 38(3), 36-39 HPLC with spectrophotometric detection (UV-VIS) and coupled with mass spectrometry (MS-APCI) was utilized for the separation and detection of six indigoids, which allowed unequivocal identification of Tyrian Purple in an extract originating from a historic painting from the Late Bronze Age (17th century B.C., Greece). Karman N, Spanier E, Remains of a Purple Dye Industry Found at Tel Shiqmona, Israel Exploration Journal, 1988, 38, 184-186 Report on a dyeing workshop from the 9th century B. C. found in Tel Shiqmona in Israel. Fragments of dyeing vessels and shells of purple snails were found there Karmous T, Alatrache A, Ayed N, Chemistry as a tool for differentiation between natural and synthetic dyes, Bulletin - Union des Physiciens Paris, 2000, 94(820), 13-23 The authors identified a dye sample represented as the natural dye Royal purple as actually being basic fuchsin, using solubility, redox behaviour, the effect of pH on colour, TLC, IR spectra, and direct dyeing behaviour Karmous T, Ayed, N, Fantar M H, Wouters J, Analysis of Punic Natural Dyes: Purple Earth from Zembra and Cosmetic Make-up from Carthage, Dyes in History and Archaeology, 1996, 14, Dibromoindigo was found in an earth specimen from Punic time on the isle of Zembra Kazumi U, Ikue H, Kiyoko I, Tousaku K, Teruko A, Color analysis by means of a color computer system - an examination into the color-changing process of the Tyrian purple and its dyeing effects, Kenkyu Kiyo - Tokyo Kasei Daigaku, 2: Shizen Kagaku, 2003, 43, 77-85 Kelley WP, Wolters AM, Sack JT, Jockusch RA, Jurchen JC, Williams ER, Sweedler JV, Gilly WF, Characterization of a novel gastropod toxin (6-Bromo-2-mercaptotryptamine) that inhibits shaker K channel activity, Journal of Biological Chemistry, 2003, 278(37), 34934 - 34942 http://www.jbc.org/cgi/reprint/M301271200v1.pdf A novel potassium channel antagonist has been purified from the defensive mucus secreted by Calliostoma canaliculatum, a marine snail found in the temperate coastal waters of the western Pacific. The toxin is expelled from the hypobranchial gland as part of a defensive response and is contained within a viscous matrix that minimizes dilution and degradation. The active compound was isolated by multistage microbore HPLC separations followed by bioactivity assays. Nuclear magnetic resonance, combined with electrospray ionization Fourier transform ion cyclotron resonance and electrospray ionization ion trap mass spectrometry indicate that the active component is a heretofore unknown indole-derivative, a disulfide-linked dimer of 6-bromo-2-mercaptotryptamine (BrMT). Exudates from the hypobranchial glands of various marine mollusks have been sources for dye compounds such as 6-6 dibromoindigo, the ancient dye Tyrian purple. BrMT represents the first correlation of a hypobranchial gland exudate with a molecular response. Voltage clamp experiments with a number of K channel subtypes indicate that BrMT inhibits certain voltage-gated K channels of the Kv1 sub-family. Kimura M, Sakamoto K, Fujii H, Studies on identification of the natural dyes on the textiles from at-Tar caves, al-Rafidan, 1993, 14, 141-148 2000 year old samples of kermes and Tyrian purple / indigo dyes on wool are distinguished by UV/VIS spectra following extraction with dimethylformamide and DMF-NaOH solutions giving wavelength maxima at 550-600 nm (two peaks) and 600-620 nm respectively Koren Z C, HPLC analysis of the natural scale insect, madder and indigoid dyes, Journal of the Society of Dyers and Colourists, 1994, 110, 273-277 A linear gradient elution method applied to dyes which are found on ancient textiles, including indigotin, its mono- and di-brominated compounds, and indirubin and a previously undetected component from Murex trunculus, tentatively identified as a dibromoindirubin Koren Z C, High-performance Liquid Chromatographic Analysis of an Ancient Tyrian Purple Dyeing Vat from Israel, Israel Journal of Chemistry, 1995, (35), 117-124 HPLC analysis of Tyrian purple from modern Murex trunculus and from a basin shard from Tel Kabri, dated to the 7th century BCE, showed similar compositions, mainly dibromoindigo with smaller amounts of monobromoindigo, indigo and dibromoindirubin Koren Z C, The First Optimal All-Murex Completely Natural Purple Dyeing in the Eastern Mediterranean in a Millennium and a Half and its Colorimetric Characterization, Dyes in History and Archaeology, 2005, 20, 136-149 Experiments with Hexaplex trunculus are described in which a dye vat is prepared at pH 9 and 50 degrees C and the solution used to dye wool. The colors obtained, purples and blues, were analysed. Koren Z C, HPLC-PDA analysis of brominated indirubinoid, indigoid, and isatinoid dyes, in Indirubin, the red shade of indigo, editors Meijer L, Guyard N, Skaltsounis LA and Eisenbrand G, France: Life in Progress Editions, ISBN 2-9518029-0-0, 2006, 45-53 A reverse-phase HPLC-PDA method has been formulated for the identification of isatinoid, indigoid and indirubinoid dyes, and applied to their detection in Tyrian Purple pigments from Murex trunculus sea snails. These pigments are spontaneously produced from indoxyl precursors in excised hypobranchial glands of various mollusca. The linear gradient elution method consists of an aqueous acidic methanolic system and separates ten brominated and unbrominated indole and biindole dione colorants in under thirty minutes. This is the first time that all of these components were analyzed by a single elution method, which would allow for the multicomponental chemical fingerprinting of modern and archaeological molluskan pigments. 40 refs. Koren Z C, Archaeo-chemical analysis of Royal Purple on a Darius I stone jar, Microchimica Acta, 2007, High-performance liquid chromatography (HPLC) coupled with photodiode array (PDA) detection was used for the microchemical analysis of a purple residue on the surface of a 2500-year old stone jar. This 30 × 37cm pear-shaped marble vessel contains carved inscriptions praising the Persian king Darius I and is unique due to the use of quadrilingual writings on a vessel of that king. The major colorants identified in the purple pigment are 6,6'-dibromoindigo, 6-monobromoindigo, and 6,6'-dibromoindirubin, with negligible contributions by indigo and 6-bromoisatin. This analysis establishes that a marine mollusk was the source of the purple pigment, which is the famous Royal Purple or Tyrian Purple of the ancients. A comparison with the relative dye compositions of various Muricidae species (Hexaplex trunculus, Bolinus brandaris, and Stramonita haemastoma), and with their newly formulated Di-Mono Index values, suggests that the biological provenance of this ancient pigment was probably an indigo-deficient Hexaplex trunculus sea snail. The entire exterior of the vessel - including its base - was originally painted purple by using a fresco-type technique. This is only the second chromatographic finding of a molluskan purple colorant in use as an ancient paint pigment and not as a textile dye, and the only example yet discovered where it is the sole paint pigment on such a large royal art object. Kosugi Y & Matsumoto K, A convenient and rapid detection method of Kaimurasaki coloring matter by MS., Bunseki Kagaku, 1994, 43(12), 1133-1136 Mass spectrometry has been applied to the analysis of Kaimurasaki (Tyrian purple) obtained from the hypobrachial glands of Akanishi-gai (Rapana venosa Valencinnes) Larsen S, Watjen F, The crystal and molecular structures of tyrian purple (6,6'-dibromoindigotin) and 2,2'-dimethoxyindigotin, Acta Chemica Scandanavica, Ser. A, 1980, A34(3), 171-176 Crystals of dibromoindigotin are monoclinic, space group P21/c, a=12.609, b=4.842, c=11.611, beta=104.42 and Z=2; the final R was 0.037 Leshchenko P, Royal purple, Khimiia i Zhizn, 1982, 51-54 The history of discovery of the title dye in mollusks is presented, including methods of isolation, availability, and chemical structure. Letellier A, Recherches sur la pourpre produite par le Purpura lapillus, Archives de Zoologie Expérimentale et Générale, deuxième série, 1890, 8, 361-403 A detailed examination of the hypobranchial gland of Purpura lapillus and the intermediates which eventually lead to the purple colour Letellier A, Recherches sur la pourpre produite par le Purpura lapillus, Comptes rendus de l'academie des sciences, 1889, 109, 82-85 A summary of Letellier (1890) Lacaze-Duthiers H, Mémoire sur le Pourpre, Annales des Sciences Naturelles comprenant la Zoologie, la Botanique, 1859, 4th series, 12, 5-84 A historical and zoological survey with drawings of the hypobranchial glands of M brandaris, P lapillus, M trunculus, M erinaceus Lacaze-Duthiers H, Mémoire sur le Pourpre, Mémoires de la Sociéte Imperiale des Sciences de l'Agriculture et des Arts de Lille, 1859, 2éme Serie, 6, 303-380 A multi-part review and research summary Lincke G, Molecular stacks as a common characteristic in the crystal lattice of organic pigment dyes. A contribution to the "soluble-insoluble" dichotomy of dyes and pigments from the technological point of view, Dyes and Pigments, 2003, 59, 1-24 Dichloroindigo and dibromoindigo have a different stack spacing from the parent indigo Magiatis P and Skaltsounis L, From Hexaplex trunculus to new kinase inhibitory indirubins, in Indirubin, the red shade of indigo, editors Meijer L, Guyard N, Skaltsounis LA and Eisenbrand G, France: Life in Progress Editions, ISBN 2-9518029-0-0, 2006, 147-156 Gastropod mollusks of the Muricidae family have been used since the antiquity to produce the "Tyrian purple" dye. In an effort to identify kinase inhibitors, we investigated the natural indirubins produced by the Mediterranean mollusk Hexaplex trunculus. Bio-guided fractionation of the extracts of that mollusk, led to the isolation of a new natural product, 6-bromoindirubin. See Meijer 2003. This product showed very strong inhibitory activity against glycogen synthase kinase (GSK-3) and was used as a lead compound for the synthesis of several derivatives, with various substituents at positions 1,4,5,6,3',6'. The product 6-bromo-indirubin 3'-oxime (BIO) showed the most powerful activity (IC50 = 5 uM), combined with very good selectivity for GSK-3. Using the co-crystal structures of various indirubins with GSK-3beta, CDK2 and CDK5/p25, we have modelled the binding of indirubins within the ATP-binding pocket of these kinases. This modelling approach provided some insight into the molecular basis of indirubins' action and selectivity and allowed us to forecast some improvements of this family of bis-indoles as kinase inhibitors. Malaszkiewicz J, Chromogene und Farbstoff-Komponenten der Purpurschnicke Murex trunculus, Thesis, Saarbrucken, 1967 The chemistry of the prochromogens of Murex trunculus are investigated Maravelaki-Kalaitzaki P and Kallithrakas-Kontos, Pigment and terracotta analyses of Hellenistic figurines in Crete, Analytica Chimica Acta, 2003, 497, 209-225 The purple colour was identified from IR measurements as dibromoindigo and bromine detected by EDXRF Mcgovern P E, The Royal Purple and the Biblical Blue (Argaman and Tekhelet) - The Study of Chief Rabbi Herzog,Isaac on the Dye Industries in Ancient-Israel and recent Scientific Contributions - Spanier,E, ISIS, 1990, 81(308), 563-565 Book review McGovern P E, Lazar J, Michel R H, Caveats on the analysis of indigoid dyes by mass spectrometry, Journal of the Society of Dyers and Colourists, 1991, 107(n7-8), 280-281 Dibromoindigotin on fibres subjected to MS gives some monobromoindigo and the amount formed is reduced by extraction of the dye with DMSO. McGovern P E, Lazar J, Michel R H, The analysis of indigoid dyes by mass spectrometry, Journal of the Society of Dyers and Colourists, 1990, 106(1), 22-25 MS was used to identify indigo and dibromoindigotin in archaeological fibres and the significance of the monobromo derivative is discussed McGovern P E, Michel R H, Royal Purple dye: its identification by complementary physicochemical techniques, Chemtracts: Inorg. Chem., 1991, 3(1), 69-76 Purple deposits on pottery at Sarepta were examined by PIXE, ESCA, FT-IR and chemical reduction - oxidation and photodebromination showed them to be dibromoindigotin. McGovern P E, Michel R H, The Photochemistry of Royal Purple, The Spectrum, 1991, 4, 6-9 The photochemical processes associated with purple production and dyeing with leuco-indigos are discussed McGovern P E, Michel R H, Royal purple dye: its identification by complementary physicochemical techniques., MASCA Res. Pap. Sci.Archaeol., 1990, 7, 69-76 Purple deposits on pottery at Sarepta were examined by PIXE, ESCA, FT-IR and chemical reduction - oxidation and photodebromination showed them to be dibromoindigotin. McGovern P E, Michel R H, Royal Purple dye: the chemical reconstruction of the ancient Mediterranean industry, Accounts of Chemical Research, 1990, 23(5), 152-158 The historical production, social and religious significance of dibromoindigotin in the Mediterranean region is discussed McGovern P E, Michel R H, Royal Purple dye: tracing the chemical origins of the industry, Analytical Chemistry, 1985, 57(14), 1514A-1522A 13th century BC pottery sherd analysis by PIXE, ESCA and FT-IR showed that a purple deposit was dibromoindigotin McGovern P E, Michel R H, Royal purple and the pre-Phoenician dye industry of Lebanon, MASCA J., 1984, 3(3), 67-70 13th century BC pottery sherd analysis by PIXE, ESCA and FT-IR showed that a purple deposit was dibromoindigotin K McLaren, a letter, COLOR research and application, 1983, 8(3), 164 A letter arguing that Tyrian purple, as produced by photochemical reactions from molluscs, is not a vat dye Meijer L, Skaltsounis A-K, Magiatis P, Polychronopoulos P, Knockaert M, Leost M, Ryan X P, Vonica C A, Brivanlou A, Dajani R, Crovace C, Tarricone C, Musacchio A, Roe S M, Pearl L, and Greengard P, GSK-3-Selective Inhibitors Derived from Tyrian Purple Indirubins, Chemistry & Biology, 2003, 10, 1255-1266 Gastropod mollusks have been used for over 2500 years to produce the "Tyrian purple" dye made famous by the Phoenicians. This dye is constituted of mixed bromine-substituted indigo and indirubin isomers. Hexaplus trunculus (60 kg) were processed to give indirubin (3.5 mg), 6'-bromoindirubin (5.5 mg), 6-bromoindirubin (2.8 mg) and 6,6'-dibromoindirubin (3 mg) Melzer R R, Brandhuber P, Zimmermann T, Smola U, Der Purpur: Farben aus dem Meer, Biologie in unserer Zeit, 2001, 31(1), 30-39 In ancient times the colour of gods and kings, Tyrian purple, was made by extracting the leucobase from myriads of purple snails (Muricidae) and light-induced oxidation. A survey of its history, production. and cultural and social relevance is given. The biology of purple snails is described in the light of old as well as of modern sources. In addition, studies on the purple stain's chemistry as well as biochemistry are reviewed, and a procedure for the making of purple is presented to be used in marine biology courses. Tyrian purple was a treasured substance, and a myth. The colour and its uncommon producers stand for the way in which humans look at the sea - and how this view changes. Michel R H, Lazar J, McGovern P E, The chemical composition of the indigoid dyes derived from the hypobranchial glandular secretions of Murex molluscs, Journal of the Society of Dyers and Colourists, 1992, 108(3), 145-150 Mass spectrometry of pigments from Murex brandaris and M. trunculus reveals indigo and mono- and di-bromo derivatives. Michel R H, Lazar J, McGovern P E, Indigoid Dyes in Peruvian and Coptic Textiles, Archeomaterials, 1992, 6, 69-83 Dibromoindigo was found on Coptic and Peruvian textiles Michel R H, McGovern P E, The chemical processing of Royal Purple dye: ancient descriptions as elucidated by modern science, part II, Archeomaterials, 1990, 4(1), 97-104 The chemistry of Tyrian Purple production is discussed with reference to ancient descriptions from Rome and Egypt, with some supporting evidence from experiments Michel R H, McGovern P E, The chemical processing of Royal Purple dye: ancient descriptions as elucidated by modern science, Archeomaterials, 1987, 1(2), 135-143 Ancient Tyrian Purple production is suggested to be via a leuco-form with tin as reductant Michel-Morfin J E, Chavez E A, Effect of repetitive dye extraction over yield and survival rate of the purple snail Plicopurpura pansa (Gould, 1853), Journal of Shellfish Research, 2000, 19(2), 913-917 The purple snail is an important economic species because of the dye obtained from it in western Mexico. This dye has been used since ancient times to color ceremonial dresses purple. Other. snails produce dye, but Plicopurpura pansa dye extraction was done without killing the snail. Repetitive dye extraction is possible. The repeat time between each milking, dye yield versus milking frequency, and effect on survival was determined by repetitive milking snail groups several times (7, 14, 21, and 28 days). Mortality in the most frequently milked groups and dye yield reduction occurred (every 7 and 14 days). When milking frequency occurred every 21 days, the best dye yield and 100% survival rate was observed. These results suggest wild populations can be exploited using optimum extraction schedules, leaving at least 21 days between each dye extraction. Michel-Morfin J E, Chavez E A, Landa V, Population parameters and dye yield of the purple snail Plicopurpura pansa (Gould, 1853) of west central Mexico, Journal of Shellfish Research, 2000, 19(2), 919-925 The purple snail (Plicopurpura pansa) is a conspicuous rocky shore species of the intertidal zone of tropical western America. It is considered a potential resource due to the dye it produces. Estimates of population density, sex ratio, growth parameters, mortality, and recruitment were obtained from bimonthly samplings from 1993 through 1995 on a rocky shore of west central Mexico. A different growth rate between sexes was observed. Mortality coefficients for the population are estimated for the first time. Recruitment to rocky shores occurs principally from September through March. The life span (longevity) was estimated as 11 y. Dye production related to size and sex was determined and is described by an exponential relation. Naegel L C A and Murillo Alvarez J I, Biological and chemical properties of the secretion from the hypobranchial gland of the purple snail Plicopurpura pansa, Journal of Shellfish Research, 2005, 24(2), 421-428 The hypobranchial gland of the muricid Plicopurpura pansa (Gould, 1853) is so active that the snails can be stimulated periodically without harming them to expulse the secretion. This property is a great advantage in the study about its biologic and chemical characteristics. No statistical difference could be determined between the incidence of expulsion and the sex of the animals. Also the test on whether the size of the animals had an influence on the frequency of expulsion showed no relation. The incidence of expulsions is the same between the different size classes. From between September 2003 and February 2005 collected snails (total number 3,577) 1,724 (48.2%) expulsed secretion. The proportion of snails that expulsed or not varied from month to month, however no clear seasonal trend could be observed. We determined in the laboratory the amount of the total organic compounds in the "milk" and found great variations (from 34.2 mg/100 animals to 337.8 mg/100 animals). We determined from 11 samples collected during different months an average of 148.9 mg organic compounds/100 animals. The "milk" expulsed from the hypobranchial gland of P. pansa contains 6.15% ([+ or -] 1.07 SD n = 3) total solids, 21.3 mg/ml ([+ or -] 17.8 SD n = 38) soluble proteins, and 6.01 mg/ml ([+ or -] 3;2 SD n = 38) carbohydrates. In organic extracts from the secretion of the hypobranchial gland we determined in a microwell assay a 50% lethal dose ([LD.sub.50]) of 81.72 µg/mL (SD 35.78 n = 5) against Anemia nanplii. In assays to determine possible antibacterial activities in organic extracts we found two inhibition zones against Staphylococcus aureus. To quantify the microbial activity we determined a lowest inhibitory concentration of 125 µg/disk. By thin layer- and column chromatography, as well as by IR spectroscopy, we could preliminary identify some of the organic compounds in the "milk" and in organic extracts. By comparing previously reported front reference values (Rf-values) we could identify the dye precursor tyrindolinone, tyriverdin and bromoisatin. By column chromatography the extract was separated with different mixtures of organic solvents. In a first step gradient fractionation we obtained three fractions, which were unstable in light and turned immediately purple, and one yellow, light stable fraction. Two light stable brownish-colored fractions turned purple after acid hydrolysis. They were united and subjected to further fractionation, where four fractions and the green insoluble tyriverdin were obtained. By IR spectrophotometry and comparison with reported spectra it could be shown that one fractionated compound was a salt of probably 6-bromo-2-methylsulfonylindoxylsulfate and the other 6-bromoisatin. In organic extracts of the secretion free radical scavenging activities were determined by the 2,2-dipbenyl-l-picrylhydrazyl radical method (DPPH). We observed two yellow patches above a purple background. By IR spectroscopy of the organic extract used we could determine the chromogen IV, probably 6-bromo-2 methylsulfonylindoxylsulfate, as a substance responsible for the free radical scavenging activity. Naegel, L and Cooksey C J, Tyrian purple from marine muricids, especially from Plicopurpura pansa (Gould, 1853), Journal of Shellfish Research, 2002, 21(1), 193-200 Most marine snails of the family Muricidae produce in the hypobranchial gland a viscous secretion containing, besides mucus and biologically-active compounds, minute amounts of chromogens. These chromogens develop enzymatically and under the influence of light and oxygen into a purple pigment known variously as "Tyrian Purple", "Royal Purple" or shellfish purple. In the hypobranchial gland the enzyme purpurase is kept apart from the chromogens, so that no pigments are formed under normal conditions. The chromogens together with the enzyme can be obtained from Plicopurpura pansa (Gould, 1853) by "milking" without harming the animals. Different species of muricids produce different pigments, depending on the number and concentration of different chromogens and on the varying light intensity and oxygen availability during pigment formation. The main pigment obtained from the hypobranchial gland from muricids contains indigoids. The "ink" of P. pansa is mainly 6,6´-dibromindigo with smaller amounts of 6-bromoindigo and 6,6'-dibromoindirubin, similar to that of Murex brandaris. de Negri G and A F, Della Porpora degli Antichi e Relazione di altri lavori eseguiti nel Laboratorio di Chimice Generale della R. Università di Genova, Atti della Reale Accademia del Lincei, 2nd series, 1875-1876, 3, 394-442 de Negri G and A F, Dell' indigotina negli animali ovvero della porpora degli antichi (On Indigotin in Animals, or the Purple of the Ancients), Gazzetta Chimia Italiana, 1875, 5, 437-438 Nuttall Z, A Curious survival in Mexico of the use of the Purpura Shell-fish for dyeing, Putnam Anniversary Volume, The Torch Press, Cedar Rapids, Iowa, 1909, 366-384 Details are given of the dyeing industry using Purpura pansa Olivier J P, Treuil R, Vandenabeele F, Malia - Nécropole de l'Ilot du Christ, Bulletin de Correspondance Hellénique, 1970, 94, 871-879 Find of shells of Hexaplex trunculus from Middle Minoan time on Christ Island at Malia/Crete Papanastasiou M, McMahon AW, The Use of Atmospheric Pressure Photoionization Mass Spectrometry for the Analysis of Indigoid Compounds in Natural Dyes, Proceedings of the 53rd ASMS Conference on Mass Spectrometry and Allied Topics, San Antonio, Texas, June 5-9, 2005, 2005 http://202.127.145.151/Dig_Lib/ReadingRoom/ASMS/2005/sessions/pdfs/A050974.pdf MS was used to detect and quantify indigo and bromoindigos in Mediterranean molluscs Pfister R, Textiles de Palmyre, Paris, 1934-1940, 1-3, Proof of purple dyestuff on textiles found in Palmyra Pietra F, Total Synthesis of Marine Natural-Products - A powerful contribution to the understanding and development of marine organic-chemistry, Gazzetta Chimica Italiana, 1985, 115(9), 443-485 Pinkney J M, Chalmers J A, Synthesizing Tyrian purple, Education in Chemistry, 1979, 16(5), 144-145 p-Toluidine is nitrated and the product converted by the Sandmeyer reaction to 4-bromo-2-nitrotoluene which is oxidised to the corresponding aldehyde then converted into dibromoindigotin with acetone in low overall yield; the vat dyeing of cotton is described Pliny the Elder, The Natural History, chapter 62: How wools are dyed with the juices of the purple, 79 An edited translation by John Bostock, M.D., F.R.S., H.T. Riley, Esq., B.A. in 1855. This chapter describes the preparation of a dye bath from molluscs. The full text can be found at http://www.perseus.tufts.edu/cgi-bin/ptext?lookup=Plin.+Nat.+9.62 Polychronopoulos P, Magiatis P, Skaltsounis A-L, Myrianthopoulos V, Mikros E, Tarricone A, Musacchio A, Roe M, Pearl L, Leost M, Greengard P,and Meijer L, Structural Basis for the Synthesis of Indirubins as Potent and Selective Inhibitors of Glycogen Synthase Kinase-3 and Cyclin-Dependent Kinases, Journal of Medicinal Chemistry, 2004, 47(4), 935-946 Syntheses of 6-bromo-, 6'-bromo- and 6,6'-dibromo-indirubin are given with 1H and 13C NMR and MS data Pouliquen J, Kossanyi J, Du Manteau de pourpre de Cesar aux blue jeans en passant par le Pays de Cocagne, New Journal of Chemistry, 1992, 16, 331-335 A review in French of the history, production and chemistry of dibromoindigotin and indigo, including historic line drawings of mollusks Puchalska M, Poe-Pawlak K, Zadrona I, Hryszko H, Jarosz M, Identification of indigoid dyes in natural organic pigments used in historical art objects by high-performance liquid chromatography coupled to electrospray ionization mass spectrometry, Journal of Mass Spectrometry, 2004, 39(12), 1441-1449 Reversed-phase liquid chromatography with electrospray ionization mass spectrometry (ESI-MS) offers detection limits in the range 0.03-5.00 µg ml-1 for the color compounds examined. The method developed made it possible to identify indigo and its isomers in genuine Indian indigo, indigo from woad and Tyrian Purple. Quiring H, Vorphönizischer Königspurpur und uquu-Stein, Forschungen und Fortschritte, 1947, 21/23, 98-99 The author tries to demonstrate that purple is not mentioned on tablets found in Ugarit. He means that realgar is mentioned in these documents Réaumur R A F de, Decouverte d'une nouvelle Teinture de Poupre, Mém de l'Acad Royale des Sciences Amsterdam, 1711, 216-258 Working with Purpura capillus on the coast of Poitou, showed that air is necessary for the purple colour to develop from hypobranchial gland extracts Réaumur R A F de, Quelques experiences sur la liqueur colorante qui fournait la pourpre, Mém Acad Roy Sci Amsterdam, 1736 Observations on the coast of Poitou Reese D S, Marine Shells, In Tristan J. Barako, Tel Mor - The Moshe Dothan Excavations, 1959-1960. IAA Reports 32. Jerusalem: Israel Antiquities Authority, 2007, ch. 12, 233-238 A description of murex shells found at Tel Mor and a referenced summary of shells found at other sites on the Levantine coast in Israel (Yavne-Yam, Apollonia-Arsuf, Tel Mevorakh, Tel Dor, Tel Megadim, Capernaum, Tel 'Akko, Tel Kabri), Lebanon (Tyre, Sarepta, Sidon) and Syria (Tell Rifa'at, Palmyra) Reese D S, Whale bones and shell purple-dye at Motya (Western Sicily, Italy, Oxford Journal of Archaeology, 2005, 24(2), 107-114 Excavations 30 years ago at 5th-6th century BC Motya produced a unique assemblage of four Sperm whale vertebrae, crushed purple-dye shells, and stone tools. Reese D S, Palaikastro Shells and Bronze Age Purple-dye production in the Mediterranean Basin, The Annual of the British School of Archaeology at Athens, 1987, 82, 201-206 Details of shells and fragments of purple-producing mollusks found at a variety of sites Reese D S, The Mediterranean Shell Purple-dye Industry, American Journal of Archaeology, 1986, 90(2), 183 Abstract of a meeting in which the author presents information on shell purple-dye collections from Greece, Turkey, Cyprus, Lebanon and Israel Reese D S, Industrial Exploitation of Murex Shells; Purple-dye and Lime Production at Sidi Khrebish, Benghazi (Berenice), Libyan Studies. The Society for Libyan Studies 11th Annual Report (1979-80), 1980, 79-93 Ancient and modern sources of mollusks and purple-dye production with 32 references Reese D S, Iron Age Shell Purple-Dye Production in the Aegean, Kommos IV, The Greek Sanctuary, Part 1. Eds: J W and M C Shaw, Princetown University Press, 2000, 643-645 A summary of recent archaeological data on shell-fish purple sources Reinhold M, The history of purple as a status symbol in antiquity, Collection Latomus, 1970, 116, 1-73 A major survey of classical references to the purple dye Reinking K, Über den Schnecken-Purpur, Melliand Textilberichte, 1929, 10, 634-636 Review on the knowledge of purple dyeing in the time of about 1930 Rios-Jara E, León H G, Lizárraga-Chávez L and Michel-Morfín J E, Produccíon y tiempo de recuperacíon del tinte de Plicopurpura patula pansa (Neogastropoda: Muricidae) en Jalisco, México, Revista de Biologia Tropical, 1994, 42(3), 537-545 In this study, it is shown that more dye is produced by larger snails; females produce more dye than males of the same size; individuals larger tham 5 cm recover from milking in 7 days and smaller ones in 15-21 days Roller R A, Rickett J D, Stickle W B, The hypobranchial gland of the estuarine snail Stramonita haemastoma canaliculata (Gray) (Prosobranchia, Muricidae) - A light and electron microscope study, American Malacological Bulletin, 1995, 11(2), 177-190 One of the secretory products of the hypobranchial gland possesses the staining characteristics of the "Tyrian Purple'' dye Ron M, Difference between tyrian purple and hyacinthine purple, Yalkut Le-sivim, Le-tekhnol. U-le-minhal Shel Tekst., 1985, 104, 38-39 Hyacinthine purple, derived from Murex trunculus, is a mixture of dibromoindigotin and indigo, and the colourant from M. brandaris and Thais hemastoma is mainly dibromoindigotin Rottig W, Uber eine einfache Synthese des antiken Purpurs, J Prakt Chem, 1935, 142, 35-36 See Wahl A Sachs F, Kempf R, Uber p-Halogen-o-nitrobenzaldehyde, Berichte der Deutschen Chemische Gesellschaft, 1903, 36, 3299-3303 Synthesis of 6,6'-dibromoindigotin from 4-bromo-2-nitrobenzaldehyde and acetone with sodium hydroxide solution. The product is soluble in warm sulfuric acid, giving a deep green solution and in warm aniline to give a blue solution Sachs F, Sichel E, Ueber p-substituirte o-Nitrobenzaldehyde, Berichte der Deutschen Chemische Gesellschaft, 1904, 37, 1861-1874 Synthesis of 6,6'-dibromoindigotin from 4-bromo-2-nitrophenyllactic acid methyl ketone and aqueous sodium hydroxide or carbonate solution. Bromination of indigotin gives a product of different colour (blue) Saltzman M, Analysis of Dyes in Museum Textiles or, You Can't Tell a Dye by Its Color, Textile Conservation Symposium in Honor of Pat Reeves, The Conservation Center, Los Angeles County Museum of Art, 1986, 27-39 The use of reflectance and solution (in chloroform and sulfuric acid) spectra to determine the presence of shellfish purple Saltzman M, Identifying Dyes in Textiles, American Scientist, 1992, 80, 474-481 Shellfish purple and indigo dyed textiles can be distinguished by light absorption reflectance maxima of 520 nm and 640 nm respectively Saltzman M, Keay A M and Christensen, J, The Identification of Colorants in Ancient Textiles, Dyestuffs, 1963, 44(8), 241-251 Use of solution absorption spectroscopy in chloroform or sulfuric acid solution to identify dibromoindigo in pre-Columbian Peruvian textiles Sasaki K, Chemical structure of ancient purple dye. Tyrian purple., Senryo To Yakuhin, 1975, 20(2), 36-45 Dibromoindigotin was found in products of Rapana thomasiana by IR and X-RAY spectroscopy Sato M and Sasaki Y, Blue and Purple Dyestuffs Used for Ancient Textiles, Dyes in History and Archaeology, 2003, 19, 100-105 XRF and visible absorption spectra of an extract of a purple dyed wool textile from Al-Tar in Iraq suggest dibromoindigo as the colorant Schaeffer A, Neuere Ansichten über den antiken Purpur, Chemiker-Zeitung, 1941, 65, 273-275 Review on the knowledge of purple dyeing in the time of about 1940 Schaeffer C F A, Une Industrie d'Ugarit - la Pourpre, Annales Archéologiques de Syrie, 1951, 1, 188-192 Report on Purple on the tablets found in Ugarit Schatz P F, Indigo and Tyrian purple - In nature and in the lab, Journal of Chemical Education, 2001, 78(11), 1442-1443 The use and synthesis of the dyes indigo and Tyrian purple are discussed. Schechter E, The Thin Blue Line, The Jerusalem Report, 1999, 10(1), 23 The origin and identity of tekhelet are described and a brief history of P'til Tekhelet given Schmidt-Colinet A, Stauffer A, AI-Ascad K., Textilien aus Palmyra - Neue und alte Funde, P. von Zabern: Mainz, 2000 New investigations of the textiles from Palmyra with information on purple dyes Schunck E, Notes on the Purple of the Ancients. 1. The Chromogen of Purpura Capillus. 2. Properties of the Colouring Matter formed by Insolation from the Chromogen of Purpura Capillus., Journal of the Chemical Society, 1879, 35, 589-596 Following a summary of literature from 1616, experiments are described in which 400 Purpura capillus collected from Hastings yielded 7 mg of purple dye, for which the name punicin is suggested, and demonstrated solubility and sublimation properties Schunck E, Notes on the Purple of the Ancients. 3. Purple dyeing in modern times, Journal of the Chemical Society, 1880, 37, 613-617 Dyeing in South America is described and the analysis of a sample from Nicaragua Schweppe H, Handbuch der Naturfarbstoffe. Vorkommen, Verwendung, Nachweis, ecomed: Landsberg/Lech., 1993, 304-318 A summary of the use of purple natural shell-fish dyes Schweppe H, Untersuchung alter Textilfärbungen, Die BASF, 1976, 26, 29-36 Description of an analysis method for the proof of purple dyeing and a report on a find of purple in a Roman grave of Wehringen near Augsburg Schweppe H, Nachweis von Farbstoffen auf alten Textilien, Fresenius' Zeitschrift fur Analytische Chemie, 1975, 276, 291-296 Use of ammonia - dithionite followed by exposure to sunlight for 30 min giving a blue colour to detect dibromoindigo in textiles Shimoyama S, Studies on the non-destructive determination of dyestuffs used in ancient colored cloths and ukiyo-e prints by the three-dimensional display of fluorescence spectra, Bunseki Kagaku, 1999, 48(10), 951-952 Using 3D fluorescence spectra, the origin of the colored textile remnant attached on a shell bracelet found at Yoshinogari ruin (B.C. 100) was identified to be deteriorated Tyrian purple Shimoyama S, Noda Y, Non-destructive three-dimensional fluorescence technique, Dyes in History and Archaeology, 1994, 12, 50-61 Identification of shellfish purple, probably from Rapana thomasiana, using a non-destructive technique. The dye was on a small fragment of silk textile dated to the 1st century BC, excavated in Japan Shimoyama S, Noda Y, Nondestructive determination of Natural Dyestuffs used for ancient coloring cloth by the 3-dimensional fluorescence-spectrum, Bunseki Kagaku, 1992, 41(6), 243-250 Sidebotham S E, Wendrich W Z, Preliminary Report of the 1995 Excavations at Berenike (Egyptian Red Sea Coast) and the Survey of the Eastern Desert, Leiden : Research School CNWS, 1996 Proof of purple dyestuff on textiles of Roman time from Berenike Sinclair R S and Thomson M, Light induced colour changes during tyrian purple dyeing, Dyes in History and Archaeology, 1994 A poster showing the different colour variations on substrates and the effect of sunlight induced photodebromination which results in a blue colour Soldt, W H van, Fabrics and Dyes at Ugarit, Ugarit-Forschungen, 1990, 321-357 Investigation of trading tablets from Ugarit, some containing mention of purple dye Soleim O, Purple - an ancient dye and a modern problem, Naturen, 1975, 99(1), 3-9 The history and mythology of Tyrian purple are discussed with no references Sotiropoulou S and Karapanagiotis I, Conchylian purple investigations in prehistoric wall paintings of the Aegean area, in Indirubin, the red shade of indigo, editors Meijer L, Guyard N, Skaltsounis LA and Eisenbrand G, France: Life in Progress Editions, ISBN 2-9518029-0-0, 2006, 71-78 According to the archaeological deductions, the origin of true purple dyeing technology is proven native of the Aegean world, dating at least from the 1700 - 1600 B.C., including indications of earlier developments belonging to Neolithic levels. Although the continuing fame of purple is always related to the prestigious garments of royalty or to high ranks of society and religion, archaeological evidence of any early dyed textile preserved is extremely unlikely to come to light, because of the fragility of the fibre substrate. The identification of the conchylian purple dyestuff in the form of a pigment, found applied on the wall paintings at Akrotiri of Thera, is shown to be of equal importance as being the earliest tangible evidence in the Aegean for the development of the vat dyeing technology in the early Late Bronze Age. 33 refs. Spanier E, Rediscovering Royal Purple and Biblical Blue, Oceanus, 1990, 33(1), 75 A brief history with details of the preparation of tekhelet, Biblical Blue, from Murex trunculus Spanier E (Ed), The Royal Blue and The Biblical Purple; Argaman and Tekhelet, Keter Publishing House Jerusalem Ltd, 1987 A major review of the Jewish connection Spanier E, Karmon N and Linder E, Bibliography concerning various aspects of the purple dye, Levantina, 1982, (37), 437-447 A bibliography with 157 references, divided into general (30), biology - chemistry (82) and history and archaeology (45) Steigerwald G, Die antike Purpurfarberi nach dem Berichte Plinius des Alteren in seiner Naturalis Historia, Traditio (Studies in ancient and medieval history, thought and religeon), 1986, 42, 1-58 Tyrian purple as it appears in Pliny's Natural History and other Roman documents Steigerwald G, Herstellungsmethode des antiken Purpurs, Naturwissenschaftliche Rundschau, 1989, 42, 417-418 Summary of Traditio (Studies in in ancient and medieval history, thought and religion), 1986, 42, pp1-58 Steigerwald G, Der kaiserliche Purpur - eine schwarz-rote Doppelfärbung, Frankfurter Allgemeine Zeitung, 1991 30.01.1991, Nr. 25. Beilage: Natur und Wissenschaft N2; Der kaiserliche Purpur der römisch-byzantinischen Zeit war der tyrische Purpur, auch "Blatta" genannt. Er war kein Pigment, sondern das Ergebnis einer Doppelfärbung Steigerwald G, Die Purpursorten im Preisedikt Diokletians vom Jahre 301, Byzantinische Forschungen (Internationale Zeitschrift für Byzantinistik), 1990, 15, 219-277 Höchstpreise für 12 verschiedene Purpurseiden und Purpurwollen- Sie unterscheiden sich nicht nur im Farbton, sondern auch durch die Farbstoffe . Ausser Schneckenpurpur sind dies Kermes und Fucus,der Farbstoff einer Rotalgenart (Rytiphloea tinctoria C. Ag) Steigerwald G, Das kaiserliche Purpurprivileg in spätrömischer und frühbyzantinischer Zeit, Jahrbuch für Antike und Christentum, 1990, 33, 209-239 Nicht alle mit Schneckenpurpur gefärbten Kleidungsstücke waren dem Kaiser und seinem Haus vorbehalten, sondern nur bestimmte blattapurpurne (=tyrischpurpurne) Kleider Steigerwald G, Purpur Spätantike und Byzantinisches Reich, Lexikon des Mittelalters, 1995, 7, 330-331 Zusammenfassung der Ergebnisse meines Aufsatzes im Jahrbuch für Antike und Christentum Steigerwald G, Purpurgewänder biblischer und kirchlicher Personen als Bedeutungsträger in der frühchristlichen Kunst, HEREDITAS (Studien zur Alten Kirchengeschichte ), 1999, 16, XXXII Diese Arbeit, konzentriert sich auf die Purpurkleider, soweit sie in Blattafarbe, so hiess der tyrische Purpur seit spätrömischer Zeit, und- wegen der besseren Farberhaltung in Mosaik dargestellt sind.. Erstmals in der Forschung werden hier die Purpurgewänder in der Kunst untersucht Steinhart C E, Biology of the blues: The snails behind the ancient dyes, Journal of Chemical Education, 2001, 78(11), 1444 Three species of marine snails were used in the ancient Mediterranean dye industry. Colorless dye precursors, sulfur-containing indole derivatives, are secreted by the hypobranchial gland of these animals. The several functions of this gland and other aspects of the lives of the snails that are interesting and relevant to the dye industry are described and the chemistry of dye production is summarized. Stieglitz R H, The Minoan Origin of Tyrian Purple, Biblical Archaeologist, 1994, 57(1), 46-54 The industry existed in the Middle Minoan period, 1750 BCE Stulz H, Die Farbe Purpur im frühen Griechentum, Stuttgart : B.G. Teubner; Beiträge zur Altertumskunde, vol 6, 1990 Investigation of the importance of purple at the Greeks, especially in the works of Homer Süsse P, Krampe C, 6,6'-Dibromo-indigo, a main component of Tyrian purple. Its crystal structure and light absorption, Naturwissenschaften, 1979, 66(2), 110 Crystals of dibromoindigotin are monoclinic, space group P21/a, a=11.50, b=4.85, c=12.60, beta=104.0 and Z=2; the final R was 0.047;crystals are strongly pleochroic with light absorption maxima at 640 or 540 nm depending on the direction in the crystal Süsse P, Polarized Light-absorption Spectra of Tyrian Purple (dibromide Indigo), Zeitschrift fur Kristallographie, 1983, 162, 216-217 Crystals of dibromoindigotin are monoclinic, space group P21/a, a=11.61, b=4.842, c=12.61, beta=104.4 and Z=2; light absorption maxima are at 580 and 640 nm depending on the direction in the crystal Tanoue Y, Terada A, Sakata K, Hashimoto M, Morishita S I, Hamada M, Kai N, Nagai T, A facile synthesis of Tyrian purple based on a biosynthetic pathway, Fisheries Science, 2001, 67(4), 726-729 A facile synthesis of Tyrian purple, a valuable purple dye derived from gastropod mollusks in ancient times, has been accomplished. Tyrian purple, 6,6'-dibromoindigo, was easily obtained by three steps of reactions from the commercially available 6-bromoindole, on the basis of a biosynthetic pathway of indigo and biological precursors of the purple. Iodination of 6-bromoindole, followed by acetoxylation with silver acetate in acetic acid, afforded 6-bromo-3-acetoxyindole, whose alkaline hydrolysis accompanying air oxidation produced Tyrian purple. Tanoue Y, Sakata K, Hashimoto M, Hamada M, Kai N, Nagai T, A facile synthesis of 6,6'- and 5,5' dihalogenoindigos, Dyes and Pigments, 2004, 62(2), 101-105 The dihaloindigos are prepared from commercially available haloindoles by acetylation (iodination; silver acetate in acetic acid), followed by alkaline hydrolysis and aerial oxidation. Taylor G W, Detection of shellfish purples on textiles, Dyes on Historical and Archaeological Textiles, 1983, 2, 20-21 Purple pigment was extracted with pyridine, diluted with water and extracted into ether. The ether evaporated and the residue taken up in methanol for spectroscopy. Wavelength maxima in pyridine: indigo, 615 nm, dibromoindigo 605nm; in methanol, 610 and 600 nm respectively. Terada A, Yahiro T, Ohanti T and Tanoue Y, Synthetic Tyrian purple and shikonin -- Dyeing with ancient purple, Baiko Jogakuin Daigaku Chiiki Bunka Kenkyusho Kiyou, 1996, 11, 14-22 Thompson J, Shellfish Purple: The Use of Purpura patula pansa on the Pacific Coast of Mexico, Dyes in History and Archaeology, 1995, 13, 3-6 A first-hand description of the use of the mollusc to dye posahuancos with comments on its cultural significance Thorpe J F, Ingold C K, Synthetic Colouring Matters. Vat Colours, London: Longmans, Green and Co, 1923, 7-20 In a chapter, the literature and chemistry from pre-Roman times to the identification by Friedlander are covered; about 15 references Thureau-Dangin F, Un Comptoir de Laine Pourpre à Ugarit d'après une Tablette de Ras-Shamra, Syrie, 1934, 15, 137-146 Investigation of trading tablets from Ugarit. Wool dyed with purple dyestuff is mentioned several times there Timmermann I, Seide, Purpur und Gold: Untersuchungen zu den Gewebefragmenten aus dem Schrein der Heiligen Drei Könige im Dom zu Köln, Köln, 1982 Proof of purple dyestuff on the silk fabrics from the so-called Dreikönigsschrein at the cathedral of Cologne Torimoto N, Morimoto S, Shingaki T, Synthesis of Tyrian Purple as a teaching material, Kagaku to Kyoiku, 1991, 39(2), 198-201 Dibromoindigotin was prepared from 2-nitrotoluene via 4-bromo-2-nitrotoluene, 4-bromo-2-nitrobenzylidene diacetate and 4-bromo-2-nitrobenzaldehyde (by reaction with acetone) and the visible spectra of the product compared to that obtained from shellfish and silk cloth was dyed with it. Travis A S, The Royal Purple and the Biblical Blue - Argaman and Tekhelet - Spanier,E, Technology and Culture, 1989, 30(3), 667-668 Book review Uerpmann M, Auswertung der Meeresmollusken aus der westphönizischen Faktorei von Toscanos, Madrider Mitteilungen, 1972, 13, 165-171 Report on investigations of shells of purple snails found at the Phoenician settlement of Toscanos in Spain Van Alphen J, Remarks on the Action of Light on several substances, most of them containing halogen, in particular several Indigo Dyes, in a Reducing Medium, Recueil des travaux chimiques des Pays-Bas, 1944, 63, 95-96 Photodebromination of leuco-dibromoindigo by UV or sunlight is described. After 10 minutes (June or July), only leuco-indigo remained in solution, and after several days had completely decomposed to give indigo Verhecken A, Experiments with the dyes from European purple-producing shellfish, Dyes in History and Archaeology, 1994, 12, 32-35 Description of collecting and dyeing with three purple-producing shellfish of Spain Verhecken A, Experiences with mollusc purple, La Conchiglia, 1990, 22, 250-252 The preparation of purple stains and dyes from three species of shellfish Verhecken A, The Indole Pigments of Mollusca, Annales de la Societe Royale Zoologique de Belgique, 1989, 119(2), 181-197 Verhecken A, Lets over de Chemie van Molluskenpurpur, Gloria Maris, 1984, 22, 163-174 Description of the dyestuff formation during purple dyeing and a discussion of this process Vogler H, The Craft of Dyeing in Ancient Egypt, Textile History, 1982, 13, 159-163 Often purple dyeing in Pharaonic Egypt is asserted and a purple dyer supposedly mentioned in old Egyptian literature is presented as a proof It was demonstrated that this is not true Vogler H, Die Spuren früher Färberei im Minoerreich auf Kreta, Deutscher Färberkalender, 1984, 88, 193-206 A discussion of purple dyeing in the scope of the description of the dyeing methods of ancient Minoans Vogler H, Die Färberei der Antike, in Müller, W., Handbuch der Farbenchemie, Landsberg, 2000 Description of ancient purple dyeing in the context of a report on dyeing of antiquity Voss G, Gerlach H, Regioselektiver Brom/Lithium-Austausch bei 2,5-Dibrom-1-nitrobenzol. Eine einfache Synthese von 4-Brom-2-nitrobenzaldehyde und 6,6'-Dibromindigo, Chemische Berichte, 1989, 122(6), 1199-1201 4-Bromo-2-nitrobenzaldehyde is prepared in 92% yield by selective lithiation of 1,4-dibromo-2-nitrobenzene followed by reaction with DMF, and converted into dibromoindigotin in 66% yield by reaction with nitromethane followed by reduction. Voss G, The analysis of indigoid dyes as leuco forms by NMR spectroscopy, Journal of the Society of Dyers and Colourists, 2000, 116, 80-90 Reduction of indigos with sodium dithionite in D2O gives the leuco products and the proton and carbon NMR spectra can be obtained. 18 examples including 6,6'-dibromoindigo Voss, G, Schramm W, Selectively C-deuterated indigotins, Helvetica Chimica Acta, 2000, 83(11), 2884-2892 Selectively C-deuterated indigotins were synthesized from halogenated indigotins as precursors. The described reactions - used already by the ancient purple dyers - allowed the introduction of D-atoms at defined positions of the indigo molecule. The exchange of halogen atoms by D-atoms was induced by UV irradiation. of the leuco compounds in D2O. The resulting leuco forms were oxidized to the deuterated indigotins. Some conclusions were drawn as to the kinetics of the reaction. The physical properties of the new compounds were determined Wahl A, Sur une facile synthese de la pourpre antique, Revue Generale des Matieres Colorantes, 1935, 39, 121-122 Attention is drawn to a published synthesis (Rottig W, J. prakt. Chem., 1935, 142, 35) in which p-toluidine is nitrated then the amino group converted to Br to give 4-bromo-2-nitrotoluene; nitrosation with ethyl nitrite gives the aldoxime which is hydrolysed to the aldehyde. 50 g of p-toluidine yields 5.4 g of dibromoindigo Walton P, Shellfish purple in a Coptic textile, Dyes in History and Archaeology, 1985, 4, 33-34 A yarn (5th century AD) extracted with pyridine for 1 hour at 60 deg showed maximum absorption at 610 nm showing the presence of dibromoindigotin rather than indigo (620 nm) Westley CB, Vine KL and Benkendorff K, A proposed functional role for indole derivatives in reproduction and defence of the Muricidae (Neogastropoda : Mollusca), in Indirubin, the red shade of indigo, editors Meijer L, Guyard N, Skaltsounis LA and Eisenbrand G, France: Life in Progress Editions, ISBN 2-9518029-0-0, 2006, 31-44 The Muricidae, also known as Murex or purple snails, are remarkable both as a source of the ancient indigoid dye, Tyrian purple and the homeopathic remedy "Murex", prescribed for the relief of women's problems. This purple secretion contains brominated indoles and indirubins with established antibiotic and anticancer properties, as well as choline esters with muscle relaxing activity. These properties have prompted considerable speculation, but little directed research, into the selective benefits of these bioactive compounds for the Muricidae. Consequently, this paper reviews the current literature on indole derivatives, their biosynthesis and associated bioactivities, with the aim of amassing evidence for a naturally selected function in the Muricidae. 82 refs. Westley C and Benkendorff K, Sex-Specific Tyrian Purple Genesis: Precursor and Pigment Distribution in the Reproductive System of the Marine Mollusc, Dicathais orbita, Journal of Chemical Ecology, Dec. 2007 Exploitation of Tyrian purple from muricid molluscs, since antiquity, has prompted much interest in its chemical composition. Nevertheless, there remains a paucity of information on the biosynthetic routes leading to observed sexual differences in pigmentation. A liquid chromatography-mass spectrometry (LQ-MS) method was developed to simultaneously quantify dye pigments and precursors in male and female Dicathais orbita. The prochromogen, tyrindoxyl sulfate, was detected for the first time, by using this method in hypobranchial gland extracts of both sexes. Intermediates tyrindoxyl, tyrindoleninone, and tyriverdin were detected in female hypobranchial glands, along with 6,6'-dibromoindigo, while males contained 6-bromoisatin and 6,6'-dibromoindirubin. Multivariate analysis revealed statistically significant differences in the dye composition of male and female hypobranchial glands (ANOSIM, P=0.002), thus providing evidence for sex-specific genesis of Tyrian purple in the Muricida. White G, Purpurschnecken aus dem römischen Grenzach, Archäologische Nachrichten aus Baden, 1986, 37, 35-37 Discovery of shells of purple snails during the excavations of a Roman villa in Grenzach/Baden Withnall R, Clark R J H, Cooksey C J and Daniels M A M, Non-destructive, in situ identification of indigo/woad and shellfish purple by Raman microscopy and visible reflectance spectroscopy, Dyes in History and Archaeology, 1992, 11, 19-24 Raman microscopy and visible reflectance spectroscopy of indigo and dibromoindigo Withnall R, Patel D, Cooksey C and Naegel L, Chemical studies of the Purple Dye of Purpura pansa, Dyes in History and Archaeology, 2003, 19, 109-117 Visible absorption and reflectance spectra of the dye from Purpura pansa were consistent with the major colorant being dibromoindigo; HPLC showed that the monobromoindigo content was higher than for others in the brandaris group of mollusks; MS of the ethanol extract of the mollusk showed the presence of tyrindoleninone Wouters J, A new method for the analysis of blue and purple dyes in textiles, Dyes in History and Archaeology, 1991, 10, 17-21 Examination by HPLC of stains and vatted dyes obtained from three different species of shellfish. It is possible to distinguish Ph. trunculus dyes from those from the group that includes Ph. brandaris and T. haemostoma, by the presence or absence of indigotin and a detectable component which may be brominated indirubin Wouters J, Verhecken A, Composition of Murex dyes, Journal of the Society of Dyers and Colourists, 1992, 108(9), 404 Monobromoindigo can be formed from dibromoindigotin under vatting conditions and by some analytical procedures, and vatting of Murex trunculus hypobranchial glands increases the indirubin content from 1% to 14% Wouters J, Verhecken A, High-performance liquid chromatography of blue and purple indigoid natural dyes., Journal of the Society of Dyers and Colourists, 1991, 107((7-8)), 266-269 HPLC and visible spectra are used to characterise dyes from Murex trunculus, identifying indigo, mono- and dibromo-indigos and indirubin. Yoshioka T and Ueno T, Chemistry of natural dyes -- Ancient purple, Kagaku to Kyoiku, 1985, 33, 488-491 Japanese language review Ziderman I, Ancient Purple Dyes - reply, Chemistry in Britain, 1985, 21(5), 447 Reference is made to the process used to prepare the purple dye and the current use of the term tekhelet Ziderman I, Tyrian Purple or Hyacinthine Purple?, Chemical & Engineering News, 1983, 61(24), 88 A letter pointing out that Hyacinthine purple from Murex trunculus is a mixture of indigo and dibromoindigotin Ziderman I I, Purple dyes made from shellfish in antiquity, Review of progress in coloration and related topics, 1986, 16, 46-52 The identity of the colourants of argaman and tekhelet is reviewed, concluding that the former is dibromoindigotin and the latter a mixture of dibromoindigotin and indigo Ziderman I I, The 3600 years of purple-shell dyeing: characterization of hyacinthine purple (tekhelet), Advances in chemistry series. 0065-2393. 212 (Historic textile and paper materials, conservation and characterization), 1986, 187-198 Chemical, archaeological,biological and talmidic studies suggest that tekhlet was prepared from Trunculariopsis trunculus and the colourant is an equal mixture of indigo and dibromoindigotin; 24 references Ziderman I I, Biblical Dyes of Animal Origin, Chemistry in Britain, 1986, 22(5), 419-421;454;638 A review of insect and shellfish dyes with 26 refs Ziderman I I, Blue Thread of the Tzitzit - was the ancient dye a Prussian Blue or Tyrian Purple, Journal of the Society of Dyers and Colourists, 1981, 97(8), 362-364 The identity of the dyes used for tekhelet and argaman is reviewed. 35 refs Ziderman I I, a letter, COLOR research and application, 1985, 10(4), 258 Arguments against (and the author's reply) McLaren's suggestion (1983) that Tyrian purple is not a vat dye Ziderman I I, Seashells and Ancient Purple Dyeing, Biblical Archaeologist, 1990, 53(2), 98-101 A brief summary of the dye-forming process, the mollusks and the importance of chemical analysis to confirm the presence of bromoindigotin; 29 refs Ziderman I I, Molluscan source of Biblical "Blue" dyestuff, Proceedings of the ninth Malacological Congress, 1992, 407-414 A review with 31 references of evidence for Hyacinthine Purple from Murex trunculus being a mixture of indigotin and 6,6'-dibromoindigotin Zollinger H, Welche Farbe hat der antike Purpur?, Textilveredlung, 1989, 24(6), 207-12 The changed perception of the hue of Tyrian Purple over the last two millenia is discussed and related to biochemistry, technology, historical and linguistic investigations. 26 refs |
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