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The aim of this work was the identification of natural
dyes employed in the manufacture of eight fragments of the collection of Coptic
textiles from the Spanish National Archaeological Museum, using HPLC-DAD. Two extraction
methods, the classical methanol/hydrochloric acid extraction and a mild extraction
using 5% formic acid in methanol, were evaluated using several reference fibres dyed with a selection of red, yellow, blue, purple
and black dyestuffs. In both cases, an additional step, extracting with methanol/dimethylform-amide, was employed. The results
showed that the number of compounds detected is higher when the mixture with 5%
formic acid was used, contributing to give more information about the
source of the dye, although the extraction efficiency was lower in
the most cases. The latter method was selected and applied for subsequent dye extraction from the samples. The dyestuffs
identified in the fragments under study are in agreement with dyestuff
commonly reported for Coptic textiles.
Introduction
The identification of natural dyes present in historical textiles can contribute to answer different questions linked with the how, when and where a textile was made [1]. Moreover, this analysis can evidence past restoration processes and provides key information for the application of an appropriate treatment in current interventions of restoration or conservation. In all parts of the world, natural dyes have been used since the most ancient times until the end of 19th century when they were replaced by synthetic dyes. The ancient dyestuffs were organic materials obtained from plants, insects, shellfish and lichens [2]. The classification of dyestuffs can be based on their application method (direct, vat and mordant dyes), according to their origin (natural or synthetic, animal or vegetal), their colour (red, yellow, blue and purple dyes) and in relation with the chemical constitution (chromophore structure) of the dyestuff molecule. The different chemical classes of chromophores present in natural dyes yield the following general classification: anthraquinoid, flavonoid, indigoid dyes and tannins. There are other chromophores existing, which are not included in this classification because they are less common [3-5]. This classification is useful for the analyst in order to choose the right sample extraction procedure to recover the components from natural dyes [6]. The extraction step is crucial, within the whole analytical method, because identification of dyestuffs will be done upon the extracted components. The standard procedure for extracting natural dyes from textiles involved heating in 6M methanolic hydrochloric acid solution. This extraction method was introduced three decades ago [7, 8] and actually is still being applied as evidenced in recent works [1, 9-11]. The process has the advantage of providing a high extraction efficiency for the majority of dyes, particularly anthraquinoid and flavonoid types, excepting indigoids, which are poorly extracted because they remain practically insoluble. Moreover, the majority of yellow dyes and some red and orange dyes are composed of glycosides, which, when heated in strong HCl, are hydrolyzing glycoside linkages, causing that only the aglycone chromophore can be detected. As a result, most information about the original dye components and their plant source is lost [12, 13]. Other limitations of this rather aggressive process are the degradation of several labile compounds and the chemical transformation of different chromophores [14]. Recently, several investigations have been carried out to overcome these problems. The most noticeable with respect to improving the solubility of indigoids dyes have been those including an exclusive extraction step for these dyes using pyridine, dimethylformamide (DMF) or dimethylsulfoxide (DMSO) [15-17] solvents, in which blue and purple dyes are more soluble, and one proposed by Surowiec et al. [18], which is based on HCl hydrolysis and involving an additional DMF/Methanol (MeOH) extraction step. The introduction of this additional step offered a notable improvement for the recovery of indigotin. Regarding preservation of labile compounds and glycosidic linkages, the development of milder extraction schemes is actually a tendency of general importance. Different approaches have been proposed herein. More systematic studies focused exclusively on dyed textiles were compared by Valianou et al. in 2009 [19]. For example, Zhang and Laursen [20] developed a mild extraction method in which HCl was replaced by 5 % formic acid (HCOOH) in MeOH solution, which is more efficient than the common HCl scheme when extracting anthraquinone and flavonoid dyes from dyed silk, wool and cotton fibres, further preserving glycosisdic linkages. Although this method was successfully applied to historical microsamples extracted from pre-Columbian Andean [21] and Chinese textiles [22], another study, focused on the extraction of Rubia tinctorum L. components from wool fibres, reported that classical HCl extraction provides the most satisfying results [23]. In another investigation, dyed wool was treated with aqueous solutions of ethylenediaminetetraacetic acid (EDTA), oxalic acid, oxalate, citrate and citric acid [24]. It was reported that none of the five procedures was better than the classical method, although the oxalic acid extraction was comparable to HCl extraction for alizarin and carminic acid. In their study, Valianou et al. [19] compared five extraction methods, including the use of HCl, citric acid, oxalic acid, trifluoroacetic acid (TFA) and a combination of HCOOH and EDTA with respect to: (a) number of compounds extracted, (b) relative quantities of compounds extracted and (c) values for the signal-to-noise ratio of the compounds extracted. It was shown that the TFA method provided in this sense the best overall results. Since dyes are mixtures of organic compounds and a fibre can be dyed employing various dyes, those chromatographic techniques which are able to separate very complex mixtures are the most appropriate tools for this type of analysis. High performance liquid chromatography (HPLC) is by far the most commonly used chromatographic technique for analysis of natural dyes, enabling the separation of dye components from a small sample amount [25]. A HPLC system can be coupled to different detectors. Because the vast majority of dye components are strong chromophores, UV-Vis absorbance detectors or, more usually, diode array detectors (DAD) are commonly applied in analysis of natural dyes in extracts from plant or animal sources [7, 8, 26-28], from contemporary dyed materials [29, 30] and from archaeological textiles [9, 18-20, 31-35]. Employing DAD, the detection can be done at any wavelength in the UV or visible spectrum and a complete spectrum of any substance eluting from HPLC column can be obtained. As a result, dye molecules can be characterised in terms of retention time from the HPLC system and their UV-Vis spectrum. However, DAD detectors have the disadvantage that they are not very specific and similar compounds present similar spectra. Therefore, identifying the particular components in the often complex dye mixtures requires a more discriminating technique than UV-Vis spectroscopy. For example, the flavonoid aglycones and their glycosides often show identical UV-Vis spectra [12]. For this reason, the actual trend goes towards the coupling of mass spectrometry detectors (MS) to the HPLC system, which offers the mass spectrum of each component separated, thus allowing to characterise unknown compounds. In fact, over the last years, most of the research in this field tends towards uniting and complementing all the information obtained by on-line coupling of these two detectors, DAD and MS [1, 9, 13, 19, 21, 22, 36-40]. Egypt was one of the first countries where dyestuffs were used, and its climatic and cultural conditions are favorable to conservation of archaeological textiles. The literature about the characterization of natural dyes in Coptic textiles is relatively extensive. For example, Wouters presented different studies using HPLC-DAD of extracts from Coptic objects [7, 41, 42]. Later on, between 2003 and 2004, results about the natural dyes present in Coptic textiles from National Museum in Warsaw were presented employing HPLC-DAD [43], LC-DAD-MS [44] and LC-DAD/fluorescence detection/MS [45 ]. Other interesting research article was presented by A. Verhecken [46], where the objective was to establish a correlation between the age of a textiles from Egypt, Syria and Israel and the dyestuff used in them. Further work was carried out by R. Hofmann-de Keijzer et al. [47], where the authors give an overview of dyes and dyeing techniques used in the Late Antiquity in Egypt presenting their results about an investigation of natural dyes in two Coptic textile fragments from the Museum für Angewandte Kunst (Vienna). The Spanish Cultural Heritage Institute (IPCE) receives numerous historical textiles from museums and excavations for their conservation, technical analysis and identification of their dye content. Over the last years, the restoration of the collection of Coptic textile belonging to the National Archeological Museum from Spain, dating from IV AD to X-XI AD, was accomplished. This collection was studied in the framework of the project “Technological and chronological characterization of the Coptic textile productions: antecedents of the high medieval Spanish textile manufactures” [48]. Characterization of natural dyes present in eleven of these fragments was carried out by thin layer chromatography (TLC) in the IPCE laboratory [49], finding the common natural dyes used in the Nile Valley, such as madder, indigo (or woad), weld, lac and probably orchil. Madder, indigo (or woad) and weld cannot be used for dating in the first millennium, but the presence of lac dye in one textile suggests that this textile was made later than the VII century, according to A. Verhecken [46]. The objective of the present study was the identification of natural dyes employed in the manufacture of another eight fragments belonging to this collection using HPLC-DAD. Prior to analysis, two extraction methods for dye were evaluated, using several reference fibres dyed with a selection of red, yellow, blue, purple and black dyestuffs obtained from a reference collection of IPCE which contains more than 300 dyed fibres, and from a personal collection of Ana Roquero. Experimental Instrumentation The chromatographic system used consisted of a model 600E Multisolvent delivery system (Waters Chromatography, USA) equipped with a Luna C18(2) HPLC column (150 x 2.1 mm id, 5 µm particle size) and a guard cartridge system (Phenomenex, USA). Samples were injected by a 717 auto sampler (Waters Chromatography, USA). Separated components of dyestuffs were detected with a 996 DAD detector, scanning from 200 nm to 600 nm at scan rate of 1 scan/second and with a resolution of 1.2 nm (Waters Chromatography, USA). The mobile phase, pumped at 0.5 ml min-1, consisted of 0.1% trifluoroacetic acid (TFA) in water (A) and acetonitrile (B). The gradient applied was the following: 10% B isocratic to 1 min, to 30% B (linear) at 30 min, to 100% B (linear) at 50 min. The column temperature was maintained at 35 ºC. Reagents, reference fibres and samples High-purity deionized water (Milli-Q Element system, Millipore, USA), trifluoroacetic acid (TFA) from Fluka (Sigma-Aldrich, Steinheim, Germany) and acetonitrile (ACN), both from J.T. Baker (Deventer, Holland) were used for preparation of the mobile phase. Gradient grade methanol (MeOH) from J.T. Baker (Deventer, Holland), formic acid (HCOOH, 98%) and dimethylformamide (DMF) both from Panreac (Barcelona, España) were employed for sample preparation. Extraction methods were evaluated using the ten before mentioned reference fibres, dyed with American cochineal (Dactylopius coccus Costa), Brazil-wood (Caesalpinia sp), madder (Rubia tinctorum L.), weld (Reseda luteola L.), old fustic (Chlorophora tinctoria), saffron (Crocus sativus L.), indigo (Indigofera sp.), Tyrian purple (Plicopurpura pansa L.), alder bark (Alnus sp.) and sumac (Rhus spp.) on wool, except the Tyrian purple reference fibre, which was dyed on silk. Fiber samples were obtained from different colored Coptic textiles from the National Archaeological Museum in Spain. Figures 1-8 show the photographs of these fragments. A total number of 29 sub-samples were taken. Sampling in Coptic fragments codes from the National Archaeological Museum. Photos by José Baztan.
From left to
right: Figure 1: 15083; Figure 2: 1976/130/12; Figure 3: 1976/130/14; Figure 4: 15059; Figure 5: 15076; Figure 6: 15064; Figure 7: 15065; Figure 8: 1976/130/11.
Extraction procedures
Extraction methods were applied according to the following general schemes: Method 1: HCl extraction + MeOH/DMF extraction Samples were placed in a conic vial and were treated with 250 µl of a mixture of H2O : MeOH : 37%HCl (1:1:2, v/v/v) for 10 minutes at 100 ºC. The solvent was then evaporated under a N2 current. A volume of 250 µl of the mixture MeOH:DMF (1:1, v/v) was added to the dry residue and the mixture was heated for 5 minutes at around 100 ºC. Then, the solution was transferred to 0.2 µm nylon filters Spin-X (micro centrifuge filter) and centrifuged at 6000 rpm for 10 minutes. The filtrate was evaporated to dryness under a N2 current and the residue was dissolved in 50 µl of MeOH:DMF (1:1, v/v) solution. After shaking it in vortex for 1 minute, the extract was injected to the HPLC-DAD system. Method 2: HCOOH extraction + MeOH/DMF extraction Samples were placed in a conic vial and treated for 30 minutes at 45-50 ºC with 250 µl of a mixture of MeOH:HCOOH (95:5, v/v). The solvent was then evaporated under a N2 current. 250 µl of a solution of MeOH:DMF (1:1, v/v) were added to the dry residue and the mixture was heated for 5 minutes at around 100 ºC. Then, the solution was transferred to 0.2 µm nylon filters Spin-X (micro centrifuge filter) and centrifuged at 6000 rpm for 10 minutes. The filtrate was evaporated to dryness under N2 and the residue was dissolved in 50 µl of MeOH:DMF (1:1, v/v) solution. After shaking it in vortex for 1 minute, the extract was injected to the HPLC-DAD system. Results and discussion Comparison between the two evaluated extraction methods The two extraction methods applied are based on classical methanolic hydrochloric acid extraction, with an additional MeOH/DMF extraction step as proposed by Surowiec et al. [18] and on the mild extraction proposed by Zhang and Laursen [20], where 5% formic acid in methanol was used. Surowiec et al. confirmed the greatest improvement in extraction efficiency for indigotin when using the additional step involving MeOH/DMF and Zhang and Laursen observed the preservation of flavonoid glycosides. To the best of our knowledge, no study has been performed comparing the method proposed by Surowiec et al. with others, where the acidic hydrochloric extraction has been replaced by a mild extraction. The objective was to join the advantages of both in one extraction method, because the sample amount available for an analysis is always very small, therefore it is crucial to obtain the maximum information in one analytical run.
The results obtained in this comparison are summarized in Figure 9. As expected, the indigoid dyes, indigo and Tyrian purple, were extracted in a similar way because they are mainly affected by the MeOH/DMF extraction, which is identical in both methods. Four reference fibres, dyed with brazilwood, old fustic, alder bark and particularly, saffron, were extracted more efficiently employing the mild extraction, or Method 2. As expected, when saffron was extracted using Method 1, no peaks were detected because crocin and crocetin, its principal components, are decomposed by hydrochloric acid to compounds non-detectable by HPLC-DAD. Regarding the rest of reference fibres, for those dyed with American cochineal, madder, weld and sumac, Method 1 was able to extract more efficiently the dyestuff. The difference for weld was not very high (with Method 2 a 95 % of what has been achieved with Method 1), for American cochineal, madder and sumac, the sum area of detected compound employing Method 2 was 40 %, 70 % and 1.5 %, respectively, compared to results using Method 1. This indicates that anthraquinone dyes and ellagic acid are poorer extracted with formic acid. For madder, this effect was also observed by other authors [23]. However, the total number of compounds detected was higher when Method 2 was employed, with the exception of only two dyes: American cochineal and sumac. These results were attributed to the milder conditions, the ones with which the glycosidic linkages were preserved, and, thus, the number of detected compounds increases. To set an example, the number of compounds increases from four to eight, from seven to eleven or from four to twelve for weld, madder and alder bark respectively. If the extraction efficiency is acceptable, the criteria to choice the best method would be the extraction of a maximum number of compounds, which will offer more valuable information about the origin of the dye. Consequently, Method 2 was selected as optimum and applied for subsequent dye extraction from the Coptic textile samples. Application of the optimum method for dye extraction from the Coptic textile samples The results obtained applying the optimum extraction method to dyestuffs from the Coptic textiles under study are summarised in Table 1. Indigotin was identified in five blue samples, eight green samples and five purple samples. These results indicate that the dye employed for these samples was in all cases indigo (Indigofera sp.) or woad (Isatis tinctoria L.), whose main component is indigotin, therefore the differentiation between the two species was impossible.
In red, purple, orange and salmon-pink samples, the red dye found always contained alizarin and purpurin as main components, indicating a madder source. According to some authors [46, 47], the two madder species most frequently employed in the manufacture of the Coptic textiles were, probably, the Rubia tinctorum L., whose principal component is alizarin and Rubia peregrina L. (wild madder), where purpurin is the main component. In mentioned publication the term “madder A” is used for dyeing which contains alizarin as the main dyestuff and “madder P” for those which contain mainly purpurin. In this study, alizarin and purpurin were found to be within the range of 60-99% and 2-12%, respectively, and the type of madder detected was “madder A”, closer to the composition of Rubia tinctorum L. Luteolin-7-O-glucoside, as main component, luteolin and traces of a glucoside of apigenin were detected in two yellow, three green and one orange samples. Although there are numerous plants which may contain these components, the most important yellow dye originally found in the Mediterranean region and in West Asia was weld (Reseda luteola L.) which presents this composition and is the major yellow dye found in Coptic textiles. Consequently, this dye can be identified as weld. Another yellow dye, though at very low concentration, was detected in three green samples. This dye had a flavonoid glycoside as main component, probably a quercetin-type flavonoid, but yet unidentified. Presence of gallic and ellagic acids in the brown sample indicate the use of tannins as dye, probably obtained from oak galls because the main component was gallic acid. Moreover, in this sample indigotin and indirubin were detected, indicating the presence of indigo (Indigofera sp.) or woad (Isatis tinctoria L.) in the mixture. Finally, in one sample of dark green to brownish colour, beside indigotin an unknown component with absorption in the UV range only, presenting one strong band at 253 nm and one shoulder at 275 nm, was detected. This absorption is possibly due to condensed tannins, although more studies are necessary to achieve concludent data. Conclusions The optimized method successfully achieves marked objectives since it employed a single extraction process. High efficiency was obtained for the indigoid dyes while labile compounds and glycosides were preserved. The efficiency for extraction of certain compounds, like anthraquinones, and especially carminic and ellagic acid shall be improved in future investigations. Dyestuffs identified in the fragments under study in this work are in agreement with commonly reported dyestuffs for Coptic textiles, in particular madder, yellow flavonoid dyes, tannins and indigo or woad. One yellow dye present in mixture to raise green colour in three samples remains unidentified because it was present at very low concentration. Unfortunately, as the identified components were employed all over the first millennium AD, the gathered information does not provide clues for a more precise dating of these fragments. As the amount of investigated samples was rather limited, the obtained results may be not very representative. Nonetheless, they provide valuable information, especially when compared with results obtained by other authors dedicated to ancient dying techniques applied in the Nile valley. Besides these results, this study represents the first milestone of an ongoing systematic characterisation by HPLC-DAD of the principal components used for dying of the textiles contained in the IPCE´s fibre reference collection. Acknowledgments The authors thank the Spanish Ministry of Culture and the Complutense University of Madrid for the establishment of the agreement of collaboration, in the frame of which the present study has been developed. Ana Roquero is also gratefully acknowledged for her important advice on dyed fibres belonging to the Reference Collection of the IPCE and for providing us reference fibres dyed with Reseda luteola L. and Rubia tinctorum L. from her personal collection. We would like to thank to the staff of the Textiles Department of IPCE for their collaboration and valuable help. References [1] D.A. Peggie, A.N. Hulme, H. McNab and A. Quye, “Towards the identification of characteristic minor components from textiles dyed with weld (Reseda luteola L.) and those dyed with Mexican cochineal (Dactylopius coccus Costa)”, Microchimica Acta 162, 2008, pp. 371-380 [2] E.S.B. Ferreira, A.N. Hulme, H. Mcnab and A. 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About the authors
Estrella Sanz Rodríguez
Conservation-scientistEstrella Sanz Rodríguez (MSc, PhD) studied at the Faculty of Chemistry in the Complutense University of Madrid (UCM), graduating in 1996. After first degree obtained in 1997 with the work “Identification of dry oils in paint layers by gas chromatography-mass spectrometry (GC-MS)”, she worked during three years as an analytical scientist in the Department of Analytical Chemistry, carrying out investigations about the identification of organic and inorganic materials in historical samples by high-performance liquid chromatography (HPLC) coupled to ultraviolet detection, Raman spectroscopy and GC-MS. From 2000 until 2003 she worked in the Spectroscopy Research Assistance Centre of the UCM. Subsequently she carried out her PhD in the group of trace analysis, speciation and metallomics (UCM), dedicated to the development of new methods for arsenic species extraction from environmental samples by HPLC and inductively coupled plasma mass spectrometry (ICP-MS), work which she completed in 2007. From 2006 until present, she works as UCM investigator in the Laboratories of the Spanish Cultural Heritage Institute (IPCE). Her research interest include the development a new extraction methods for natural dyes from historical and archaeological textiles samples and their analysis by liquid chromatography coupled to array and mass detector (LC-DAD-MS).
Angela Arteaga Rodríguez
Conservation-scientist
Angela Arteaga Rodríguez received her CINE-5b (1972) in Chemistry by the School of Industrial Masters of Madrid. Since 1992
she develops her professional work in the Area of Laboratories of the Spanish Cultural Heritage Institute (IPCE). Her work consists
in the analyses of natural dyes, binding media from works of art by different techniques like FTIR, TLC and HPLC-DAD. She has also
participated in several publications, congresses and other professional meetings, both national and international.
María Antonia García
Rodríguez
Conservation-scientistAngela Arteaga Rodríguez received her CINE-5b (1972) in Chemistry by the School of Industrial Masters of Madrid. Since 1992 she develops her professional work in the Area of Laboratories of the Spanish Cultural Heritage Institute (IPCE). Her work consists in the analyses of natural dyes, binding media from works of art by different techniques like FTIR, TLC and HPLC-DAD. She has also participated in several publications, congresses and other professional meetings, both national and international. María Antonia García Rodríguez Conservation-scientist María Antonia García Rodríguez received her MSc (1991) in Analytical Chemistry from the Complutense University of Madrid. From 1992 to 1997 she developed her professional work in the Laboratory of Doping Control in Madrid (The Sports Council, CSD). In 1998 and 1999, she collaborated with the Laboratory of Public Health of the Community of Madrid. Between 2001 and 2005 she worked as technical attendance in the study of instrumental techniques applied to the Investigation and documentation on artworks in restoration process in the IPCE, where since 2006, she belongs to the technical staff in the Area of Laboratories. Her work consists in studies related to mural paintings and archaeological material, as well as the analysis of organic materials in other art objects. She is author of several articles that appear in various publications Marián del Egido Conservation-scientist Marián del Egido received her MSc in Physics from the Complutense University of Madrid in 2003. From 1995 to 2000, she worked as researcher in the National Museum of Science and Technology (Madrid), where she participated in projects related to documentation and publication of historical collections of scientific instruments and she was attending national and international meetings organized by the Scientific Instrument Society and the International Union of the History and Philosophy of Science. She is author of several publications on History of Science and History of Scientific Instruments. Since 2000, she is Head of the department of Scientific Conservation of the IPCE. During this period, she has participated in national and international projects related to scientific conservation of cultural heritage, has coordinated and directed several interventions and researches on scientific methods in conservation and organized many courses and seminars. Carmen Cámara Chemist Carmen Cámara is a professor in Analytical Chemistry at the Complutense University since 1992. She is the leader of the Research Group of Trace Determination and Speciation, belonging to the department of Analytical Chemistry. Her main research interest is focused on the development of new analytical methods for trace metal speciation, emergent contaminants, bioaccumulation studies of trace metals and organic compounds in zebra fish embryo, proteomics and other topics related with a wide variety of samples. She has coordinated more than six European and several National projects. She has also participated in more than 30 European projects. Carmen Cámara has extensive experience within quality assurance, development of validation methodologies and the use of hyphenated techniques, among others. She has published more than 250 papers in international journals, was invited to held plenary lectures in the most relevant international meetings related with her activity and helds two patents. She has also been, from 2005 to 2009, the president of the Spanish Analytical Chemistry Society.
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