Early Synthetic Dyes Research Articles

Chemical analysis of dyes on an Uzbek ceremonial coat: Objective evidence for artifact dating and the chemistry of early synthetic dyes

A silk cross-stitched man's overcoat in traditional Uzbek style in the Indianapolis Museum of Art was thought to originate from late 1800s to early 1900s. To shed light on its history and associated textile dye chemistry, threads from the coat were subjected to dye analysis by LC-DAD-ESI-MS. Dyes identified include seventeen natural colorants from barberry, larkspur, madder and cochineal, and forty-two synthetic compounds in the diazo, xanthene, and triarylmethine class. Many of the synthetic dyes were heterogeneous, attributable either to crudeness in synthetic process or to age related degradation. The different shades of red and green in the threads were obtained from blending two or three synthetic dyes as well as, in one case, the combination of natural and synthetic components. Direct Red 23, C.I. 29160, first reported in 1900, was the most recent, thus refining the creation date of the garment to the early twentieth century or later.

Identification of early synthetic dyes in historical Chinese textiles of the late nineteenth century by high‐performance liquid chromatography coupled with diode array detection and mass spectrometry

In the present study, five classes of synthetic dyes – nitrophenol (picric acid), azo (Orange II), diarylmethane (auramine O), triarylmethine (fuchsine, methyl violet, and malachite green), and anthraquinone (alizarin) dyes – were identified in late-nineteenth-century textiles from the China National Silk Museum by high-performance liquid chromatography coupled with diode array detection and mass spectrometry. Data-dependent acquisition of tandem mass spectra provided some information not only on the molecular mass but also on the fragment ions obtained from precursor ions. These fragmentation patterns, obtained in a single experiment, proved to be useful for identification of the synthetic dyes extracted from the textile samples. In addition, it is worth noting that two anthraquinones, which are probably anthrapurpurin and flavopurpurin, and which were detected in printed cotton, can be used as the markers for distinguishing synthetic alizarin from natural alizarin.

Characterization of synthetic dyes by comprehensive two-dimensional liquid chromatography combining ion-exchange chromatography and fast ion-pair reversed-phase chromatography

In the late 19th century, newly invented synthetic dyes rapidly replaced the natural dyes on the market. The characterization of mixtures of these so-called early synthetic dyes is complicated through the occurrence of many impurities and degradation products. Conventional one-dimensional liquid chromatography does not suffice to obtain fingerprints with sufficient resolution and baseline integrity. Comprehensive two-dimensional liquid chromatography (LC×LC) is employed in this study, with ion-exchange chromatography in the first dimension and fast ion-pair liquid chromatography in the second. Retention in the first dimension is largely determined by the number of charges, while the selection of a small ion-pair reagent (tetramethylammonium hydroxide) in the second dimension causes retention to be largely determined by the molecular structure of the dye. As a result, there is a high degree of orthogonality of the two dimensions, similar to the values typically encountered in GC×GC. The proposed LC×LC method shows a theroretical peak capacity of about 2000 in an analysis time of about three hours. Clear, informative fingerprints are obtained that open a way to a more efficient characterization of dyes used in objects of cultural heritage.

Identification of Natural and Early Synthetic Dyes Used in Violet Silk Fabrics Dated to the Late of Edo-Meiji Era

Identification of Natural and Early Synthetic Dyes Used in Violet Silk Fabrics Dated to the Late of Edo-Meiji Era

A vibrational spectroscopic and principal component analysis of triarylmethane dyes by comparative laboratory and portable instrumentation

This contribution examines the utility of vibrational spectroscopy by bench and portable Raman/surface enhanced Raman and infrared methods for the investigation of ten early triarlymethane dye powder references and dye solutions applied on paper. The complementary information afforded by the techniques is shown to play a key role in the identification of specific spectral marker ranges to distiguish early synthetic dyes of art-historical interest through the elaboration of an in-house database of modern organic dyes. Chemometric analysis has permitted a separation of data by the discrimination of di-phenyl-naphthalenes and triphenylmethanes (di-amino and tri-amino derivatives). This work serves as a prelude to the validation of a non-invasive working method for in situ characterization of these synthetic dyes through a careful comparison of respective strengths and limitations of each portable technique.

Dye class identification of early synthetic dyes used in silk fabrics dated to the end of edo - meiji era

Dye class identification of early synthetic dyes used in silk fabrics dated to the end of edo - meiji era

Early synthetic dyes – a challenge for tandem mass spectrometry

The present study concerns identification of early yellow synthetic dyes from silk fibers taken from the 1930 spring color palette of the Lyon Dyers' Guild (La Chambre Syndicale des Teinturiers). The identification was based mainly on the electrospray ionization tandem mass spectrometry spectra obtained in the positive and negative ion modes. This technique was combined with high-performance liquid chromatography, which enabled separation of the analyzed compounds. Spectra registered for each of the examined synthetic dye allowed identification of their lost fragments. Moreover, isotopic profiles and exact measurements of m/z by using time of flight analyzer made possible to evaluate their elemental composition. In consequence, all obtained data, including UV-vis spectra, allowed to reconstruct molecular structures of examined colorants. Due to the lack of standards, the identification of the dyes was based only on the registration of fragment and quasi-molecular ions, what is rather uncommon in such analysis and means groping for the correct structure rather than proving signal identity by comparison with standards. Depending on substituents present in dye molecules, the lost fragments of the examined compounds involved SO(2), NO(•), NO(2)(•), CH(4), C(2)H(4), C(2)H(5)(•), C(2)H(6), CH(2)=N-CH(3), (CH(3))(2)NH, CH(2)= NH, CH(3)-NH(2), as well as CO and CO(2). The performed study led to identification of various colorants: rhodamine 6 G, rhodamine B, malachite green, quinoline yellow, picric acid and acetoquinone yellow 5JZ.

Identification of Natural and Early Synthetic Red Dyes Used in Silk Fabrics Dated to the Late Edo-Meiji Period

Identification of Natural and Early Synthetic Red Dyes Used in Silk Fabrics Dated to the Late Edo-Meiji Period

Application of LC‐MS and LC‐MS‐MS to the analysis of photo‐decomposed crystal violet in the investigation of cultural heritage materials aging

In this work, the accurate liquid chromatography-ultraviolet-visible (LC-UV-Vis), LC-mass spectrometry (MS) and LC-MS-MS analysis of the photo-degradation products of crystal violet (CV) is reported. CV is a light fugitive early synthetic dye which had a widespread diffusion into the market starting from the end of the XIX century and was used among others by V. Van Gogh and P. Gauguin in their writings, drawings or paintings. On-line photodiode array detector enabled simultaneous UV-Vis spectra acquisition. Many degradation compounds were identified through their exact mass (2 ppm accuracy) and MS-MS technique. In particular, all CV demethylated products, demethylated Michler's ketone and particularly some compounds that most likely contain oxygen, such as N-oxides, were found. Fragmentation products are all justified by the proposed fragmentation scheme, in term of precursor exact mass and isotopic profile, characteristic losses in fragmentation and rebuilt structure formula. In particular, we hypothesized the presence of N-imido oxides and hydroxylamine derivates, never reported before, together with the demethylated derivatives of the studied dyes. All these compounds, although at trace level in our samples, contribute to the discoloration and fading of works of arts made with CV. In particular, demethylation of CV by UV light leads to formation of compounds absorbing at shorter wavelengths than CV (blue shift) or no-absorbing in visible range (yellow-colourless) with an overall effect that may appear reddish-brown. This phenomenon justifies drawings appearing grey or brown on aged yellowed paper, when CV-based inks or paints were used. The final aim was to better characterize the photo-degradation of early synthetic dyes (in particular of CV) and to gain a better insight into the discoloration and fading of purple ink strokes made of CV.

Direct identification of early synthetic dyes: FT-Raman study of the illustrated broadside prints of José Gaudalupe Posada (1852–1913)

Fourier Transform (FT)-Raman spectroscopy was used for the non-invasive, direct identification of colorants used to dye historical printed papers, overcoming obstacles such as low concentration of the dye, faded colors and fluorescence interference of the aged paper substrate.

Synthetic organic dyes, 1856–1901: an introductory literature review of their use and related issues in textile conservation

The aim of this literature review is to provide a broad introduction to the little-researched subject of early synthetic organic dyestuffs and their use on historic textiles. Early synthetic organic dyes are briefly described, as is the relevant terminology. A brief history of the development of synthetic dyes up to 1901 is given, followed by a discussion of the problems arising from their use in the nineteenth century. Conservation issues relating to early synthetic dyes addressed in the literature from 1950 to 2003 are cited. The extent of use on historic textiles is described. The role of dye analysis in the study of early synthetic organic dyestuffs is indicated, with examples to illustrate its importance. A table of the 22 most commonly used early synthetic dyes is provided with International Colour Index numbers.

High-performance liquid chromatography and non-destructive three-dimensional fluorescence analysis of early synthetic dyes

Chromatographic and spectroscopic techniques are evaluated for the analysis of early synthetic dyes. The research focuses on the analysis of dyestuffs that were developed and used in the period 1850–1900, which has not been well investigated so far. The aim of this study was to develop and evaluate techniques that can be applied in the field of culture and art. A selection of 65 synthetic dyestuffs was chosen to investigate the usefulness of the analytical techniques applied. As a case study three embroideries designed by the well-known 19th century French painter Emile Bernard, were investigated to obtain more information about the use and behaviour of synthetic dyes.

Identification of Natural and Early Synthetic Textile Dyes with HPLC and UV/Vis-Spectroscopy by Diode Array Detection

Abstract The separation and identification of complex mixtures of natural and synthetic textile dyes was investigated using HPLC with diode array detection. Separation was carried out on a reversed phase column with acetonitrile-phosphoric acid gradient elution. The results show that the anthraquinones from madder root and the insect dye cocheneal present in ancient red dyes can easily be distinguished from azo-dyes present in later textile fibres. They further show that for an analysis of the numerous flavones and flavonoles, constituting most of the yellow natural dyestuffs, the combination of HPLC with on-line optical spectroscopy is particularly useful. Even when retention times are identical - as for instance for quercetin and luteolin - the ratio of a mixture can still be estimated by evaluating the ratio-chromatogram.