Abstract
Organic dyes of animal and plant origin have often been used by our ancestors to create textiles with polychromic ornamental patterns, and dyestuff analyses reveal how ancient cultures used these natural colorants. Mass spectrometry can characterize ancient colorants from these textiles, but its combination with separation techniques such as liquid chromatography requires the destruction of the pattern to extract organic dyes from the fabrics. In this study we applied mass spectrometry imaging (MS imaging) on colorful patterned textiles to show the spatial distribution of indigo-type and anthraquinone-type dyes. We evaluated different sample preparation techniques for matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF)-MS imaging, e.g. the production of imprints in TLC (thin layer chromatography) aluminum sheets and the embedding of the material in Technovit7100 to produce thin sections. Our protocol enabled the detection of indigo-type dyes directly on a historic textile of more than 2,000 years old embedded in Technovit7100. This is the first-time application of MALDI-TOF-MS imaging to map different organic dyestuffs on archeological remains.
Highlights
To characterize natural colorants in historic textile samples, dyestuff analyses have been performed successfully on textile fragments or a few fibers using commonly (U)HPLC-DAD [(ultra) high performance liquid chromatography – diode array detection], (U)HPLC-ESI-MS/MS [(U)HPLC - electrospray ionization tandem mass spectrometry) or HPLC-APCI-MS/MS (HPLC - atmospheric pressure chemical ionization tandem mass spectrometry) combined with a previous extraction of textile materials[4,5,6,7,8]
The application of matrices led to increased analyte signal intensities, and best results were achieved for indigo-type dyestuffs with Universal MALDI matrix in positive ionization mode and for anthraquinone colorants with 9-AA in negative ionization mode
We reported on the application of MALDI-TOF-MS imaging to study archeological textiles respecting their colorful pattern
Summary
To characterize natural colorants in historic textile samples, dyestuff analyses have been performed successfully on textile fragments or a few fibers using commonly (U)HPLC-DAD [(ultra) high performance liquid chromatography – diode array detection], (U)HPLC-ESI-MS/MS [(U)HPLC - electrospray ionization tandem mass spectrometry) or HPLC-APCI-MS/MS (HPLC - atmospheric pressure chemical ionization tandem mass spectrometry) combined with a previous extraction of textile materials[4,5,6,7,8]. MS is an excellent tool for the characterization of ancient colorants and the combination with different separation techniques allows a sensitive and selective determination of coloring components and degradation products. In this context, high separation efficiency is usually achieved by the application of LC9. The utilization of GC- (gas chromatography)[10,11] and CE-MS (capillary electrophoresis)[12,13] has been described These analytical techniques require the destruction of the pattern to extract organic dyes from the fabrics, they are unable to provide information about the distribution of colorants in polychromic textiles with complex patterns. Most commercial MALDI-TOF-MS instruments routinely achieve lateral resolution of 20 μm and special modifications of the imaging source combined with an appropriate sample preparation and data processing even enable lateral resolutions
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