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In the present study, an application of a silver colloid substrate in order to obtain Fourier-transform surface-enhanced Raman (FT-SER) spectra of natural historical dyes is presented. In detail, we collected a spectral database from solutions of pure dyes and then we carried out extractionless both hydrolysis and non-hydrolysis FT-SERS analyses on wool fibers previously dyed in our laboratory and on ancient textiles. The term 'extractionless' refers to a method of SERS analysis applied directly on the fiber, thus avoiding the extraction of dyes from textile samples. The combination of a low-energy source of radiation, as in the FT-Raman technique, with SER spectroscopy can bring the important advantage of reducing the fluorescence typical of ancient samples and organic dyes. In some historical textile samples, for which SER spectra by use of visible excitation could not be obtained, the FT-SER spectrum of an iron-gall dye was recorded without hydrolysis, while, with an HF hydrolysis pre-treatment on ancient fibers, madder, lac dye and brazilwood were clearly recognized.

High‐performance liquid chromatography (HPLC) is still, today, the technique of choice for the analysis of natural dyes in artistic objects and historical textiles, particularly in association with photodiode array (PDA) detection. In the last two decades, surface‐enhanced Raman spectroscopy (SERS) gained also increasing importance for these investigations thanks to its sensitivity and limited requirements in terms of sample quantity. In favor of SERS, its high specificity in molecular recognition typical of vibrational spectroscopy should be mentioned, whereas this non‐separative technique is obviously disadvantaged in the analyses of mixed chromophores, as is often the case of many natural dyes and also of tints obtained by the combined use of different colorants. An optimized experimental setup combining the two techniques, HPLC‐PDA and SERS, is proposed in the present work, allowing online SERS detection of different dyeing compounds eluted from the HPLC column. Examples are presented concerning some of the colorants most widely used in history, such as morin and luteolin for yellow dyes, alizarin, purpurin, laccaic, kermesic, and carminic acids for red ones, and indigotin for blue tints. Copyright © 2016 John Wiley & Sons, Ltd.

The aim of the present study was to provide experimental procedures for the identification of anthocyanin‐based dyes used in antiquity. In particular, we assessed the possibility to identify anthocyanins, both in plant extracts and in dyed textiles, by means of surface‐enhanced Raman spectroscopy (SERS), a very chemically specific technique that is moreover sensitive to the changes in structures of molecules, phenomena that occur extensively in the chemistry of anthocyanins. The choice of the plant sources (bilberry, elderberry, sumac, purple corn and hollyhock) was based on their attested use in history as dyeing matters. Suitable extraction and pre‐treatment procedures were optimized both for plant sources (berries, cob glumes and flowers) and textiles dyed with such sources in the laboratory, followed by SERS analyses at different pH values. Finally, special attention was paid to the well‐known instability of anthocyanins: dyed wool samples were exposed to artificial aging in order to verify the possibility to identify such molecules also in faded textiles. The achievement of reliable surface‐enhanced Raman spectra from these samples encourages us to suggest the protocol for the analysis of historical objects. Copyright © 2015 John Wiley & Sons, Ltd.