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E. S. Rodríguez, A. A. Rodríguez, M. A. García and R. C. Cámara, "Characterization of Natural and Synthetic Dyes Employed in the Manufacture of Chinese Garment Pieces by LC-DAD and LC-DAD-QTOF", e-conservation magazine, No. 21 (2011) pp. 38-55, http://www.e-conservationline.com/content/view/1021

Characterization of Natural and Synthetic Dyes Employed in the Manufacture of Chinese Garment Pieces by LC-DAD and LC-DAD-QTOF

By Estrella Sanz Rodríguez, Angela Arteaga Rodríguez,
María Antonia García and Rodríguez Carmen Cámara


 

In this work we present the results obtained for the characterization of dyes found in seven Chinese garment pieces, which came from the Museum of Arts and Design in Madrid to Spanish Cultural Heritage Institute (IPCE) for their restoration. They were dated to the times of the Qing Dynasty, between 1700 and 1900 AD. The samples were analyzed by liquid chromatography coupled to a diode array detector (LC-DAD) and liquid chromatography tandem diode array quadrupole time-of-flight mass spectrometry (LC-DAD-QTOF). Dyes identified in the pieces under study were clearly correlated with two important features, their oriental origin and the date of manufacture, making them a particularly complex matrix. Thus, on one hand, the natural dyes found, such as indigo, brazilwood, curcuma, Asian berberis yellow dye, pagoda tree and safflower, are characteristic for Asia and the Middle East. On the other hand, these pieces date from the transition period between the exclusive use of natural dyes and the widespread introduction of synthetic ones during the late 19th century. Therefore, some early synthetic dyes such as Prussian blue, picric acid, basic fuchsine and Victoria blue B were also detected.



Introduction


In all parts of the world, natural dyes have been used since the oldest times until the end of the 19th century, when synthetic dyes became available. The organic compounds responsible for the colour in ancient dyestuffs were obtained from plants, insects, shellfish and lichens [1] and included hundreds of dyes like cochineal, brazilwood, madder, kermes, weld, young fustic, saffron, indigo, orchil, Tyrian purple, etc. In 1740, indigo carmine appeared as the first semi-synthetic dye, followed by picric acid in 1771. Aniline Purple (or Perkin´s Mauve), considered to be the first really synthetic dye, was accidentally discovered by William H. Perkin in 1856 in an attempt to produce artificial quinine. Since 1897, when 404 new dye-stuffs had been developed, the synthetic dyes soon replaced most of the natural ones [2].

Due to the fact that the particular dyes employed in each culture were related to locally available dyeing technology, the identification of dyestuffs present in historical textiles can contribute to answer different questions linked with dyeing techniques, time of manufacture and geographical origin of a particular textile [1], offering important information for the establishment of their historical-artistic profile. Moreover, these analyses can evidence past restoration processes and provide keys for the application of an appropriate treatment in modern interventions of restoration or conservation.

Since each dye can be a mixture of various organic compounds and a fibre can be dyed with several of them, chromatographic techniques that are able to separate very complex mixtures are the most appropriate tools for this type of analysis. In between all of them, high performance liquid chromatography (HPLC) is by far the most commonly used, because it enables the separation of non-volatile compounds such as the components of dyestuffs [3]. A HPLC system can be coupled to different detectors. Evidently, most of the dye components are strong chromophores, therefore UV-Vis absorbance detectors, most commonly with a diode array configuration (DAD) are suitable for the demands of their analysis from plant extracts or animal sources [4-8]. The same applies for analysis from other matrices such as modern dyed materials [2,9] or archaeological textiles [10-18]. Employing DAD, detection can be carried out over the whole range of the UV and visible spectrum, hence the complete spectrum of all the compounds subsequently eluting from the liquid chromatography (LC) column can be obtained, which are then characterised by their retention time on one hand and by their corresponding UV-Vis spectrum on the other. Even though, this technique is not very specific and different chemical compounds may have rather similar spectra. This is the reason for that the actual trend within the field of identification of complex mixtures of dyestuffs goes towards the use of higher discriminating techni-ques such as hyphenation of liquid chromatography to detection by mass spectrometry (MS). In fact, over the last years, most research tends towards uniting and complementing all the infor-mation obtained by on-line coupling of DAD and different mass spectrometer configurations, such as ion trap (IT), single quadrupole (Q) or time of flight (TOF) [10, 12,19-28]. The use of a hybrid LC-QTOF, a quadrupole-time of flight instrument such as the one employed in this study has, to best of the author’s knowledge, not yet been employed for the analysis of natural organic dye-stuff. This system allows the separation of the compounds present in each sample and their subsequent characterisation due to its powerful analytical capabilities for detection and identification. The TOF detector delivers the high mass accuracy (1-2 ppm MS) needed for positive identifications with absolute confidence. This instrument also performs MS-MS using a quadrupole, a hexapole (collision cell) and a TOF portion to produce spectra (2-4 ppm MS-MS). The MS-MS spectra combined with accurate mass can be used to confirm ion identity and structure.

With respect to commonly used mass detectors, such as single quadrupole, the high mass accuracy that a QTOF provides reduces drastically the possible formulas for a given compound. This    information allows confirming the presence of a compound, helping to identify unknowns and to reduce risk of spending effort on the wrong mole-cule. The MS- MS spectrum yields a fragmentation pattern which is exclusive and unique for each compound and it is used helping to identify and to confirm unknowns via elucidation of their chemical structure. Summarising, the QTOF detector is an extremely powerful tool for compound identification.

The collection studied in this work consists of seven Chinese garment pieces provided by the Museum of Arts and Design of Madrid for conservation purposes to IPCE. There is not much histo-rical information available; all pieces were dated between 1700 and 1900, corresponding to the Qing Dynasty period and, most probably, came to Spain from Manila when the Philippines was a Spanish colony [29]. All pieces were produced using the typical traditional Chinese techniques and decoration patterns. Their state of preservation is acceptable, except the backside of a pair of trousers, which is heavily damaged. Mainly silk, but also other types of fibres such as cotton, flax, hemp or jute, were employed in their manufacture [30].

The objective of the present study was the identification of the dyestuffs employed in the manufacture of fragments from this collection using LC-DAD and LC-DAD-QTOF. This identification can contribute to obtain relevant information for their historical documentation and to extend the knowledge of the dyeing technology used in their production.


Experimental

Reagents and reference fibres


High-purity deionised water (Milli-Q Element system, Millipore, USA), formic acid (HCOOH) from Fluka (Sigma-Aldrich, Steinheim, Germany) and acetonitrile (ACN), from J.T. Baker (Deventer, Netherlands) were used for preparation of the mobile phase. Gradient grade methanol (MeOH) from J.T. Baker (Deventer, Netherlands), formic acid and dimethylformamide (DMF) from Panreac (Barcelona, Spain) were employed for sample preparation.

Extraction methods, chromatographic conditions and instrumental parameters of the detectors were previously optimised using reference fibres dyed with several natural dyes, such as American cochineal (Dactylopius coccus Costa), brazilwood (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.) or sumac (Rhus spp.), in between others.

Samples


Figures 1-7 show photos of each piece under study: a theatre costume, a nuptial tunic, a chi-fu, a belt, a jacket, a pair of trousers and child shoes. The first step in the identification of a dyestuff present in an historical textile is the sampling procedure. This was carried out taking as few amount of sample possible, but always keeping the sample representative. To cover the different colours discovered over every piece, a total amount of 52 samples were taken. Subsequently, these were examined under an optical microscope to determine the macroscopic sample composition and to detect impurities and fading phenomena.
 
From left to right:
Figure 1. Nuptial tunic from the “Oriental garment” collection of the Museum of Arts and Design (Madrid).
Photo by Eduardo Seco.
Figure 2. Theatre costume from the “Oriental garment” collection of the Museum of Arts and Design (Madrid).
Photo by Teresa García.
Figure 3. Chi-fu from the “Oriental garment” collection of the Museum of Arts and Design (Madrid).
Photo by Esther Galiana.
Figure 4. Jacket from the the “Oriental garment” collection of the Museum of Arts and Design (Madrid).
Photo by Esther Galiana.
Figure1-12.jpg
Figure2-18.jpg
Figure3-12.jpg
Figure4-12.jpg
 


From left to right:
Figure 5. Belt from the “Oriental garment” collection of the Museum of Arts and Design (Madrid).
Photo by Esther Galiana.
Figure 6. Pair of trousers from the “Oriental garment” collection of the Museum of Arts and Design (Madrid).
Photo by Eduardo Seco.
Figure 7. Child shoes from the “Oriental garment” collection of the Museum of Arts and Design (Madrid).
Photos by Eduardo Seco.
Figure5-12.jpg
Figure6-18.jpg
Figure7-12.jpg
 

Instrumentation

The samples were chemically analyzed employing two rather different liquid chromatography systems. First, a commonly used liquid chromatography system coupled to diode array detector (LC-DAD) and, after, a liquid chromatography coupled to diode array detector and mass spectrometer with a quadrupole-time-of–flight analyzers (LC-DAD-QTOF).

System I (LC-DAD)

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 a rate of 1 scan/second and with a resolution of 1.2 nm (Waters Chromatography, USA). The mobile phase, delivered at 0.5 ml/min, 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 constant at 35 ºC.

System II (LC-DAD-QTOF)

All the modules of LC-DAD-QTOF instrument (automatic injector, pump, column oven, diode array detector and mass spectrometer) were from Agilent Technologies (USA).

Chromatography

The liquid chromatography system used consisted of a model 1200 Series equipped with a ZORBAX Extend-C18 Rapid Resolution High Throughput (RRHT) column (50 x 2.1 mm i.d.; 1.8 μm particle size). The mobile phase, pumped at 0.8 ml/min, consisted of 0.1% formic acid in water (A) and acetonitrile (B). The gradient applied was the following: 10% B isocratic to 0.4 min, to 35% B (linear) at 12 min, to 95% B (linear) at 18 min, 95% B isocratic to 21 min and to 10% B (linear) at 25 min. The column temperature was maintained at 35 ºC by a model 1200 Series thermostatic column compartment. Separated components were detected with a 1200 Series diode array detector, scanning from 200 nm to 800 nm and the chromatograms were recorded at 275 and 550 nm.

Mass spectrometry

Mass spectrometry was performed on a 6530 Accurate-Mass QTOF operating in ESI positive and negative modes. The ionisation source was a Jet Stream Thermal Focusing technology which uses super-heated nitrogen (N2) to improve ion generation and desolvation for greater signal and reduced noise. The acquisition mode was Auto MS-MS to obtain the MS-MS spectrum for each single dye component. The precursor selection was sorting by abundance, being three the maximum number of precursors per cycle. The mass spectrometer operating conditions are summarised in Table I. Data acquisition and processing were performed using MassHunter Workstation software.
 
 
ESR_table1.png


 
   Table I. Mass spectrometer operation conditions.
 

Extraction procedure

In a first study, working with the LC-DAD system, we employed a previously optimised and published extraction method [31], which can be resumed as follows:

Extraction procedure I

Bulk samples were added to a conic glass vial containing a (95:5, v/v) mixture of MeOH:HCOOH and then heated for 30 minutes to 45-50 ºC. Subsequently the solvent was evaporated under a N2 current. To the dry residue, a (1:1, v/v) mixture of MeOH:DMF was added and the solution again heated to about 100 ºC during 5 minutes, then transferred to 0.2 µm Spin-X nylon micro centrifuge filters and centrifuged at 6000 rpm for 10 min. After evaporation of the filtrate to dryness with N2, the residue was again dissolved in 50 µL of a (1:1, v/v) MeOH:DMF mixture and shaked in vortex for 1 minute. This extract was injected onto the LC-DAD system.

Later on, the method was further optimised [32], basically regarding the first extraction medium, and was employed with the second chromatographic system, LC-DAD-QTOF.

Extraction procedure II

Samples were placed in a conic vial and treated with 250 µL of a mixture of HCOOH:MeOH:H2O (15:25:60, v/v/v) for 10 minutes at 50-55 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 90 ºC. Then, the solution was transferred to 0.2 µm nylon filters Spin-X (micro centrifuge filter) and centrifuged at 6000 rpm for 10 min. The filtrate was evaporated to dryness under a N2 current and the residue was dissolved in 5-10 µL of MeOH:DMF (1:1, v/v) solution. After shaking it in vortex for 1 min, the extract was injected onto the LC-DAD-QTOF system.


Results and discussion

From observation under optical microscope it was concluded that none of the samples were constituted by a mixture of differently coloured fibres, except for one orange-red sample from a child shoe, where the fibres were first yellow dyed and afterwards superficially in red-orange. It is worth mentioning that an important decolouration process was observed in this particular sample.

Results of the analysed samples using the system I (LC-DAD), are summarised in Table II. The compounds were identified based on matching their retention time and UV-Vis spectra.
 
 
  ESR_table2.png
 
   Table II. Summary of the dyestuffs found in the seven Chinese pieces of garment studied.  

In the brown samples, gallic acid, ellagic acid and traces of flavonoids were detected, indicating the use of tannins as dye (probably obtained from galls and/or bark of oak species).

Indigotin, as main component, and indirubin were detected in the blue samples and those colours deriving from blue, such as green or purple (Figure 8(c)). The percentage of each component was in concordance with the composition of indigo (Indigofera sp.) or woad (Isatis tinctoria L.) but due to the origin of these textiles, the dye was most probably indigo obtained from some Indigofera species.

Another type of indigo in dark blue, green and purple samples containing indirubin, either present as a main component or at very high concentration, was found (Figure 8(d)).
 

  Figure8-18.jpg
 
  Figure 8. (a) UV-Vis spectrum of indigotin; (b) UV-Vis spectrum of indirubin; (c) DAD chromatogram at 275 nm of blue sample from theatre costume where indigotin (majority) and indirubin were detected; (d) DAD chromatogram at 275 nm of dark blue sample from a pair of trousers where indirubin (majority) and indigotin were detected; (e) relation of indigotin and indirubin in blue, green and purple samples with different shades (n= 17).
 
 

 

Figure9-18.jpg

 
 

 

Figure 9. (a) DAD chromatogram obtained for a red sample from theatre costume and UV-Vis spectra of the three main red components detected; (b) Extract compound MS chromatograms; (c), (d) and (e) the accurate mass and the mass-mass spectrum for the fuchsine, magenta II and new fuchsine, respectively. Note: the ion precursor is marked with a little red rhomb over it and has been fragmented in the collision cell to give the corresponding mass-mass spectra.

 
 
 
When the ratio indigotin to indirubin in 17 samples of different shades of blue, green and purple is represented (Figure 8(e)), it is clearly shown that two different types of indigo dyes were present. Available literature refers in only two occasions to an indirubin content of blue dye-stuff different from Indigofera or Isatis tinctoria. Wouters and Rosario-Chirinos [14] reported that “in the early Peruvian samples, indirubin was often more abundant than indigotin [...]” and concluded that “more studies will be needed to interpret the high indirubin amounts that were often encountered [...]”. Equally, Cardon [33] reported, about the dye composition of a plant from Asia, Rum or Assam Indigo (Strobilanthes cusia): “Recently, the Japanese chemist Satoshi Ushida concluded that the rather high pH of Strobilanthes juice may explain the production of high proportions of indirubin when dyeing with fresh leaves at elevated temperatures”. About the dyeing and colours obtained with this dye, Cardon reported that “intensive blue-black or dark blue colour was obtained with this dye by repeated immersions in a vat of osak indigo (Strobilanthes sp.)[…]”.

The only chromatographic pattern where we found amounts of indirubin very close or higher than indigotin has been in the analysis of a product called Ching-Dai (Indigo Naturalis) or in Chinese qing dai [34-36]. Indigo naturalis is a dark blue power used to treat several health problems in Chinese and Taiwanese medicine and it is prepared from leaves of plants such as Baphicacavthus cusia, Polygonum tinctorium, Isatis indigotica, Indigofera tinctoria and/or Strobilanthes cusia. Thus, we think that the dark blue colour in the samples from the Chinese garments was obtained from a dye prepared from such Asian species which, due to the dyeing method employed or to the composition of some of the plant used, contains a high amount of indirubin. Moreover, a blue pigment used like a paint layer in a decoration of the chi-fu could be identified as Prussian blue by FTIR and XRF [30]. Two other blue dyes could not be identified by LC-DAD because they did not match any available reference.

Regarding red samples, we found that they were dyed with cochineal, brazilwood and possibly safflower, although the presence of the latter could not be confirmed because a carthamin standard was not available. Additionally, two red dyes could  not be identified.

Four different yellow dyes were found. Two of them could be identified as curcuma and Asian berberis. A third yellow containing rutin as a possible main component, the principal component of Chinese yellow berries (the Japanese pagoda tree, Sophora japonica L.), but its identification was doubtful because the UV-Vis spectra of flavonoids are all very similar. Furthermore, no corresponding reference fibre was available (e.g. dyed with pagoda tree), which would have allowed confirmation of its specific retention time. The last yellow could be identified as picric acid, one of the first semi-synthetic dyes based on matching its UV-Vis spectra with data kindly provided by M. van Bommel.

Summarising, after the LC-DAD analysis, dyes such as tannins, indigo, cochineal, brazilwood, curcuma, Asian berberis and picric acid could be identified. The possible presence of safflower and Chinese yellow berries could be detected and four dyes, two blue and two red, remained unidentified.

In order to improve these results, samples containing doubtful and unidentified compounds were subsequently analyzed using LC-DAD-QTOF.

These analyses allowed the confirmation of the presence of carthamin and rutin via its accurate mass and mass-mass spectrum and consequently the use of safflower and Asian berries dyes. The use of safflower in the orange sample from a child shoe explained the decolouration phenomena observed due to the wellknown poor light fastness of this dye.

In the characterisation of one of the unknown blue dyes, a mixture of blue components (according to their UV-Vis spectra) was obtained. One of the main compounds could now be identified as the synthethic dye Victoria blue B, introduced in 1883 [37]. The identication was based on its UV-Vis spectrum, exact mass (m/z 470.2583; error 0.53 ppm), corresponding to the [M-Cl]+ ion, distinguishable from other Victoria Blue dyes [38] and on its mass-mass spectrum matching with its chemical structure. However, the other blue dye still remains unidentified because the entire sample was used in the analysis on system I.

Equally, only one of the two unknown red dyes could be identified. In this case, the analysis reveals the presence of three main red components. From the extracts MS chromatograms, three compounds were identified as fuchsine, magenta II and new fuchsine, components of basic fuchsine dye, a synthetic dye which was introduced in 1856 [2]. All compounds were detected as [M+H]+ (m/z 302.1655, error -0.96 ppm; 316.1807, error 0.49 ppm and 330.165, error -0.02 ppm, respectively) and were identified based on their accurate mass, comparison with literature data [39], MS-MS fragmentation pattern according to their chemical structure and UV-Vis spectra  (Figure 9).

Finally, Table III shows the dyestuffs identified for each piece studied. These dyes were found alone or mixed in different proportions to create different shades, though colour degradation effects also took place such as in the bands of the chi-fu.
 
  ESR_table3.jpg
 
   Table III. Dyestuffs identified and dating for each piece studied.  


Conclusion

Dyes identified in the pieces under study could be clearly correlated to two important aspects: their oriental origin and their date of manufacture, because the pieces date from the transition period between the exclusive use of natural dyes and the widespread introduction of synthetic ones during the late 19th century. Consequently, natural dyes found, such as indigo, brazilwood, curcuma, Asian berberin yellow dye, Chinese yellow berries and safflower, are characteristic for Asia and the Middle East, but some early synthetic dyes such as Prussian blue, picric acid, basic fuchsine and Victoria Blue B were also detected. Knowing the year of introduction of these synthetic dyes helps to improve the initially wide range of uncertainty when dating the pieces, as shown in Table III. Prussian blue was introduced in 1724-1725, picric acid in 1771, fuchsine in 1856 and Victoria Blue B in 1883. Hence, for the shoes, belt, jacket and pair of trousers, which were dyed employing natural dyes only, the initial date range between 1700 and 1900 AD could not be narrowed. For the chi-fu and the theatre costume, natural dyes were found mixed with some early synthetic dyes (picric acid and fuchsine) and Prussian blue was used to elaborate a paint layer decoration; in particular the presence of fuchsine indicates a fabrication date later than 1856. The case of nuptial tunic is different because though synthetic dyes were identified (fuchsine and Victoria blue B), these were found in parts of the textile (interior sewing thread and typical Chinese bottom, respectively) which could be attributed to later interventions dating from after 1856 AD for the sewing thread and 1883 AD for the blue bottom.

Regarding the applied techniques, the LC-DAD-QTOF system has demonstrated to be an excellent tool for both, to confirm the presence of a compound and to provide a confident identification of unknowns in a single analytical run without the essential use of previous standard analysis because this technique combines UV-Vis data, excellent mass accuracy and MS-MS structural information.


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. We would like to thank to the staff of the Textiles Department of the IPCE for their collaboration and valuable help and to the Museum of Arts and Design in Madrid. We also would like to say thank you to Maarten R. Van Bommel, Edith Oberhumer and Maria Melo for always attending our doubts and questions and for their valuable input. Finally, we would like to thank Ana Roquero for her important advice on dyed fibres belonging to the Reference Collection of IPCE and for her collaboration and valuable help.





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[27] R. Marques, M. M. Sousa, M. C. Oliveira and M. J. Melo, “Characterization of weld (Reseda luteola L.) and spurge flax (Daphne gnidium L.) by high-performance liquid chromatography–diode array detection–mass spectrometry in Arraiolos historical textiles”, Journal of Chromatography A 1216(9), 2009, pp. 1395–1402, doi:10.1016/j.chroma.2008.12.083

[28] Y. Lee, J. Lee, Y. Kim, S. Choi, S. Wook Ham and K.-J. Kim, “Investigation of natural dyes and ancient textiles from korea using TOF-SIMS”, Applied Surface Science 255(4), 2008, pp. 1033-1036, doi:10.1016/j.apsusc.2008.05.097

[29] Catalogue of the Museum of Arts and Design (Madrid), ed. Ministry of Culture, Spain, available at URL

[30] E. Galiana, T. García, A. Platero, M. Algueró, A. Arteaga, C. Martín De Hijas, E. González and E. Sanz, “Proceso de intervención de un conjunto de siete piezas de indumentaria oriental: tratamiento de conservación-restauración y análisis de materiales constitutivos”, Publicaciones del IPCE: Monografías, Investigación y Conservación de obras de arte oriental del Museo de Artes Decorativas, Ministerio de Cultura, Madrid, 2010, pp. 43-69, available at URL

[31] E. Sanz, A. Arteaga, M. A. García, M.A. Del Egido and C. Cámara, “Identification of natural dyes in historical Coptic textiles from the National Archaeological Museum of Spain”, e-conservation magazine 15, 2010, pp. 32-45, available at URL

[32] E. Sanz, A. Arteaga, M.A. García and C. Cámara, “Characterization of natural dyes from the reference collection of American dyestuff of the Spanish Cultural Heritage Institute (IPCE)”, 28th Meeting of Dyes in History and Archaeology (DHA28), Poznan (Poland), 21-24th October 2009

[33] D. Cardon, Natural Dyes: Sources, Tradition, Technology and Science, Archetype, London, 2007

[34] Y.-K. Lin, Y-L. Leu, S.-H. Yang, H.-W. Chen, C.-T. Wang and J.-H. Su Pang, “Antipsoriatic effects of indigo naturalis on the proliferation and differentiation of keratinocytes with indirubin as the active component”, Journal of Dermatology Science 54, 2009, pp. 168-174, doi:10.1016/j.jdermsci.2009.02.007

[35] B. C. Liau T. T. Jong, M. R. Lee and S. S. Chen, “LC-APCI-MS method for detection and analysis of tryptanthrin, indigo, and indirubin in Daqingye and Banlangen”, Journal of Pharmaceutical and Biomedical Analysis 43(1), 2007, pp. 346-351, doi:10.1016/j.jpba.2006.06.029

[36] Yuan Shiun Chang, Yu Ling Ho, “Studies on the Homonymic Chinese Crude Drug Species in Taiwan. Evaluation of the Quality of Da-Ching-Yeh and Ching-Dai”, Analytical Sciences 17, 2011, pp. a243-a426, available at URL

[37] A. Bowes, S. Collins, S. Elliott, L.T. Harris, L. Hazlett, E. Methé, M. Razak and P. Y. Subagiyo, “Important Early Synthetic Dyes: Chemistry, Constitution, Date, Properties”, M. W. Ballard (ed.), Conservation Analytical Laboratory, Smithsonian Institution, 1991, URL 

[38] J. D. Brewer, K. A. Hagan and J. M. Egan, “Forensic Analysis of Black Ballpoint Pen Inks Using Capillary Electrophoresis”, Forensic Science Communications 7(3), 2005, pp. 1-10

[39] R. Köhling, “Colors of the world: fast separation of dyes with Ascentis Express”, Reporter 38, 2009, pp. 3-5, also available at URL  [pdf]
 
 
 
About the authors
 

Estrella Sanz Rodríguez
Conservation-Scientist

Estrella Sanz Rodríguez (MSc, PhD) studied at the Faculty of Chemistry in the Complutense University of Madrid (UCM), graduating in 1996. She worked for three years as an analytical scientist in the Department of Analytical Chemistry, carrying out research 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 to 2003 she worked in the Spectroscopy Research Assistance Centre of the UCM. Subsequently she carried out her PhD dedicated to the development of new methods for arsenic species extraction from environmental samples by HPLC and inductively coupled plasma mass spectrometry (ICP-MS). Presently she works as UCM investigator in the Laboratories of the Spanish Cultural Heritage Institute (IPCE). Her research interest include the development of 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-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.


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. 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.


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