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Identification of anthraquinone markers for distinguishing Rubia species in madder-dyed textiles by HPLC
Abstract
The anthraquinone components of the roots of various species of madder (Rubia spp.) have been used for millennia as red colorants in textiles, carpets and other objects. Although many species of Rubia are known, only a few of them have been used widely for dyeing. Furthermore, though nearly 70 anthraquinones have been found in Rubia species, only a few of these occur consistently at relatively high levels. Knowledge of the plant dyestuffs is helpful for establishing the location of production, production method and/or history of the dyed object. Using plant material and dyed textile fibers obtained from a number of sources, and HPLC with photodiode array and mass spectrometric detection for analysis, we have been able to identify marker anthraquinones that permit differentiation of the more common species of madder used for dyeing in Eurasia. Textiles dyed with all of the species examined contain varying amounts of purpurin, but only those dyed with Rubia akane contain large amounts of 6-hydroxyrubiadin (1,3,6-trihydroxy-2-methylanthraquinone) or its glycosides. Textiles dyed with R. tinctorum contain primarily alizarin, whereas those dyed with R. cordifolia and R. peregrina contain mostly purpurin, munjistin and pseudopurpurin, but little or no alizarin or 6-hydroxyrubiadin. The latter two species cannot reliably be distinguished from each other, however. The plants themselves often contain glycoside precursors not usually seen in the dyed materials.
Figure
The analysis, based on HPLC retention time, UV/Visible spectra and molecular mass, of ancient madder (Rubia)-dyed textile extracts can identify the species used for dyeing.
... Among the several madder species possible, all are known to contain anthraquinone-based colorants. However, common madder (Rubia tinctorum) can be distinguished by the presence of both alizarin (M5) and purpurin (M6) [34,35]. In addition, common madder also contains significant peaks for pseudopurpurin (M3) and munjistin (M4), which are the carboxylated forms of purpurin and xanthopurpurin (1,3-dihydroxy-anthraquinone), respectively [34,35]. ...
... However, common madder (Rubia tinctorum) can be distinguished by the presence of both alizarin (M5) and purpurin (M6) [34,35]. In addition, common madder also contains significant peaks for pseudopurpurin (M3) and munjistin (M4), which are the carboxylated forms of purpurin and xanthopurpurin (1,3-dihydroxy-anthraquinone), respectively [34,35]. These acidic compounds coelute under the chromatographic conditions used here, but they are easily identifiable by their mass differences [17,19]. ...
... These acidic compounds coelute under the chromatographic conditions used here, but they are easily identifiable by their mass differences [17,19]. The glycosides lucidin primeveroside (M1) and alizarin primeveroside, also known as ruberythric acid (M2), usually occur in low amounts due to endogenous enzymatic breakdown of the glycosides following harvest of the dye plant [35], but they were also detected. The identification of these colorants is exemplified by sample 1, as shown in Figure 2c. ...
This paper describes the identification of dyes on fifty yarn samples from a tapestry created by the well-known 17th-century Flemish workshop of the Mattens family. The design of the tapestry is based on the first of ten drawings known as the Acts of the Apostles by the famed 16th-century Italian painter Raphael. The drawings were commissioned by Pope Leo X and translated into tapestries by Pieter van Aelst; these original tapestries are still in the collection of the Vatican Museums. The present work was reproduced over a century later from the original drawing and is one in a possible set of nearly fifty known copies of the original tapestry cycle. Most of the Mattens yarn samples were found to be dyed by weld, indigo, and madder, as well as a few using brazilwood and lichen, but no insect dyes were detected. A significant finding in the present study was the detection of the dye component pseudoindirubin 1, alongside indigotin and indirubin, as well as yarns that only yielded the latter two dyes. The implication of using this new marker as objective evidence of the use of both woad and most likely Asian indigo is explored. The historical and conservation significance of the dyestuffs identified is also discussed.
... 112-113, 122-123 and 127, 3, 12-14]. Rubia peregrina L. and G. verum L. often contain significant quantities of rubiadin, which is not normally a major component in R. tinctorum L. [15], but it has been questioned whether rubiadin is a useful species indicator [10]. ...
... are rich in a variety of hydroxyanthraquinones, of which the most significant are shown in Figure 3 [1; pp. 112-113, 122-123 and 127, 3,10,12,13,25,26]. The aglycone forms of the main dye components such as alizarin, purpurin and pseudopurpurin are sparingly soluble in water and within the fresh root are often found as water-soluble sugar derivatives or glycosides. ...
... A number of recent studies have described the colourant composition in different Rubia spp. (collected, stored and analysed under various conditions) and in dyes or pigments derived from them [10,12,13]. Rubia tinctorum L. is typically rich in ruberythric acid, lucidin primeveroside, alizarin and purpurin (from galiosin) while R. peregrina L. is rich in galiosin and lucidin primeveroside and also contains pseudopurpurin, munjistin and variable amounts of purpurin and rubiadin. ...
... The molecules extracted from the fibers are chromatographically separated and identified singularly, thus enabling complex mixtures to be characterized. Dye sources can often be identified down to the species of the plant or animal from which they were produced [23][24][25][26][27]. The molecular detection and identification is usually possible by using a diode array detector (DAD), as the typical UV-Vis absorption spectra and retention times produce sufficient information to identify the most common sources of natural dyes [28][29][30]. ...
... For both HPLC-DAD and HPLC-DAD-MS analysis, dye components were associated with natural and synthetic dye sources using data measured from reference materials (retention times, UV-Vis spectra and mass measurements) made available by the Getty Conservation Institute (Los Angeles, USA) [61], as well as from the published literature [14,23,24,27,37,38,40,44,[62][63][64]. (3) ...
... Madder was identified in most red areas of the textiles under investigation (Table 1) [23,40]. All the samples containing madder showed a relatively higher amount of alizarin compared to purpurin, except for S2004.91 and S2006.21 in which alizarin and purpurin were present with comparable amounts. ...
This study focuses on the dye analysis of 26 ikat textiles present in the collection of the Arthur M. Sackler Gallery and originally collected by Dr. Guido Goldman with the aim to gain additional information about their provenance and dating. The investigation exploits the full potential of a multi-analytical approach, starting with a non-invasive survey of all the colors using fiber optic reflectance spectroscopy (FORS), which revealed the presence of indigo and insect-based red dyes. These data were used to select areas from which samples were taken and analyzed by high performance liquid chromatography diode array detector (HPLC–DAD). These results enabled most of the natural sources of dyes to be fully identified, including American cochineal (Dactylopius coccus), madder (probably Rubia tinctorum), lac (probably Kerria lacca), larkspur (Delphinum semibarbatum), pagoda tree flower buds (Sophora japonica), grape vine leaves (Vitis vinifera), indigo and tannins. Complex mixtures of dyes were present in most samples, as a result of both the ikat making process itself and traditional dyeing practices. Synthetic dyes were identified in 9 of the textiles. Samples were re-analyzed using HPLC–DAD coupled to mass spectrometry (HPLC–DAD-MS). Malachite green (basic green 4, C.I. 42000), fuchsine (basic violet 14, C.I. 42510), rhodamine B (basic violet 10, C.I. 45170) and methyl violet (basic violet 1, C.I. 42535) were identified, and a few other tentatively identified synthetic dyes (probably orange I, II and IV, rhodamine 6G, patent blue V and alizarin yellow GG) were detected. As the first synthesis of early synthetic dyes is well documented, their presence was used to refine the dating of these textiles. The contextualization of the results also appeared to support the stylistic assumption that more intricate and colorful designs with a higher level of complexity are dated earlier than simpler, larger and more graphic ones. The overall information acquired reveals a dynamic scenario and an interesting window into the dyers’ experiments and adjustments to the economic and technological changes of the nineteenth century.
... Despite the pioneering character of the Wouters method and application to LC analyses, this extraction method, although achieving very high yields, led to a variety of degradative phenomena such as decarboxylation, excessive hydrolysis (such as partial hydrolysis of pseudopurpurin and munjistin (Shahid et al., 2019;Wouters, 1985), and for the fiber itself, and especially glycosidic bond disruption in the chromophoric components, which are naturally present in the source employed and are fixed on the yarns during the dyeing process (Derksen et al., 2002;Lombardi et al., 2016;Serafini et al., 2017;Hofenk de Graaff, 2004;Delamare & Monasse, 2005;Mouri & Laursen, 2012;Shahid et al., 2019;Blackburn, 2017;Serrano et al., 2015). For example, for the cochineal dyes, other papers confirmed that the HCl method is not a suitable protocol to distinguish the cochineal source, because of several O-glucosides that must be considered to have a correct identification (Shahid et al., 2019;Lech et al., 2015;Lech & Jarosz, 2016;Serrano et al., 2015;Serafini et al., 2017). ...
... Unlike using acids is the approach in a basic environment, starting from the proposal of the use of pyridine/water/1.0 M oxalic acid in water (95:95:10) at 100 °C for 15 min, even if the use of pyridine should be avoided for health issues (Mouri & Laursen, 2012). ...
The analysis of archaeological textiles is a challenging undertaking, because of the high information content that characterizes these precious remains. Their realization, from the point of view of the dyes and yarns used, can have multiple meanings, for example the wealth of the commissioner and reflect the cultural taste of the society. The raw materials also can reveal the commercial routes, this may not be evident from literary sources and become clear from the archaeometric study of these artifacts. However, the alteration processes to which these materials have been subjected to, such as thermal aging and carbonization, mineralization, etc., represent an extremely critical point for their study and conservation, because these chemical processes are not entirely known and could bring to a complete modification. For these reasons, the identification of their composition requires high sensitivity techniques, characterized also by great versatility.
Recently, multi-technical approaches, based on spectroscopic and spectrometric techniques, have been revealed as powerful strategies in providing information about chemical composition of archaeological relics; they have been employed for characterization of dyes and moreover proteomics and genomics. In this chapter a review of the state of the art of FTIR, Raman and mass spectrometry analyses applied to archaeological fabrics will be provided, also reporting several case studies to highlight the potential of these multi-technical analyses.
... Une solution aqueuse d'ammoniac permet la dissociation du complexe métalcolorant associé à l'acide éthylènediaminetétraacétique (EDTA), un agent chélatant qui piège les ions métalliques(Lombardi et al. 2016). Les agents chélatants sont souvent utilisés, on retrouve l'EDTA, le DTPA, mais aussi l'acide oxalique qui présente des capacités importantes de liaison avec des ions métalliques(Chen et al. 2016;Marques et al. 2009;Mouri et Laursen 2012). D'autres études s'appuient sur l'utilisation de différents solvants tels que le N,Ndiméthylformamide (DMF) ou la pyridine, pour l'extraction d'anthraquinones de textiles anciens(Mouri et Laursen 2012;Serrano, van Bommel, et Hallett 2013). ...
... Les agents chélatants sont souvent utilisés, on retrouve l'EDTA, le DTPA, mais aussi l'acide oxalique qui présente des capacités importantes de liaison avec des ions métalliques(Chen et al. 2016;Marques et al. 2009;Mouri et Laursen 2012). D'autres études s'appuient sur l'utilisation de différents solvants tels que le N,Ndiméthylformamide (DMF) ou la pyridine, pour l'extraction d'anthraquinones de textiles anciens(Mouri et Laursen 2012;Serrano, van Bommel, et Hallett 2013). Plus récemment, un procédé d'extraction basé sur une solution de glucose a été développé pour l'extraction non dénaturante d'aglycones et de composés glycosylés sur des textiles teints à la garance(Ford et al. 2017).L'acide chlorhydrique est l'acide fort le plus utilisé avec de nombreuses variations concernant la composition du solvant d'extraction où le méthanol peut être remplacé par de l'éthanol. ...
La garance est une plante tinctoriale qui a eu une importance économique et culturelle considérable pour le territoire du Vaucluse aux XVIIIème et XIXème siècles. Après être tombée en désuétude avec le développement des colorants synthétiques, face à une demande croissante des acteurs de l'industrie et des consommateurs, la garance suscite de nouveau de l’intérêt. L’objectif de ce projet en collaboration avec la société Erubescence est de réintroduire la culture de la garance dans la région en valorisation des procédés d’extraction utilisant des solvants naturels dans le contexte d'une chimie dite « verte », et par la stimulation de la production de colorant dans les racines.Ces travaux de recherche s’inscrivent dans ce contexte à travers l’étude de différents procédés d’extraction, utilisant des techniques novatrices telles que les ultrasons et les micro-ondes, afin d’optimiser les rendements d’extraction en molécules colorantes sans les dénaturer. La technique séparative par chromatographie liquide haute performance (CLHP) a été utilisée pour la quantification des colorants anthraquinoniques rouges. Dans les conditions testées, le temps d'analyse a été réduit de 80 % et l'extraction optimale des colorants a été réalisée dans un mélange EtOH/H2O, 5/5, (v/v) par micro-ondes.Par ailleurs, cette étude s’appuie sur la stimulation des voies métaboliques impliquées dans les mécanismes de réponse aux stress. La méthode envisagée a été l’application de stress abiotiques tels que la variation du pH de culture en hydroponie et l'application d'un rayonnement UV-C. La culture de garance et la production de colorants ont été optimales pour un pH de 4. Les UV-C ont mis en évidence la stimulation de la biosynthèse de ces métabolites d'intérêt.
... The HPLC results, collected from the analysis of samples extracted from cultural heritage objects, are often used to identify the exact plant species of madder dyes, lakes and paints [10,12,[47][48][49][50][51]. In particular, the ratio of the HPLC peak areas of alizarin and purpurin was suggested as a criterion to identify R. tinctorum and R. peregrina [52]. ...
... It should be noted, however, that purpurin is the main colouring compound in Galium and Asperula species [43]. Moreover, the large amount of rubiadin might be another marker for identifying R. peregrina [10,52], but more recent studies have raised concerns about the reliability of this criterion [49]. ...
High Performance Liquid Chromatography coupled to a Diode-Array-Detector (HPLC-DAD) is used to investigate samples which were extracted from ancient Egyptian textiles (4th–5th c. AD) of the Museum of Faculty of Archaeology, Cairo University. Madder is identified in several samples. According to semi-quantitative results, which are obtained from HPLC peak areas measured at 254 nm, madder that is rich in purpurin and poor in alizarin is identified in samples which were treated (i) only with madder and (ii) with madder and either indigo/woad (Indigofera species and other/Isatis tinctoria L.) or weld (Reseda luteola L.). The madder dye used in these samples could have been originated from Rubia peregrina L. However, the possible use of Rubia tinctorum L. (or other plants of the Rubiaceae family) by the Egyptian dyers cannot be ruled out, particularly if methods were developed by the ancient dyers to affect and control the relative composition of madder dye. The HPLC peak area ratio of alizarin versus purpurin is very high (>2.2) for samples which were treated with madder (probably originated from R. tinctorum) and a tannin source. Finally, in some samples, only indigoid dyes (indigo/woad) are identified.
... The non-faded areas were found to be dyed with madder and tannins (Figure 3a). The molecular composition of the anthraquinones suggests the use of Rubia tinctorum, as relatively abundant alizarin and the presence of ruberythric acid are generally indicative of this plant [34,49]. The presence of ellagic acid and ellagic acid glucoside is not sufficient to ascertain the botanical source of tannins. ...
The dyes used to produce two Palestinian garments from the British Museum’s collection attributed to the late 19th–early 20th century were investigated by high pressure liquid chromatography coupled with diode array detector and tandem mass spectrometry (HPLC-DAD-MS/MS). Palestinian embroidery is a symbol of national identity and the topic of scholarly research. However, little attention has been given to the dyes and how these changed with the introduction of new synthetic formulations in the second half of the 19th century. The results revealed the use of natural indigoid blue and red madder (Rubia tinctorum), in combination with tannins. Yellow from buckthorn (probably Rhamnus saxatilis) and red from cochineal (probably Dactylopius coccus) were found mixed with synthetic dyes in green and dark red embroidery threads, respectively. Early synthetic dyes were identified in all the other colours. These include Rhodamine B (C.I. 45170), Orange II (C.I. 15510), Orange IV (C.I. 13080), Metanil Yellow (C.I. 13065), Chrysoidine R (C.I. 11320), Methyl Violet (C.I. 42535), Malachite Green (C.I. 42000), Fuchsin (C.I. 42510), Auramine O (C.I. 41000) and Methyl Blue (C.I. 42780). As the date of the first synthesis of these dyes is known, the production date of the garments was refined, suggesting that these were likely to be produced towards the end of the 1880s/beginning of the 1890s. The continuous use of historical local sources of natural dyes, alongside new synthetic dyes, is of particular interest, adding rightful nuances to the development of textile-making practices in this region.
... However, high-performance liquid chromatography coupled to diode array detector and high resolution mass spectrometry (HPLC-DAD-MS) is the state of the art technique for the identification of most dyes at a molecular level 20 and has been applied to characterise and identify dyes on Pacific barkcloth 4,10 . Chromatographic separation followed by the molecular detail provided by MS detectors is often necessary to distinguish between plant species, characterise complex molecular compositions and identify mixtures of dyes without neglecting significant minor components [21][22][23][24] . Despite its recognised advantages, the technique has some limitations, especially related to full differentiation of isomers, including the exact position of C-and O-glycosidic bonds, without retention time matching of pure standards 25,26 . ...
Various natural dye sources have been historically used and are still used today to decorate Pacific barkcloth. The identification of these natural dyes is a challenging task due to their molecular complexity and the scarcity of scientific investigations. In this study, barkcloth samples collected in Tahiti and dyed using local plants, including fruits of Thespesia populnea (L.) Sol. ex Corrêa, leaves of Cordia subcordata Lam., fruits of Ficus tinctoria G.Forst. and flower stalks of Musa troglodytarum L., were analysed by high-performance liquid chromatography coupled to diode array detector and mass spectrometry (HPLC–DAD–MS). The combination of extracts from the leaves of C. subcordata Lam. and fruits of F. tinctoria G.Forst. represents a Tahitian recipe to produce mati dye, which has never been analysed so far nor identified in historic barkcloth, despite being mentioned in historical accounts. The complex analytical results enabled molecular markers to be annotated in all samples. Gossypol and its derivatives are the main components of the dye from T. populnea (L.) Sol. ex Corrêa. Various anthocyanin O-glycosides, flavonoid C-glycosides as well as phenolic compounds are present in mati dye alongside condensed tannins. Anthocyanin O-hexoside-deoxyhexosides and polyacetylated O-p-coumaroylsucrose esters are found in the dye from M. troglodytarum L. These results constitute a precious molecular database and prompted a re-evaluation of the findings of a previous analytical study on samples from the Tahitian mourner’s costume in the British Museum collection. The new analytical evidence enabled mati dye to be identified in most red areas of the costume, correcting previous interpretations and providing the first scientific confirmation of the use of this dye in historical context. This study enhances the possibility of identifying traditional dye sources in historic artefacts from the Pacific islands and emphasises the benefits of sharing and exchanging knowledge with local communities.
... Rubiaceae, with over 13,000 species, is mostly known for its it many uses based on its content of alkaloids. Its common name (madder family) is based on the common madder, Rubia tinctorum, which produces a red pigment in its roots, which has been used as a colorant [89][90][91]. Lamiaceae, the mint family, is also large, with nearly 7000 species distributed globally. Species of that family also have many uses, mostly based on their content of ethereal oils and their pigments, such as chlorophyll and carotene, which are used as colorants [92][93][94][95]. ...
Growing concerns regarding health and eco-safety have led to a resurgence in the recognition of natural products. Although plant colorants are often mentioned in ethnobotanical studies in northern Thailand, they have not been comprehensively examined. This study aims to (i) investigate the colorant plants used by ethnic minorities in northern Thailand and (ii) compare colorant plants used among the groups in northern Thailand with other regions worldwide. Data on colorant plants used by ten ethnic groups across 142 villages in northern Thailand were extracted in a systematic review of 42 published references. The importance of the colorant plant species was evaluated using the ethnobotanical index “use value” (UV), and the homogeneity of knowledge was assessed using the “information consensus factor” (ICF). The similarity of colorant plants used among the ethnic minority groups and beyond was evaluated using Jaccard’s index. The 42 published references included information about 104 colorant plant species belonging to 85 genera and 43 families from seven provinces in northern Thailand. This represents nearly half of the 212 colorant plant species reported across all 72 provinces in Thailand. The most important species were Strobilanthes cusia and Morinda angustifolia, which are sources of blue and red colors. Fabaceae, Rubiaceae, and Lamiaceae were the plant families with most species used as colorants. The colorant plant species yielded ten different color shades, with blue being the most prevalent. The Jaccard’s index varied from 0 to 0.27 among the northern Thai ethnic minorities and from 0 to 0.13 for regions outside of northern Thailand. The regions located closest to northern Thailand exhibited the highest degree of similarity. This study provides valuable insights into the traditional knowledge and usage of dye plants in northern Thailand, contributing to preserving the cultural heritage and providing basic knowledge for the sustainable use of natural colorants for modern applications.
... The study of ancient silk dyeing processes has also gained significant attention, with LC-MS/MS being the most widely utilized detection technique. For instance, on historical fabrics, it can identify yellow dyes based on flavonoids [30][31][32], red dyes based on anthraquinones [1,[33][34][35], blue dyes from indigo plants [36], and cochineal and violet bugloss dyes [37,38]. ...
The Liao Dynasty's highly developed textile industry was characterized as "the best in the world" in ancient Chi-nese literature. This study analyzed two textiles on a 蹀躞 (DieXie) belt excavated from the No.1 Liao Dynasty noble tomb of Zhangjiayao Forest (Shenyang, China), with one wrapping around the leather belt (T1) and the other on the surface of a leather pouch hanging on the belt (X1). They were identified as silk based on structures by morphological observation and chemical components revealed by Fourier Transform Infrared spectroscopy (FTIR). Proteomics and enzyme-linked immunosorbent assay (ELISA) were used to investigate the animal origin of the silk, and the original color and dyestuffs of T1 were examined by liquid chromatography-mass spectrometer (LC-MS/ MS). The results have shown that T1 consists of three layers of Bombyx mori silk plain fabric, and its original color was yellow-red dyed with madder and plants containing flavonoid dyeing tissue, consistent with the color of DieXie belts recorded in the ancient literature. The silk on the pouch is a layer of plain fabric, while the upper layer is embroidery on the Four-end-complex gauze, which was made of twisted Bombyx mori silk. We believe that the silk wrapping around the leather belt was to provide additional comfort and aesthetics after dyeing while protecting the leather, which is prone to warping and moisture. This study suggests that such silk fabrics with high specifications are one of the manifestations of the distinguished status of the tomb owner. The integration of various analytical methods on ancient silk fabrics enables us to learn various information about their textile forms, silk animal origins, colors and dyestuffs, revealing the highly developed silk waving techniques and prosperous costume culture of the Liao Dynasty.
... The study of ancient silk dyeing processes has also gained signi cant attention, with LC-MS/MS being the most widely utilized detection technique. For instance, on historical fabrics, it can identify yellow dyes based on avonoids [30][31][32], red dyes based on anthraquinones [1,[33][34][35], blue dyes from indigo plants [36], and cochineal and violet bugloss dyes [37,38]. ...
The Liao dynasty's highly developed textile industry was characterized as "the best in the world" in ancient Chinese literature. This study analyzed two textiles on a 蹀躞(DieXie)belt excavated from the No.1 Liao dynasty noble tomb of Zhangjiayao Forest (Shenyang, China), with one wrapping around the leather belt (T1) and the other on the surface of a leather pouch hanging on the belt (X1). They were identified as silk based on structures by morphological observation and chemical components revealed by Fourier Transform Infrared spectroscopy (FTIR). Proteomics and enzyme-linked immunosorbent assay (ELISA) were used to investigate the animal origin of the silk, and the original color and dyestuffs of T1 were examined by liquid chromatography-mass spectrometer (LC-MS/MS). The results have shown that T1 consists of three layers of Bombyx mori silk plain fabric, and its original color was yellow-red dyed with madder and plants containing flavonoid dyeing tissue, consistent with the color of DieXie belts recorded in the ancient literature. The silk on the pouch is a layer of plain fabric, while the upper layer is embroidery on the Four-end-complex gauze, which was made of twisted Bombyx mori silk. We believe that the silk wrapping around the leather belt was to provide additional comfort and aesthetics after dyeing while protecting the leather, which is prone to warping and moisture. This study suggests that such silk fabrics with high specifications are one of the manifestations of the distinguished status of the tomb owner. The integration of various analytical methods on ancient silk fabrics enables us to learn various information about their textile forms, silk animal origins, colors and dyestuffs, revealing the highly developed silk waving techniques and prosperous costume culture of the Liao Dynasty.
... Its roots give a distinctive red dye due to its high content of anthraquinones [6,7]. Madder pigments are especially suitable for the green transition as they display good stability under washing, UV, and temperature [1, 8,9]. ...
Water is one of the greenest and most accessible solvents. To harness its potential, the water-based microwave-assisted extraction (MAE) of pigments from madder was optimized by the response surface methodology (RSM) using a Box–Behnken experimental design. The extract that presented both the highest extraction yield and the most intense color was obtained after a 30-s cycle at 1000 W using 100 mg of madder for 20 mL of water. This water-based MAE was more efficient than Soxhlet extraction and proved comparable to hydroalcoholic MAE. The optimized extract was further characterized using UHPLC-HRMS/MS to identify its main compounds. Glycosylated flavonoids and anthraquinones were putatively identified, as well as free anthraquinones, generally found in madder. The microwave-assisted extraction extended the range of polarity of the extracted compounds, making the water more versatile.
... It was found that textiles dyed with R. tinctorum mainly contain alizarin; those dyed with R. cordifolia and R. peregrina contain mostly purpurin, munjistin, and pseudopurpurin; and those dyed with R. akane contain large amounts of 6-hydroxyrubiadin or its glycosides. These results promoted the differentiation of the more common species of madder used for dyeing, and the sourcing of madder-dyed textiles in ancient Eurasia [64]. In ancient times, red dyes not only came from plants but also from insects. ...
Cultural relics are man-made objects left from ancient times, with historical, artistic and scientific values. Multi-interdisciplinary research of cultural relics would enable people to obtain a variety of information, from which the restoration of ancient civilization is possible. Due to natural weathering, many cultural relics are in a fragile state, and conservation treatments that can prolong their lifetime are important, which may involve the use of conservation materials. In this paper, we define the new term “Herit-Materials” as two type of materials, including ancient cultural relics themselves and novel functional materials for conservation purposes. For the first type of Herit-Materials- cultural relics themselves, as one type of ancient materials, the concept on the relationship between the structure, composition, performance and technology of them has been introduced, along with the research paradigm for ancient cultural relics. Following such a paradigm, the way how analysis and research has been performed on ancient cultural relics are illustrated in detail with examples of ancient ceramics and textile dyes. Meanwhile, as the second type of Herit-Materials, three categories of conservation materials, such as emergent conservation materials on archaeological sites, consolidation materials and cleaning materials have been reviewed in detail, including basic concepts, criteria for choosing appropriate materials for conservation purposes, evaluation of the conservation effects after application, along with the application methods of those conservation materials. Finally, as Herit-Materials’ studies have attracted many researchers and have also created new inter-disciplinary research fields, the following research directions are recommended for scholars who have interest, including the development of advanced and comprehensive analytical technique of Herit-Materials, non-destructive and in-situ characterization & testing of Herit-Materials, the database of composition-structure-performance for Herit-Materials and their real-time environmental conditions, the green Herit-Materials for conservation purposes and their application methods, as well as the type and pattern analysis research of Herit-Materials.
... The mass spectrum obtained from the powder sample shows a less complex matrix than the fresh sample, likely due to processes during the drying step. Similar phenomena can be seen in the analysis of fresh and dried madder (Rubia tinctorum L.) [29], which is also a root used for dyeing. The noisier baseline in the turmeric powder spectrum ( Figure 4B) compared to the fresh turmeric spectrum ( Figure 4A) suggests that the chromophores are less concentrated in the powder sample. ...
Desorption electrospray ionization mass spectrometry (DESI-MS) is an ambient mass spectrometry technique that shows great potential for the analysis of fragile heritage objects in situ. This article focuses on the application of a recently built DESI source to characterize natural dyestuffs in historical textiles and a presentation of initial imaging experiments. Optimization of the instrumental settings, geometrical parameters, and solvent system on the DESI-MS analysis was conducted on rhodamine B samples. Some variables, including an increased flow rate, a narrower range of optimized geometrical variables and a solvent system without additives, were applicable to both early synthetic and natural dyes. Direct dye turmeric (Curcuma longa L.) could be reliably analyzed on both silk and wool, as could anthraquinone standards without mordanting. These preliminary results suggest that the dye application process (direct, mordant, vat) has a large impact on the ionization efficiency of DESI-MS. Imaging trials highlighted the suitability of DESI-MS for the analysis of patterned textiles that are difficult to sample, such as calico fabrics, or other currently inaccessible objects.
... The latter can cause undesirable changes in the heritage objects' original visual appearance [8,[13][14][15]. Nevertheless, great efforts have been made to improve their detection in heritage objects, including by in situ techniques such as Raman Microscopy, Fibre Optics Reflectance Spectroscopy (FORS) and Hyperspectral Imaging and Microspectrofluorimetry [16][17][18][19][20][21]; however, unequivocal identification is still only possible by fingerprinting techniques using micro-samples such as High-Performance Liquid Chromatography-Diode Array Detector (HPLC-DAD) and Surface-enhanced Raman spectroscopy (SERS) [22][23][24]. ...
This paper focuses on the first investigation of the 19th-century manufacture of red lake pigments obtained from madder by Winsor & Newton (W&N), prominent artists’ colourman at that time. The first approach to their manufacture was carried out by studying the madder entries of the company’s book P1, found in the W&N 19th Century Archive Database. Eleven production records were discovered under names such as Rose Madder, Madder Carmine, Madder Lake and Madder Rose. Three main methods of synthesis were identified and reproduced, revealing three main steps: washing of the madder roots (Rubia tinctorum L.); extraction in acid media and complexation with Al³⁺ using alum; and precipitation by the addition of salts such as ammonium carbonate and sodium borate. The syntheses were followed by UV-VIS spectroscopy, and the pigments were further characterised by colourimetry, Energy-Dispersive X-Ray Fluorescence Spectrometry (XRF), Fourier Transform Infrared Spectroscopy (FTIR) and High-Performance Liquid Chromatography-Diode Array Detector (HPLC-DAD). They all exhibited a rose hue in a highly insoluble aluminate matrix. Although the dye extraction was incomplete, alizarin, purpurin and pseudopurpurin were identified. An analytical comparison with a Rose Madder 19th-century oil paint tube was also performed by micro-FTIR and microspectrofluorimetry. This work intends to be foundational to a systematic study of the W&N’s 19th-century madder colours aiming to contribute new knowledge towards their identification and preservation in heritage objects.
... 27 As is well known, R. cordifolia contains large amounts of purpurin along with very small amounts of alizarin, whereas R. tinctorum has a very large alizarin peak. 28,29 Thus, it is inferred that the red textile has been dyed with R. tinctorum from the result of total ion current. R. tinctorum in South Asia may have been imported to the Central Plains through the route that passed through the Shu Kingdom (Sichuan Province of China). ...
In this paper, a series of modern analysis methods, including Raman spectroscopy, X-ray diffraction, UV-vis spectrophotometry, and ultra-high-pressure liquid chromatography coupled with a thermoelectric LTQ-Orbitrap XL ETD mass spectrometer (UHPLC-MS/MS), were applied to analyze and accurately identify the chemical composition of plant dyes and the mineral pigment from the samples collected from grave goods. As a result, the textiles were dyed by the madder, Kermes, Phellodendron chinense, indigo, Lithospermum L., and so forth. In addition, the mineral pigment, charcoal, hematite, minium, cinnabar, azurite, and malachite were used to paint the exquisite artifacts in the tomb of Murongzhi. This research demonstrates the profound impact on cultural transmission and fusion in the "Tuyuhong" dynasty and explores the Silk Road in Tang dynasty.
... This is considered the state-of-the-art technique for identifying natural and synthetic dyes at a molecular level [22][23][24][25][26][27][28][29]. The technique requires minimal sampling (1-2 mm of a single thread) and provides insight into the molecular composition of dyes and dye mixtures, which is fundamental information for achieving straightforward identifications [11,[30][31][32]. ...
In the framework of the ‘Amorepacific Project for the conservation of Korean pictorial art’ (2018–2023) at the British Museum, three traditional Korean paintings have been investigated with the aim of supporting their conservation and obtaining information about the dyes used in the mounting textiles and other mounting elements. The paintings include a rare example of late 18th-century traditional Korean portraiture (accession number 1996,0329,0.1); a late 19th-century two-panel screen silk painting of Pyeongsaeng-do-Scenes of life (accession number 2016,3028.1); and a late 19th-century twelve-panel screen silk painting representing the Five Confucian virtues (accession number 1957,1214,0.1). The mounting textiles were investigated non-invasively by using digital microscopy and fibre optic reflectance spectroscopy (FORS), and the results guided a minimally invasive sampling campaign. Fourteen samples were analysed by using high-pressure liquid chromatography coupled with diode array and tandem mass spectrometry detectors (HPLC-DAD-MS/MS), leading to the identification of the natural dyes indigo, sappanwood (Biancaea sappan, formerly Caesalpinia sappan), amur cork tree (Phellodendron amurense) and safflower (Carthamus tinctorius) in the mounting elements of the 18th-century portrait. These results confirmed some of the non-invasive observations and were in agreement with the production date of the painting. Both natural and synthetic dyes were identified in the mounting textiles of the panel screens. Among the synthetic dyes, fuchsin (C.I. 42510), methyl violet 3B (C.I. 42536), methyl blue (C.I. 42780) and benzopurpurin 4B (C.I. 23500) were identified. These are early synthetic dyes first synthesised between the 1860s and the 1880s, suggesting that the silk textiles are likely to have been dyed in the last part of the 19th century.
... Traditional textile fibres detection methods include visual inspection, microscopic observation, and combustion. With the continuous improvement and updating of detection technology, the current detection methods for textile fibres are chromatography [8][9][10] and spectral methods. Chromatography is destructive to textile fibre samples and cannot maintain the samples ' integrity. ...
Textile fibre is very common in daily life, and its classification and identification play an important role in textile recycling, archaeology, public security, and other industries. However, traditional identification methods are time-consuming, laborious, and often destructive to the samples. In order to quickly, accurately, and nondestructively classify and recognize textile fibres, this study established a textile fibre classification and recognition method based on hyperspectral imaging (HSI) and a one-dimensional convolutional neural network (1D-CNN) model. Hyperspectral images of 25 kinds of commercial textile fibres were collected and denoised by pixel fusion. Four traditional machine learning classification models, k-nearest neighbors (KNN), support vector machine (SVM), random forest (RF), and partial least squares-discriminant analysis (PLS-DA), were used to identify the data. The results show that RF has the highest classification accuracy, reaching 91.4%. Then a back propagation neural network (BPNN) model and a one-dimensional convolutional neural network (1D-CNN) model were constructed and compared with the traditional machine learning methods. The results show that the 1D-CNN models have 97.9% and 98.6% accuracy on the training and test sets, respectively. The precision (Pr), sensitivity (Se), specificity (Sp), and F1 score (F1 score) of the models reached 98.7%, 98.6%, 99.9%, and 98.6%, respectively, which were significantly better than the four traditional machine learning models. It seems that 1D-CNN combined with the HSI technique may be a potential method in the detection and classification of textile fibres.
... AD Degano (2015) The proportion of purpurin with respect to alizarin is often considered as a criterion for distinguishing the two types of madder (i.e. Rubia tinctorum and Rubia peregrina) although several factors may influence the relative amount of the identified compounds such as the extraction procedure from the raw material, the dying technique employed and the state of preservation of the dyed textile (Mouri and Laursen 2012). Experimental dyeing and subsequent analysis have shown that the ratio between alizarin and purpurin in Rubia peregrina is opposite with respect to that of Rubia tinctorum, being Rubia peregrina richer in purpurin (Wouters et al. 2008). ...
Fibres and dyes in four Coptic textiles preserved at the Moghadam Museum in Tehran, Iran, were characterised using scanning electron microscopy (SEM) and high-performance liquid chromatography coupled with photodiode array detector (HPLC–DAD) and high-resolution mass spectrometry (HPLC-HRMS). The results showed that natural plant dyes including madder, indigo/woad and tannins were used to dye wool and linen fibres with different size and quality. Furthermore, the beige colour was identified to have been achieved by plants from a Rhamnus specie (Persian berries) rarely reported from Coptic textiles. Mixtures of the dyes were also identified in the textiles consistent with what we know from Coptic textiles. Both stylistic and technical studies suggest that these textiles have been woven some time between the fourth and the seventh century AD.
... By contrast, when sampling is possible, highly detailed information relating to the molecular structure of the dye molecules can be obtained by using high-performance liquid chromatography (HPLC) [37]. The technique enables all the molecular components present in the sample to be chromatographically separated and identified singularly so that the exact plant or animal source(s) of the dye(s) are identified at the species level [38][39][40][41][42]. The identification is achieved by recording the UV/Vis absorption spectra of the dye molecules with a photodiode array (PDA) detector [43][44][45], their fluorescence spectra with fluorescence (FL) detector [46], and/or their masses with a mass spectrometer (MS) [12,[18][19][20]22,23,47,48]. ...
Mount components and textile borders represent important elements of Asian paintings. However, they are often side-lined or not considered an integral part of the original piece, as they may be later additions or may have been replaced during historic conservation or mounting interventions. Nevertheless, evidence is sometimes present that textile borders are contemporaneous to the production of the paintings they frame or, in the case of paintings found in archaeological contexts, to the time of deposition. Even when not contemporaneous with the paintings, the mount textiles are often of significant historic interest in themselves, showing a range of complex textile techniques and materials, and highlighting the re-use of fabrics. In all these cases, the study and reconstruction of the original colours of the borders enable further understanding of the holistic visual impact originally intended for the composition, as well as of the role of colour itself, which was used to emphasise, complement or contrast important pictorial themes or motifs in the paintings. Furthermore, the identification of dyes and dyeing techniques has the potential to support the production date and provenance of the paintings. In this study, the textile borders and some additional mounting elements of six paintings (late 9th–10th century CE) from the Library Cave, Mogao Grottoes, Dunhuang, China, one rare Korean portrait painting dated 1789 CE, and two Tibetan thangkas (18th century) were investigated with the aim to identify the dyes present. Fibre optic reflectance spectroscopy (FORS) was used to obtain information non-invasively and, when sampling was possible, high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) was used to obtain molecular identification of the dyestuffs employed in their production. Typical Asian dyes, such as gromwell (Lithospermum erythrorhizon), sappanwood (Biancaea sappan), safflower (Carthamus tinctorius), turmeric (Curcuma longa) and pagoda tree flower buds (Sophora japonica), were identified. Some of the dyeing techniques were commensurate with the geographical and temporal provenance assigned to these pieces. Considerations about fading and discolouration of the dyes enabled valuable additional information to be obtained that complements the evidence gleaned from the study of the paintings and informs conservators and curators on best practices in the preservation and display of these precious and delicate artworks.
... 27 The identification of individual madder species in several of the coloured yarns (red-brown, orange) was limited, as alizarin was not systematically observed to be the predominant anthraquinone present. 28 This is probably due to the fact that the concentration of the different anthraquinones found within the same Rubia species can be highly variable and is known to depend on both the age of the plant and the environment in which it is grown. 29 However Rubia tinctorum L. is likely to be the primary madder source used in England during this period. ...
We present a comprehensive investigation of two rare examples of turkeywork carpets held in Scottish collections: the Kinghorne carpet at National Museums Scotland and the Chaloner carpet in the Burrell Collection. Analysis by ultra-high-performance liquid chromatography (UHPLC-PDA) showed that the colours used in the making of the carpets were achieved by subtle dyeing sequences utilising a range of dye sources (cochineal, weld, dyer's greenweed, madder, brazilwood and young fustic) combined with overdyeing processes (indigo/woad). The levels of photodegradation of the flavonoid-based yarns are also discussed.
... The results showed, in order of elution, the presence of lucidin primeveroside (m/z 563), ruberythric acid (533 m/ z), munjistin (m/z 283), alizarin (m/z 239), xanthopurpurin (m/z 239), and purpurin (m/z 255), apparently markers for madder, the dye extracted from different Rubiaceae species. The presence or absence of one or more of these compounds, and the ratio among them, could suggest the original species from which the madder dye was obtained, but in this case the contextual presence of ruberythric acid and alizarin points to Rubia tinctorum as the source [30][31][32]. ...
The folded almanac Western MS.8932 (Wellcome Collection, London), produced in England between 1387 and 1405, is a calendar with astrological tables and diagrams used by medical practitioners to harness astrological information relating to health. Apart from the great interest for its use in medicine, this object has a unique feature in its exquisite, unique embroidered binding that indicates a prestigious artefact. Considering the scarceness of information on such items, a diagnostic study on the materials used for the outstanding embroidery of MS.8932 is a unique occasion of having information on the methods of production of medieval embroideries. A diagnostic campaign has been carried out to identify the dyes used for this task and the colourants used for the illuminations, and to evaluate them with reference to their commercial value. Preliminary information on the dyes was yielded by means of UV-visible diffuse reflectance spectrophotometry with fibre optics (FORS) and spectrofluorimetry with fibre optics (FOMF). Then a final identification was yielded by micro-invasive analysis involving Surface Enhanced Raman Spectroscopy (SERS) and High Performance Liquid Chromatography-Diode Array Detector-Mass Spectrometry (HPLC-DAD-MS)[¹]. Analysis on the micro samples (5-10 mm of very thin threads) taken from the embroidery revealed the presence of orchil for pink hues, indigo/madder double dyeing for purple hues, red safflower for salmon pink hues and indigo/weld double dyeing for green hues. Particularly remarkable was the additional identification of aloe in the purple threads, possibly used as mordant and/or as antibacterial agent, which evidence is the first ever recorded in such materials. This information is very important to understand the significance of the artefact and its historical-artistic location, and will allow to make comparison with similar artworks.
... In addition, several components consistent with the use of the natural plant-based dye madder were identified in the red dyed silk: munjistin, pseudopurpurin, purpurin, and a small amount of alizarin. Of the Rubia species used as dyestuffs previously examined by LC methods, only Rubia tinctorum is known to contain both alizarin and purpurin [52]. Their combined presence in the red fiber suggests this is the plant species used to generate the dye appearing as a minor color component in the carpet fragment. ...
The use of forensic dye analysis in the field of cultural heritage is introduced, and a case study is presented determining the dating of a potentially important textile fragment from the Cleveland Museum of Art. The fragment, attributed on stylistic grounds to the 15th century, is purportedly the oldest surviving example of a Persian knotted-pile silk carpet. Raman spectroscopy combined with liquid chromatography – mass spectrometry determined the dyes used in the fragment include Metanil yellow, Congo red, and indigo, possibly in its synthetic form. Based on the dates of introduction for these dyes (1879, 1884, and 1897, respectively) and the first appearance of the textile fragment in 1928, the object is shown to be almost certainly a late 19th or early 20th century creation. Furthermore, impurities found in the red dye are suggested as potential markers of a pre-1970s synthetic route for manufacturing Congo red or possibly degraded Congo red due to environmental pollutants.
... This technique gives information on the exact molecular composition of a sample, as all the dye molecules present are chromatographically separated and identified singularly 32,33 . Mixtures are therefore easily resolved, and dye sources can be identified with extreme precision, down to the exact plant or animal species 34,35 . Unfortunately, so far, the amount of sample reported to be needed for such analysis, although very small, does not appear to be suitable to analyze Japanese woodblock prints. ...
Three Japanese woodblock prints from the Edo period (1603–1868) underwent a scientific investigation with the aim of understanding the changes in the colorants used in Japanese printing techniques. A multi-analytical approach was adopted, combining non-invasive techniques, such as fiber optic reflectance spectroscopy (FORS), Raman spectroscopy, multispectral imaging (MSI), and macro X-ray fluorescence (MA-XRF) with minimally invasive surface-enhanced Raman spectroscopy (SERS). The results enabled many of the pigments to be identified and their distribution to be studied, apart from two shades of purple of organic composition. Consequently, the potential of high-pressure liquid chromatography tandem mass spectrometry (HPLC–MS/MS) was explored for the first time with application to Japanese woodblock prints. The intrinsic sensitivity of the instrument and an effective extraction protocol allowed us to identify a mixture of dayflower (Commelina communis) blue and safflower (Carthamus tinctorius) red in purple samples constituted of 2–3 single fibers. In addition to the innovative integration of MA-XRF and HPLC–MS/MS to investigate these delicate artworks, the study concluded on the use of traditional sources of colors alongside newly introduced pigments in late Edo-period Japan. This information is extremely important for understanding the printing practices, as well as for making decisions about display, conservation, and preservation of such artworks.
... Those reactions may also affect the dyeing potential, as the products of hydrolysis, i.e. aglycone structures, differ in their properties and affinities to various materials compared to their derivatives [9,13]. The historical background does not necessarily give any guarantee of safeness as even widely-used dye sources can contain toxic secondary metabolites: madder root extracts (R. tinctorum) having alizarin (1) as the main anthraquinone aglycone, also contained toxic lucidin (2), rubiadin (3) and xanthopurpurin (4) ( Table 1) [26][27][28][29][30], of which lucidin and xanthopurpurin were hydrolysis and decarboxylation products of lucidin primeveroside and munjistin. Furthermore, it has been proposed that lucidin is converted into other compounds, such as nordamnacanthal or quinone methide [26,28,31] or degrade to xanthopurpurin. ...
Biocolourants have been investigated as alternatives to synthetic dyes. However, natural origin per se is not a label of harmlessness and research is needed to obtain safe dyes. We studied the cytotoxicity of the extracts from fungal (Cortinarius semisanguineus, Tapinella atrotomentosa) and plant (Tanacetum vulgare, Salix phylicifolia) sources and the woollen fabrics dyed with the extracts. Cytotoxicity in vitro using hepa-1 mouse hepatoma cells for 24 h and 72 h exposure was observed as the highest tolerated dose. All biocolourants produced intensive colour on fabrics with fastness properties from moderate to good. The Salix and Cortinarius samples did not show any cytotoxic effects, whereas the Tanacetum and Tapinella samples had slightly higher test values but were not interpreted as being significantly toxic. Higher than zero values of the undyed fabrics showed the importance of examining their toxicity as well. It was found that the cytotoxicity of the samples dyed with the biocolourants did not differ significantly from the undyed wool fabric. The concentrations of dyes used in the assays were very low, imitating the dose of the user. In addition to colouring properties, natural dyes may have pharmaceutical and antibacterial properties which would enhance the interest in using them in products for added value.
Unlike synthetic dyes that produce a single hue, natural dyes offer a rich spectrum of colors. Traditionally, artisans controlled these colors through intuition. Modern computational chemistry now enables precise predictions...
Agricultural biomass is a well‐known renewable resource with a strong possibility of recycling. The current work focuses on extracting, preparing and colouring Napier grass fibre (NGF) with a colourant extracted from Rubia tinctorum (RT) (which is generally known as madder). NGF that had been water‐retted was alkaline scoured and bleached using hydrogen peroxide to increase the material's whiteness index and water absorption capacity without degrading its breaking strength. After being mordanted with tannic acid, the bleached NGF was coloured with an aqueous extract of the colourant extracted from RT. The Box–Behnken response surface methodology design model was employed to optimise the dyeing concentration, temperature and time. The dyed fibre showed good colour strength ( K/S ) and adequate wash, rub and light fastness. Adopting the findings from the current study would increase the efficient utilisation of biomass for use in textiles, which is unnecessarily wasted.
Rapid manufacturing of medical devices during unforeseen pandemics is imperative. In striving for manufacturing efficiency, photopolymerization has emerged as a viable approach for diverse healthcare applications in recent decades. Photopolymerization‐based 3D printing offers significant potential with a range of biocompatible materials (e.g., poly(ethylene glycol), cellulose, etc.) while minimizing waste generation. However, prevalent commercial photoinitiators used in this process are synthetic and environmentally unfriendly. Therefore, the naturally occurring and derived photoinitiators have drawn tremendous research interest due to their bioactivities and inherent environmental safety. This review comprehensively outlines the medical applications implemented by these photoinitiators, highlighting their inherent photoinitiation abilities. Moreover, it delves into the impact of substituent effects on the photoinitiation abilities of naturally derived photoinitiators.
Dye analysis is an important subject in historical textile research because it helps researchers understand the structural and chemical features of colorants and provides a solid base to determine the date, provenance, and trade of textile artifacts. This study is the first investigation of dyes used in historical silk of Indonesia using high-performance liquid chromatography coupled with a diode array detector and mass spectrometry (HPLC-DAD-MS). Three Indonesian silk textiles dating from the nineteenth (19th) and twentieth (20th) centuries are selected from the Southeast Asian textile collection of the China National Silk Museum. Dyes are extracted from the representative silk threads of these artifacts and subjected to chromatographic analysis. The characterization results indicated the use of a variety of natural dyes in the studied threads. In particular, madder dye (Rubia spp.), lac dye (Laccifer lacca Kerr.), and Morindone dye (Morinda citrifolia L.) were used for producing red shades, while green yarns were dyed by a combination of indigo and safflower (Carthamus tinctorius L.) yellow dyes. Furthermore, this study provides the first proposal of the use of saffron (Crocus sativus L.) dye in Indonesian textile dyeing during this period. In addition, Congo Red (C.I. 22,120), Orange I (C.I. 14,600), and Diamond Green B (C.I. 42,000) were identified, signifying the adoption of early synthetic dyes by Indonesian dyers. The current work takes advantage of the sensitivity and reliability of the HPLC-DAD-MS technique in dye analysis in order to give a report on the chemical aspects of coloring materials used in Southeast Asian textiles in the 19th and 20th centuries.
Central Asian ikat textiles are characterised by their bold and large abstract patterns, made up of vibrant colours with a characteristic “blurred edge” effect, which makes them some of the most recognisable fabrics worldwide. Eleven ikats from the collection of the National Museum of Asian Art, Smithsonian Institution (Washington, DC, USA) and six ikats from the collection of the British Museum (London, UK) were investigated by high pressure liquid chromatography coupled to diode array detector and high-resolution tandem mass spectrometry (HPLC-DAD-HRMS/MS) to identify the dyes and expand on recent research focused on the integration of synthetic dyes in ikat dyeing during the second half of the 19th century. The results confirmed that the palette of natural dyes includes cochineal (probably mostly from a local species native to central Asia) for red, larkspur (Delphinium semibarbatum) for yellow, and indigo for blue as the main dye sources. In some of the textiles, madder (Rubia tinctorum) for red and pagoda tree (Sophora japonica) for yellow were also detected as minor components mixed with cochineal and larkspur, respectively. Synthetic dyes, such as scarlet reds (C.I. 16150 and 16155), rose bengale (C.I. 45435), eosin (C.I. 45380), erythrosine (C.I. 45430), fuchsin (C.I. 42510/42520), methyl violet (C.I. 42535/42555), malachite green (C.I. 42000) and brilliant green (C.I. 42040) were detected in eight textiles. In three textiles, natural dyes were identified in the ikat-dyed silk warp threads and synthetic dyes in the red cotton weft threads, highlighting interesting mixtures of materials and textile-making practices. Natural yellow dyes were used in all textiles, even those for which all the other colours are synthetic. These results provide significant new information about the changes in ikat production that occurred during the 19th century in Central Asia.
Background:
Rubia cordifolia L., Rubiaceae, is globally reported to treat skin-related problems. The study aimed to assess the antityrosinase potential of RC and the development of gel formulation.
Methods:
AutoDock vina (version V.1.2.0) program package was used for molecular docking to check for the binding affinity of ligands with protein. Response surface methodology (RSM) software was used to optimize extraction parameters for an alcoholic extract of Rubia cordifolia (ARC). The developed HPTLC method for the quantification of purpurin in ARC was validated as per the ICH guidelines, also the bioautographic study for evaluation of antityrosinase effects was performed, anthraquinone enriched fraction (AEF)-loaded gel formulation was developed and so evaluated which could be used to reduce skin pigmentation.
Results:
Purpurin showed optimum binding affinity (-7.4 kcal/mol) with the molecular target (tyrosinase) when compared to that of standard kojic acid (-5.3 kcal/mol). Quantification of purpurin in ARC, optimized by RSM software was validated and physiologically significant results were observed for the antityrosinase potential of AEF, along with TLC-MS-bioautographic identification for antityrosinase compounds: purpurin (m/z 256.21) and ellagic acid (m/z 302.19). Evaluation of AEF-loaded gel formulation by in vitro and ex vivo permeation studies was performed.
Conclusion:
ARC extraction parameters optimized by RSM, and bioautographic study helped identify antityrosinase compounds. The development of gel formulation could be a cost-effective option for the treatment of depigmentation in the future.
The current study provides the first review of alizarin, a natural dye, in terms of its historical aspects and its potential for functional applications in textiles. The review begins with a brief overview of natural alizarin and its occurrence in Rubiaceae family plants, followed by a discussion of alizarin acquisition from its botanical sources through conventional and advanced extraction methods. A special emphasis of this study is on the identification of natural alizarin colourants in archaeological and cultural textiles by using analytical methods based on reflectance, Raman spectroscopy, mass spectrometry and chromatographic profiles. In addition, the functional properties of natural alizarin, including its antimicrobial activity, anti‐oxidant activity, insect repellence and ultraviolet protection, are analysed. This paper summarises the methods for obtaining alizarin for coloration, as well as advanced techniques for detecting alizarin in historical textiles, and potential applications of natural alizarin as a functional textile dye.
Children can encounter art materials that contain hazardous substances at school, in the home, and during outside activities. Hazardous substances can be found in both art materials that are made to be used by children and art materials used by adults. Some of these materials can be severe irritants, allergens, carcinogens, or other chronic disease hazards. Many of the most frequently used and potentially most hazardous materials are found in the categories of solvents, pigments, and adhesives. Selected members of these categories and where they may be found in common art materials are briefly discussed. Preventive techniques that specifically address the potential hazards of each category are included. [ Pediatr Ann . 2023;52(6):e219–e230.]
Natural organic red and yellow materials were among the major colorants in woodblock prints of the Edo period in Japan (1603–1868). Noninvasive analyses of these colorants by fiber optics reflectance spectroscopy (FORS) have successfully identified some of the colorants, but many cannot be reliably characterized by this technique. Some reds and yellows exhibit fluorescence, in certain cases quite strong, in others relatively weak. Fluorescence spectroscopy with external fiber-optic probes has been applied to the luminescent materials, with excellent results in some cases but more problematic ones in others. Challenges include the natural variability of luminescence for specific materials, due to methods of preparation and interaction with substrate or other admixed colorants. In addition, the important red colorants have excitation and emission spectra that overlap. This case study examines the application of excitation–emission matrix (EEM) spectroscopy for the characterization of a variety of colorants, supplemented by individual excitation and emission spectra extracted from the EEM data files. Examples are from the collection of the Museum of Fine Arts, Boston, drawn from an extensive study that has involved several hundreds of prints to date.KeywordsExcitation–emission matrix spectroscopyFiber optics reflectance spectroscopy (FORS)
Ukiyo-e
Wool fabrics can be dyed with synthetic dyes and even with natural dyes. To present a different aspect to the coloration of wool, the study was focused on a topping process (dyeing of wool which was already dyed) with different natural dye sources. For this purpose, the fabrics that were already dyed with a natural dye source were once again dyed with two different natural dyes. In bottom dyeing (bottoming), fabrics were dyed with hops (Humulus lupulus L.) in the presence of different mordanting agents. Then the dyed, washed, and dried samples were once again dyed (topping) with two different natural dye sources. For topping, the powdered madder and acorn were tested in direct dyeing of wool samples. Finally, the colour changes were analysed with the use of a spectrophotometer. The study demonstrated that such a process (bottoming with hop in the presence of different mordanting agents and then topping with madder or acorn) can be a way to obtain different shades and colours with sufficient/good fastness values by natural dyeing.
Recent interests of scientists in the natural dyes for not only textile colouration but also clean production of functional fabric materials, has led to the development and application of ancient nature-based sources of colourants. Historical textiles are considered as important artefacts that present the culture and society from antient time to contemporary centuries, as well as the database to develop the functional materials. Study of organic colourants in ancient textiles is an effective approach to investigate the historical dyeing science and technology, likewise evolve the bio-colourants for modern applications. Plant-based colouring matters were widely utilized since the early textile civilization until the early 20th century. Currently, several anthraquinone colourants are discovered from vegetation, especially the morindone which was widely used in traditional fabric dyeing techniques of Southeast Asia, India and the Pacific Islands. In this context, the principal focus of this study is anthraquinone-based morindone dye, started from a brief overview of natural anthraquinone dyes in historical textiles, followed by the detailed discussion on biological sources, extraction of morindin, modification to red morindone pigment, as well as the summary of mordanting and dyeing method. For intensive investigation of the practical utilization of organic morindone in historical textiles, some recent works using analytical methods including high performance liquid chromatography (HPLC) and surface-enhanced Raman spectroscopy (SERS), are thoroughly discussed. Furthermore, the potential antimicrobial and ultraviolet protective performances of morindone dye are analysed with respect to effective application of morindone in functional textiles.
The anthraquinone components of the roots of various species of madder (like Rubia tinctorum L. and Rubia peregrina L.) have been used for millennia as red colorants in textiles, carpets, tapestries, and other objects. To understand the selection and preparation of dyestuffs in various cultures and historical periods, these dyes (mainly alizarin and purpurin) are traditionally analyzed by means of separation methods that require sampling. This contribution focuses on establishing a fast, noninvasive, and in situ analytical procedure based on visible reflectance spectroscopy for the characterization and quantification of anthraquinones in ancient wool yarns. The method was successfully applied to Coptic textiles, and the analytical results are in agreement with prior observations obtained on samples by separation techniques.
The Douzlākh salt mine Chehrābād in northern Iran offers good preservation conditions for organic finds of all kinds (wood, botanical remains, human faeces, textiles, ropes, leather and fur objects, human mummies). More than 15% of all artefacts found in the waste layers of the salt mine are textiles, most of them covering roughly a timespan between the fifth century BCE to the sixth century CE, which refers to the Achaemenid and Sassanid periods of the Persian Empires. Within the framework of a recent research project, our focus lies on interdisciplinary textile research, including diverse analytical tools to gain basic data, radiocarbon dating, isotopic tracing, fibre analysis and wool measurements, dyestuff analysis and advanced conservation methods. The textiles from Chehrābād are an important source for our understanding of textile technology of the Ancient Near East and the Persian Empires. This chapter deals with the dyeing research of selected Sassanid textiles (approx. 400–600 CE) and discusses how the outcome of the research, in terms of the biological dye sources applied in the material, can contribute to the geographical and historical context of the finds. This will provide knowledge about the dyeing tradition in Iranian territory and possible trade in dyes and textiles between Iran and other contemporary Mediterranean cultures.
A new A2B2-type porphyrin, namely: 5,15-bis-(3-hydroxyphenyl)-10,20-bis(3-methoxyphenyl)-porphyrin (trans-A2B2-porphyrin), and its platinum(II) derivative (Pt-trans-A2B2-porphyrin) were synthesized and completely characterized by UV–vis, FT-IR, 1H-NMR, 13C-NMR and AFM methods. The Pt-metalloporphyrin was complexed with colloidal gold (AuNPs) and the obtained nanomaterial (Pt-trans-A2B2-AuNPs) was able to optically detect the potassium salt of 1-anthraquinonsulfonic acid (AQ) in the concentration range 2.419 × 10–8 M to 2.5 × 10–7 M with relevance in medical investigations of microbial, congestive and cancer diseases, in diabetes and pancreatic fibrosis. The tested interfering species, selected from those usually present in physiological media, did not strongly influence the detection capacity of the complex nanomaterial toward AQ, even if the used concentrations are 50 times higher than that of the detected AQ. The AFM images of Pt-trans-A2B2-porphyrin, Pt-trans-A2B2-AuNPs and the hybrid material after 1-anthraquinonsulfonic acid detection (Pt-trans-A2B2-AuNPs-AQ) show significant morphologic differences from an uneven coverage with conical aggregates and holes having various sizes in the case of Pt-trans-A2B2-porphyrin, to columnar aggregates in the case of Pt-trans-A2B2-AuNPs hybrid material and finally to a relatively uniform distribution of self-assemblies for Pt-trans-A2B2-AuNPs after interacting with AQ, having lower dimensions than those of the used hybrid material. The detection mechanism was proposed and justified.Graphical abstract
We present here a novel strategy for textile sample treatment, using galvanic displacement-based substrates, to identify anthraquinone dyes by surface enhanced Raman spectroscopy (SERS). This global procedure of SERS analysis, using several silver microparticles, in particularly those of dendritic shape, formed by reducing silver nitrate with zinc or copper, can be accomplished within 20 min. Compared to the synthesis of standard Lee-Meisel colloids, the preparation of silver dendrites provides a simple, fast and cost-effective route to produce reliable SERS substrates. The most fascinating feature is that the textile fibers analyzed are almost simultaneously covered with the substrates once the galvanic displacement reaction is triggered. This method was successfully applied to discriminating between alizarin and purpurin in a 6th-9th century samite with bird roundels, and carminic acid and laccaic acid in a 1740s chinoiserie brocade. However, as is the case with other silver substrates, the Raman signals of the insect dyes normally overlapped those of the plant dyes in the SERS profiles.
A sample preparation workflow for historical dye analysis requiring less sample has been developed. Samples as small as 0.01 ± 0.005 mg have been successfully analysed and high percentage recoveries (>85%), more automation and shorter preparation time have been achieved using filtration by centrifugation and only one manual transfer. The optimised workflow based on 96 well plates together with the shorter UHPLC method developed makes dye analysis data collection faster from unprocessed sample to result, facilitating the creation of larger datasets and application of chemometric approaches. The method was evaluated on 85 samples from 12 dye sources (RSD < 5.1%, n = 5) as well as 22 samples from a 17th century embroidered stomacher from the National Museums Scotland (NMS) collection.
Among the artists’ materials of the nineteenth century, pastel crayons merit scientific interest since their early commercial formulations are mostly unknown and, until now, have been considerably less studied with respect to other contemporary painting materials. In this framework, research herein reports the results of a comprehensive multi-analytical study of 44 pastel crayons of two recognized brands (LeFranc and Dr. F. Schoenfeld) from the Munch museum collection of original materials belonging to Edvard Munch. The integrated use of complementary spectroscopic and hyphenated mass-spectrometry techniques allowed the compositional profiles of the crayons to be traced providing the identification of the inorganic and organic pigments, the fillers/extenders and the binders. All crayons resulted to be oil- based and the binder was identified to be a mixture of a drying oil (safflower or linseed oil), palm oil or Japan wax and beeswax. Among others, pigments such as ultramarine, chrome yellows, Prussian blue, manganese violet, viridian and madder lake have been identified. A significant alignment in formulations of the brands was observed with the only exception of the greens which showed distinctive pigment and filler compositions. The analytical information provided for these commercial artists’ materials will be of great interest for academia, museum and other institutions hosting art collections dating from the same period and it will be used by the Munch museum to draw proper conservation strategies of its own artwork collections.
Bu çalışmada, kökboya (Rubia tinctorum L.) bitkisinde kök ve adventif kök indüksiyonuna eksplant kaynağı ve oksin grubu hormonların etkilerinin belirlenmesi ve elde edilen köklerin sekonder metabolit içeriği ve antioksidan aktivitelerinin belirlenmesi amaçlanmıştır. Kök ve adventif kök kültürünün oluşturulmasında in vitro koşullarda yetiştirilen 45 günlük bitkilerin gövde, yaprak ve kök kısımları eksplant kaynağı olarak kullanılmıştır. Eksplantlar 4.4 g L-1 MS (Murashige ve Skoog), 30 g L-1 sukroz ve 2 g L-1 phytagel ve 2 mg L-1 oksin içeren besin ortamında karanlık koşullarda kültüre alınmıştır. Besin ortamına oksin grubu hormonlardan indol-3-bütirik asit (IBA), naftalenasetik asit (NAA) ve indol-3-asetik asit (IAA) ilave edilmiştir. Bu ortamda gelişen kök ve adventif kökler 30. gün hasat edilerek kök gelişim parametreleri belirlendikten sonra kökler kurutularak toplam antrakinon, fenolik ve flavonoid içeriği belirlenmiştir. Ayrıca köklerin antioksidan kapasiteleri katyon radikali giderme (ABTS), indirgeme gücü (FRAP) ve serbest radikal giderme (DPPH) metotları ile belirlenmiştir. Toplam antrakinon, toplam fenolik ve flavonoid içeriği en yüksek IAA besin ortamında gövde eksplantlarından gelişen adventif köklerde sırasıyla 9.83 ± 0.11 mg g-1, 14.45 ± 0.29 mg GAE g-1 ve 3.85 ± 0.03 mg KUE g-1 olarak belirlenmiştir. En yüksek DPPH, ABTS ve FRAP aktivitesi de IAA besin ortamında gövde eksplantlarından gelişen adventif köklerde belirlenmiştir.
Plants and insects have been the main sources of natural dyes in the past and have been utilized for several millennia. A large number of well-preserved textiles unearthed from archaeological sites has provided us with opportunities to understand systematically the use of natural dyes in Northwest China. In the present study, dye analyses of about 400 samples from archaeological textiles dating from the 17th century BCE to the 10th century CE were carried out by high performance liquid chromatography coupled with a diode array detector and a mass spectrometer detector (HPLC-DAD-MSD), revealing a 2500-year history of natural dyes in Northwest China. At least 16 dyes were used to color the archaeological textiles. Of these, Rubia tinctorum is considered to be the earliest dye source in Northwest China, but the presence of Porphyrophora species in Subeixi textiles (the 5th-3rd centuries BCE) suggests that the early transmission of the steppes culture from the south of Siberia to the Turpan Basin occurred in the early Iron Age. The geographical origins of the dyestuffs identified in Mogao Grottoes textiles indirectly indicate that the four most influential cultures--Chinese, Hellenic, Islamic and Indian--in Eurasia all converged at Dunhuang in the Tang Dynasty.
A reverse phase liquid chromatography-photodiode array detection method is developed for the characterization of ancient samples of madder. In the past, modifications of the madder chemical composition were carried out by hydrolysing the plant dye precursors in order to increase its red power, the aim of this transformation being to concentrate the red colour of the matter. After extraction of madder dyes in a water-methanol mixture, different anthraquinonic compounds were identified through the chemical constituents present in a garancine sample and in the two madder species growing in the Mediterranean area: Rubia tinctorum and R. peregrina. These two species comprise alizarin, purpurin, lucidin, rubiadin and pseudopurpurin for aglycones and, lucidin primeveroside, ruberythric acid, galiosin and rubiadin primeveroside for heterosidic precursors. These compounds were identified through retention times and UV spectra in comparison with pure standards. Six ancient materials belonging to the collection of the Roure Museum in Avignon (France) and dating from the nineteenth century are characterized as hydrolysed madder (garancine), synthetic alizarin and R. tinctorum roots. A colorimetric study is performed to compare the colour of each sample according to its chemical composition.
Plants and their derived cell and tissue cultures in the family Rubiaceae accumulate a number of anthraquinones. There are two main biosynthetic pathways leading to anthraquinones in higher plants: the polyketide pathway and the chorismate/o-succinylbenzoic acid pathway. The latter occurs in the Rubiaceae for the biosynthesis of Rubia type anthraquinones. In this pathway, ring A and B of the Rubia type anthraquinones are derived from shikimic acid, -ketoglutarate via o-succinylbenzoate, whereas ring C is derived from isopentenyl diphosphate, a universal building block for all isoprenoids. At present, it is known that isopentenyl diphosphate is formed via the mevalonic acid pathway or the 2-C-methyl-D-erythritol 4-phosphate pathway. Recent findings demonstrate that the 2-C-methyl-D-erythritol 4-phosphate pathway, not the mevalonic acid pathway, is involved in the formation of isopentenyl diphosphate, which constitutes ring C of anthraquinones in the Rubiaceae. This review summarizes the latest results of studies on the biosynthetic pathways, the enzymology and regulation of anthraquinone biosynthesis, as well as aspects of the metabolic engineering. Furthermore, biochemical and molecular approaches in functional genomics, which facilitate elucidation of anthraquinone biosynthetic pathways, are briefly described.
The possibilities in the identification and quantitation of the constituents of Rubia tinctorum L.'s root, called also madder root, was described and compared by gas chromatography (GC)-MS, high-performance liquid chromatography (HPLC)-UV/photodiode array detection (DAD) and HPLC-MS: chromatographic analyses were carried out in parallel, from the same samples/extracts/hydrolyzates. Anthraquinone glycosides, anthraquinones, carboxylic acids and sugars were determined directly in the presence of the matrix and in its extracts without and subsequently to hydrolyses. Hydrolyses were performed as a function of time, with hydrochloric and trifluoroacetic acids, as well as enzymatically. Data revealed that as hydrolyzing agent trifluoroacetic acid is to be preferred. Madder root's anthraquinones (pseudopurpurin/purpurin, alizarin, lucidin, munjistin, nordamnacanthal) were identified on the basis of their absorption spectra (HPLC-DAD) and fragmentation patterns by GC-MS and HPLC-MS, equally. Reproducibility of anthraquinone's quantitation, by HPLC-DAD and GC-MS, in the concentration ranges of 4 x 10(-5) to 3 x 10(-2)g/g dried sample, provided an average reproducibility of 4.2% (varying between 0.9 and 9.4% relative standard deviation (RSD percentages)). Carboxylic acids (malic, citric, quinic, rosmarinic acids) and saccharides (xylose, ribose, fructose, glucose, sucrose, primverose) were quantified as their trimethylsilyl (oxime) ether/ester derivatives by GC-MS, in the concentration ranges of 10(-5)g to 10(-2)g/g dried sample, with an average reproducibility of 4.7% RSD.
This review has been written in order to update the literature on anthraquinones occurring in the Rubiaceae. Since appearance of the excellent book on naturally-occurring quinones by R.H. Thomson (120) in 1971 about 50 new anthraquinones have been isolated from members of the Rubiaceae. Also several new methods have been used for structure analysis and separation of the anthraquinones which have not been subject to review before. For this review we have confined ourselves to the naturally occurring anthraquinones and therefore the synthesis of anthraquinones is not included. The article covers the literature from 1969 to 1984.
Separation and quantitative determination of anthraquinones is achieved by high performance liquid chromatography in mixtures of methanol, water and formic acid on a reversed-phase stationary phase. The products are identified by retention time and, more accurately, by standard additions and UV-visible spectroscopy. This methodology has been applied to extracts of plant roots and insects, commonly used in earlier times as the source of red dyestuffs for dyeing textiles. Quantitative evaluation of the anthraquinone derivatives present in ancient red dyes was earned out after acid hydrolysis of 0·2 to 2·0mg of textile fibre. Due to the great sensitivity of the method, important minor constituents, such as kermesic acid in cochineal, can be detected.
A series of textiles belonging to various pre-Columbian civilizations as well as a series of present-day Peruvian natural dyes were analyzed using high-performance liquid chromatography and diode-array detection. The analytical results were classified according to the composition of known dyes or to specific compositional patterns of unknown dyes. Plant reds (from Relbunium species) and animal reds (cochineal from the scale insect Dactylopius coccus) were each predominantly present before and after the Huari and Tiahuanaco cultural periods (700-1100 A.D.), respectively. During these periods both reds were found together. One red and one yellow vegetal dye were both found to occur in the Paracas necropolis only. The analysis of the complex yellow dyes may be useful for the determination of early Peruvian dyes.
Preface Introduction Chapter I. Trade or Raid Chapter II. Peace or War Chapter III. Frontier Markets Chapter IV. Tribute and Bestowals Chapter V. Intermarriage Chapter VI. Conflict or Calm Notes Bibliography Glossary Index
The secondary metabolites isolated from Rubia species, their biological activities, and colouration
properties have been reviewed. Over 150 chemical constituents belonging to different classes of bioactive
compounds such as anthraquinones and their glycosides, naphthoquinones and glycosides, terpenes, bicyclic
hexapeptides, iridoids, and carbohydrates are listed together with their source(s) and corresponding references.
Flavonoids in the grasses (Poaceae family), Arthraxon hispidus (Thunb.) Makino and Miscanthus tinctorius (Steudel) Hackel have long histories of use for producing yellow dyes in Japan and China, but up to now there have been no analytical procedures for characterizing the dye components in textiles dyed with these materials. LC-MS analysis of plant material and of silk dyed with extracts of these plants shows the presence, primarily, of flavonoid C-glycosides, three of which have been tentatively identified as luteolin 8-C-rhamnoside, apigenin 8-C-rhamnoside and luteolin 8-C-(4-ketorhamnoside). Two of these compounds, luteolin 8-C-rhamnoside (M=432), apigenin 8-C-rhamnoside (M=416), along with the previously known tricin (M=330) and several other flavonoids that appear in varying amounts, serve as unique markers for identifying A. hispidus and M. tinctorius as the source of yellow dyes in textiles. Using this information, we have been able to identify grass-derived dyes in Japanese textiles dated to the Nara and Heian periods. However, due to the high variability in the amounts of various flavonoid components, our goal of distinguishing between the two plant sources remains elusive.
Lucidin-3-O- primeveroside (LuP) is one of the components of madder root (Rubia tinctorum L.; MR) which is reported to be carcinogenic in the kidney and liver of rats. Since metabolism of LuP generates genotoxic compounds such as lucidin (Luc) and rubiadin (Rub), it is likely that LuP plays a key role in MR carcinogenesis. In the present study, the chemical structures of Luc-specific 2'-deoxyguanosine (dG) and 2'-deoxyadenosine (dA) adducts following the reactions of dG and dA with a Luc carbocation or quinone methide intermediate derived from Acetoxy-Luc were determined by liquid chromatography with photodiode array and electron spray ionizaion-mass spectrometry (LC-PDA-ESI/MS). The identification of the two measurable adducts as Luc-N(2)-dG and Luc-N(6)-dA was confirmed by NMR analysis. Subsequently, using a newly developed quantitative analytical method using LC-ESI/MS, the formation of Luc-N(2)-dG and Luc-N(6)-dA from the reaction of calf thymus DNA with Luc in the presence of S9 mixture was observed. The fact that this reaction with Rub also gave rise to the same dG and dA adducts strongly suggests that Rub genotoxicity involves a metabolic conversion to Luc. The precise determination of the modified DNA bases generated by LuP and the method for their analysis may contribute to further comprehension of the mode of action underlying carcinogenesis by MR and related anthraquinones.
The roots of Rubia tinctorum L. (madder) are the source of a natural dye. In this review for the first time all the different information on Rubia tinctorum available in the literature is summarised. The dye components are anthraquinones whichprobably contribute to the resistance of the plant against fungi in the soil. Madder roots have been used to dye textiles in many parts of the world since ancient timesand an overview of the historical development, cultivation, harvesting and dyeing techniques of madder is given. The anthraquinone alizarin, the hydrolysis product of ruberythric acid, is supposed to be the main dye component of Rubia tinctorum. The chemical synthesis of alizarin and the biosynthesis of the anthraquinones in Rubia tinctorum are described. As far as the purification, structure elucidation and structures of isolated compounds are concerned, the review confines itself to the anthraquinones of madder. Finally the pharmacology and medicinal uses of madder and pure anthraquinones are discussed. This review supplements and updates earlier partial reviews on madder or anthraquinones by Schweppe, Thomson and Wijnsma.
A liquid chromatographic (LC) method for the separation of both anthraquinone glycosides and aglycones in extracts of Rubia tinctorum was improved. For on-line MS detection atmospheric pressure chemical ionisation as well as electrospray ionisation (ESI) were used. The glycosides were ionised in both positive and negative ionisation (NI) mode, the aglycones only in the NI mode. With ESI ammonia was added to the eluent post-column to deprotonate the compounds. The efficiency of mass detection of the hydroxyanthraquinone aglycones was found to depend on the pKa value of the component. LC-diode-array detection and LC-MS provide useful complementary information for the identification of anthraquinones in plant extracts, which was proven with the identification of munjistin and pseudopurpurin.
For the production of a commercially useful dye extract from madder, the glycoside ruberythric acid has to be hydrolysed to the aglycone alizarin which is the main dye component. An intrinsic problem is the simultaneous hydrolysis of the glycoside lucidin primeveroside to the unwanted mutagenic aglycone lucidin. Madder root was treated with strong acid, strong base or enzymes to convert ruberythric acid into alizarin and the anthraquinone compositions of the suspensions were analysed by HPLC. A cheap and easy method to hydrolyse ruberythric acid in madder root to alizarin without the formation of lucidin turned out to be the stirring of dried madder roots in water at room temperature for 90 min: this gave a suspension containing pseudopurpurin, munjistin, alizarin and nordamnacanthal. Native enzymes are responsible for the hydrolysis, after which lucidin is converted to nordamnacanthal by an endogenous oxidase.
Analysis of dyes extracted from textiles of historical interest can give valuable information as to where, when, and how the textiles were made. The most widely used method for extraction of colorants involves heating with HCl, which frequently decomposes glycosidic dye components to their parent aglycons, with consequent loss of information about the source of the dye. This is particularly true for flavonoid dyes, many of which are glycosides. We have developed or improved upon two mild textile extraction methods that use ethylenediaminetetraacetic acid (EDTA) and formic acid and are efficient in extracting dyes, but preserve glycosidic linkages. The relative efficiencies of the HCl, EDTA, and formic acid extraction methods are compared by analyzing extracts of dyed samples of silk using HPLC coupled with diode array and mass spectrometric detection. HPLC profiles of EDTA or formic acid extracts of silk dyed, for example, with pagoda tree buds and onionskins are clearly distinguishable as to the plant material used, whereas profiles of HCl extracts are not. Thus, extraction of textiles with EDTA or formic acid reagents can yield significantly more information about the original dyestuff than can extraction with a strong acid.
The secondary metabolites isolated from Rubia species, their biological activities, and colouration properties have been reviewed. Over 150 chemical constituents belonging to different classes of bioactive compounds such as anthraquinones and their glycosides, naphthoquinones and glycosides, terpenes, bicyclic hexapeptides, iridoids, and carbohydrates are listed together with their source(s) and corresponding references.
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