Madder Dyes Research Articles

Experimental and Theoretical Study of Madder-Associated Dyestuffs on Silk: Adsorption of Kinetics, Thermodynamics and Molecular Docking

ABSTRACT In this work, dyed samples were self-prepared from two methods including madder dyeing and mordant dyeing by madder combined with Al3+ at different temperatures, and their kinetics and isothermal adsorption were both discussed. Weber–Morris diffusion model and Freundlich model were found to be more suitable in dyeing for kinetics and thermodynamics. Through SEM, FTIR and fastness tests, the dyeing performances were displayed and the possible structure between madder dyes and the complex with Al3+ were illustrated. By molecular docking, madder dyes showed combination with glutamic acid predominantly. After introducing metal ion, the shortage of hydrogen bonds length was observed. It was initially employed to elucidate the potential binding modes between dyes and proteinaceous fibers. Overall, through experimental dyeing and curve fitting, this study provided insights into the dyeing mechanism of madder-associated dyestuffs on silk. Moreover, molecular docking elucidated the dyeing mechanism further, highlighting that the presence of metal ion enhances the firmness of the staining. The elucidation of dyeing mechanism not only provided valuable theoretical support for color restoration but also shed light on the practically modify of methods in obtaining ideal color. These results could serve as inspiration for conservators to maintain the vibrancy and longevity of dyed silks.

Gel microextraction from hydrophilic paint layers: A comparison between Agar-gel and Nanorestore Gel® HWR for spectroscopic identification of madder

While non-invasive analyses are widespread for the study of inorganic components in cultural heritage, the identification of organic substances can be very challenging when sampling is forbidden. In particular, organic dyes are hardly detectable because of their low concentration and tendency to fade. Hydrogels retention and release properties make them suitable for microextraction of dyes directly from the artifact, maintaining its integrity. After extraction, the hydrogels versatility makes them ideal for a multi-analytical study of the dyes. In this work, the gel microextraction procedure was put to the test of hydrophilic paint layers. Different Agar-gel weight concentrations were tested and compared with Nanorestore Gel® High Water Retention for the extraction of madder dyes from Arabic gum paint layers. UV–vis spectroscopy and SER spectroscopy were effective in identifying the analytes. Nonetheless, the sampling mechanism and the procedure invasiveness have proved to be dependent on the hydrogels retention power.

A multi-analytical approach to identify red colorants on woodblock prints attributed to Suzuki Harunobu

Red organic dye identification is an important topic for conservation of Japanese ukiyo-e prints. Of particular interest are the works of Suzuki Harunobu, who was working at the inception of full-color printmaking. These prints were made on thin kōzo paper and woodblock printed with semi-transparent to opaque regions of dye(s) and/or pigment(s) mixed with binder. This study used imaging analysis, X-ray fluorescence (XRF), Raman, and surface-enhanced Raman spectroscopies (SERS) to identify the red dyes and pigments on Harunobu prints in the collection of the Portland Art Museum. Through image analysis (visible, UV, and IR illuminations), 23 prints were categorized by appearance. XRF results provided identification of vermilion and ochre pigments, and identified color fields that contained lead. Raman analysis allowed the identification of red lead, and SERS was used to identify both safflower and madder dyes. This work is expected to contribute to the body of knowledge regarding the red dye and pigment palette and mixtures in use in the mid- to late eighteenth century, in the critical early years of full-color printmaking.Graphical

A novel efficient method for eco-friendly deep dyeing of wool yarns by extracted madder dyes in the presence of additives

Zinc sulfate and magnesium sulfate were used as additives to provide an effective simultaneous mordanting and dyeing process (meta mordant) for wool yarns with madder dyes extracted by ultrasound. In the dyeing procedure, aluminum sulfate and ferrous sulfate were used as mordants. A response surface methodology (RSM) experimental design was used to optimize the dyeing technique. Results showed that the highest color strength of dyed samples was achieved at 105–110 min at 1:30 ratio of aluminum sulfate to zinc sulfate, 1:10 ratio of aluminum sulfate to magnesium sulfate, and pH of 2.5–3. It was observed that the dyeing of yarns with extracted dye and ferrous sulfate could be carried out without using additives. The color properties of dyed yarns using the novel approach were compared to samples dyed using the conventional method (pre-mordant). The findings revealed that dyed samples using the novel approach had the same or greater color strength as dyed samples using the pre-mordant procedure. L* , a* , and b* of the dyed yarns by extracted dyes and aluminum sulfate in the presence of magnesium sulfate were approximately the same with yarns dyed by the pre-mordant method. Also, the color fastness properties of dyed samples by meta mordant method were acceptable in terms of wash, light, and rub fastnesses. Nearly similar or better color stability was achieved compared to the common method. In this respect, a novel efficient one bath method was introduced for deep dyeing of wool yarns with extracted madder dyes which can decrease the negative environmental impacts such as pollutants, water consumption, and energy in comparison to other conventional methods.

Optimized micro-sampling and computational analysis for SERS identification of red organic dyes on prints

The goals of this study were to develop a robust methodology and data analysis procedure to identify red dyes in artwork where dye collection is inaccessible by traditional methods. With Surface-Enhanced Raman Spectroscopy (SERS) it is possible to obtain identifying molecular information from dilute and degraded dyes. A minimally invasive, soft-mechanical sampling method to gently contact printed paper is described; using a customized polymeric hydrogel surface with an exposure area of about 1 mm2, micrometer-diameter colorant particles were collected. To validate that the sample collection methodology is minimally invasive, test papers were photographed before and after sampling under UV and white light; and DART-MS analysis of the sampled area was conducted. A reference library of SERS spectra from binder (hide glue), dyes (safflower, sappan, and madder), and binder-dye mixtures was built and used by a spectral-matching genetic algorithm (GA). Fifty individual GA runs returned results that precisely matched at least one dye component in 48–50 of the 50 runs, and matched both dyes in a mixture between 29 and 50 of the 50 runs. Finally, in an artwork application, the methodologies were demonstrated on micro-samples from three areas of an 18th century Japanese woodblock print by Suzuki Harunobu in the collection of the Portland Art Museum, on which, madder dyes were positively identified. Conclusions and extensions from this work are expected to contribute to the body of knowledge about 18th c. Japanese woodblock prints.

Fiat Lux ... how Alessandro Volta illuminated his scripts

The ink used by Volta in his scripts appears to be a very complex mixture. Our analysis of the eluates from the EVA diskettes (via GCXGC/TOFMS) has revealed the presence of more than 1800 unique metabolites. The ink thus appears to be a very complex combination of different ingredients, mainly consisting of tannins, vegetable oils and resins together with root and wood dyes. In particular, the presence of hydroxy and dihydroxyanthraquinones, as well as natural quinoids, evidenced the use of madder dyes from Rubiaceae as an important component of this ink. Natural quinoids, based on a 9, 10-anthraquinone skeleton, hydroquinone and anthrone derivatives, and even the specific marker of alizarin, indicate the use of the Rubia tinctorum. Additionally, the presence of several signals of fatty acids, saturated and unsaturated mono and dicarboxylic acids, as well as of the typical signals of Pinaceae resins substantiated the use of a vegetable oil and colophony. Several signals of cyclic monosaccharides suggested also the use of natural gum (Acacia Senegal also known as Arabic gum). It is known that Arabic gum, as well as linseed oil, were often employed as thickeners to increase the viscosity of the ink and to protect it from excess absorption of atmospheric oxygen. Curiously, we also found characteristic signals from alkaloids such as Dioncophyllin A and B, typical metabolites from tropical/exotic plants such as Triphyophyllum, Habropeltatum and Dioncophyllum. To our reckoning such an extensive array of ingredients in inks adopted over millennia has never been reported.

Identification of dyes in Egyptian textiles of the first millennium ad from the collection Fill-Trevisiol

High-performance liquid chromatography coupled to a diode-array detector (HPLC-DAD) is used to investigate 30 samples which were removed from 27 ancient Egyptian fabrics of the Fill-Trevisiol collection. Attention is focused in this paper on fabrics of the Roman and Byzantine periods, with red and deep violet–blue wool weft threads which are Z-spun. The following dyes are identified in fabrics which date to the Roman period (first–fifth c. ad): mollusc purple, madder, and indigo/woad (Indigofera species and other, Isatis tinctoria L.). The results for the Byzantine (fifth–seventh c. ad) fabrics are richer in terms of identified dyes: apart from the three aforementioned dyes, the use of kermes (Kermes vermilio Planchon) and cochineal is revealed as the two coccid dyes have been detected in six Egyptian–Byzantine fabrics. Moreover, a yellow dye (probably Reseda luteola L.) is identified in one sample. Finally, samples taken from two fabrics, which date to the Islamic period, were dyed using indigo/woad and lac (Kerria lacca, Kerr). Mixing madder and indigo/woad to imitate true purple was a common practice in ancient Egypt and this is confirmed by the HPLC results in several samples. Semi-quantitative results are obtained from the HPLC peak areas and lead to the following conclusions. Madder dyes which were rich or poor in alizarin, compared to purpurin, and could have been therefore obtained from Rubia tinctorum L. and Rubia peregrina L., respectively are detected in Byzantine fabrics. Only alizarin-rich madder dyes are identified in some samples from Roman fabrics, but in some other samples the relative alizarin-to-purpurin ratio cannot be measured with confidence. Cochineal is found in two samples. The biological source of cochineal (Porphyrophora hamelii Brandt) is possible to be chemically identified only in one sample. The HPLC results of the molluscan dye detected in a Roman fabric are compared with the relative compositions of extracts of the three Mediterranean molluscs leading to the speculation that the Roman purple sample was probably dyed using Hexaplex trunculus L. The molluscan dye was furthermore detected in a Byzantine sample where it was combined with madder. Finally, it is reported that the standard (hydrochloric) acid hydrolysis method which is commonly applied to extract dyes from archaeological samples does not have any noticeable effect on the relative composition of the molluscan dye.

A new approach to the mild extraction of madder dyes from lake and textile

In this paper, we present a new alkaline mild extraction technique of madder dyes in lake and textile, based on the use of ammonia, in association with disodium EDTA. This method was developed in order to preserve the glycoside compounds fixed on the fiber or present in the lake. This new methodology was performed on samples of dyed textile and lake, prepared following the ancient recipes. At first, the extracts, obtained from these samples, were analyzed and characterized by 1D and 2D NMR (DOSY) and ESI-MS. In the second step, we evaluated the applicability and the efficiency of extraction on real samples of 1mg, analyzed by HPLC–DAD and HPLC–MS. These analyses allow us to recognize the signals, referable to glycoside compounds, also in 1mg samples. The new proposed method was compared with a commonly applied mild extraction method reported in literature (DMF–Na2EDTA method). Finally, the results obtained from the different analytical techniques applied allow us to conclude that the ammonia extracts of madder dyed yarn and lake are mainly composed of glycosylated anthraquinones, according to literature.

Surface‐enhanced Raman spectroscopy of various madder species on wool fibers: the role of pseudopurpurin in the interpretation of the spectra

Madder has been used as a textile dye and pigment in works of art since antiquity. Madder dyes from different botanical species are characterized by different series of anthraquinone derivatives. The occurrence of one or more of these compounds in various relative amounts may provide a useful indication of the plant species used to obtain the dye. In this work, surface‐enhanced Raman spectroscopy (SERS) was applied to the analysis of textile fibers dyed with madder from two different botanical species, Oldenlandia umbellata L. and Rubia tinctorum L. The resulting SERS spectra were interpreted in light of the actual composition of the madder dyes as determined by high‐performance liquid chromatography. Interestingly, the SERS spectra were found to exhibit very distinctive spectral features depending on the different anthraquinone derivatives present in the dyes. In particular, the SERS spectrum of O. umbellata L. was found to match the spectrum of alizarin, while the SERS spectrum of R. tinctorum L. was surprisingly dominated by signals due to the less studied anthraquinone compound pseudopurpurin. With this study, we demonstrate that SERS spectra may offer valuable information regarding the major coloring constituents present in different madder species. Moreover, our work shows that not only can SERS be used successfully to differentiate among closely related anthraquinone derivatives, but also that this technique is particularly suitable for the detection of pseudopurpurin, leading to the identification of this compound in a number of works of art. Copyright © 2015 John Wiley & Sons, Ltd.

Characterization of madder and garancine in historic French red materials by liquid chromatography-photodiode array detection

Abstract A reverse phase liquid chromatography-photodiode array detection method is developed for the characterization of ancient samples of madder. In the past, modifications of the madder chemical composition were carried out by hydrolysing the plant dye precursors in order to increase its red power, the aim of this transformation being to concentrate the red colour of the matter. After extraction of madder dyes in a water-methanol mixture, different anthraquinonic compounds were identified through the chemical constituents present in a garancine sample and in the two madder species growing in the Mediterranean area: Rubia tinctorum and R. peregrina . These two species comprise alizarin, purpurin, lucidin, rubiadin and pseudopurpurin for aglycones and, lucidin primeveroside, ruberythric acid, galiosin and rubiadin primeveroside for heterosidic precursors. These compounds were identified through retention times and UV spectra in comparison with pure standards. Six ancient materials belonging to the collection of the Roure Museum in Avignon (France) and dating from the nineteenth century are characterized as hydrolysed madder (garancine), synthetic alizarin and R. tinctorum roots. A colorimetric study is performed to compare the colour of each sample according to its chemical composition.

Cytohistological and phytochemical study of madder root extracts obtained by ultrasonic and classical extractions

Madder (Rubia tinctorum) has been used since ancient times as a source of pigments for dyeing and painting. Madder dyes are localised in roots and the native chemical population is composed of glycosiled and aglycone compounds. The aim of this study is to elaborate an efficient extraction process without any chemical denaturation of dyes. To compare an optimised ultrasonic process, using for madder dye extraction, with two conventional procedures and to determine the efficiency of ultrasound on these vegetable matrix. Madder roots were extract in a methanol-water mixture in 37 : 63 (v/v) for ultrasound and 80 : 20 (v/v) for reflux and agitation. HPLC-PAD analyses showed the anthraquinone proportion for each extraction process and their denaturing effects. Finally, cytohistological observations were made to show the consequence of each process on the cell organisation in madder roots. The results showed that the amount of extracted dyes was higher with UAE than with agitation and reflux. HPLC-PAD analysis revealed that the anthraquinone composition differed according to the extraction procedure. The UAE extracts presented an important richness in terms of anthraquinonic compounds that suggests a preserving effect. Cytohistological observations showed that the main alterations concerned the cell walls of phloem. After UAE the walls exhibited numerous pitted areas reflecting an ultrasound-induced cavitation that enhances the extraction effectiveness of this method. The study has shown the improvement of madder roots extraction both quantitatively and qualitatively using the efficiency of ultrasound-assisted extraction in comparison with magnetic agitation and reflux techniques.

A multivariate study of the performance of an ultrasound-assisted madder dyes extraction and characterization by liquid chromatography-photodiode array detection

An extraction method of madder ( Rubia tinctorum) roots dyes is established and optimized to obtain the original chemical composition. A central composite design (CCD) was developed to specify the importance of the three major factors studied (time, temperature and solvent composition) affecting the ultrasound-assisted extraction of this matrix. A preliminary granulometric study of madder roots is realized in the aim to determine the optimal particles size corresponding to the best ultrasound effects. A comparison with the classical extraction method of madder dyes by reflux is described. The identification of the constituents of R. tinctorum is carried out by liquid chromatography coupled with a photodiode array detector (LC–PDA). Anthraquinonic aglycone and heterosidic dyes compounds are characterized by retention time and UV spectrum: alizarin (1,2-dihydroxyanthraquinone), purpurin (1,2,4-trihydroxyanthraquinone), lucidin (1,3-dihydroxy-2-hydroxymethylanthraquinone), rubiadin (1,3-dihydroxy-2-methylanthraquinone), xanthopurpurin (1,3-dihydroxyanthraquinone), pseudopurpurin (1,2,4-trihydroxy-3-carboxyanthraquinone), lucidin primeveroside, ruberythric acid (alizarin primeveroside), galiosin (pseudopurpurin primeveroside) and rubiadin primeveroside. The optimal experimental conditions are 18 min, 36 °C and 37/63 MeOH/H 2O (v/v).

Analysis of anthraquinoid and indigoid dyes used in ancient artistic works by thermally assisted hydrolysis and methylation in the presence of tetramethylammonium hydroxide

Thermally assisted hydrolysis and methylation (THM) in the presence of tetramethylammonium hydroxide (TMAH) was applied to the analysis of red dyes based on the 9,10-anthracenedione skeleton (anthraquinone), namely alizarin, quinizarin, purpurin, carminic acid, and the blue pigment indigo. Alizarin and purpurin are the principal coloured compounds of madder, and carminic acid of cochineal red. Synthetic dyes were dissolved in aqueous TMAH, pyrolysed at 700°C for 10 s and the evolved thermochemolytic products were analysed by gas chromatography/mass spectrometry (GC/MS). The resulting chromatograms of all the madder dyes were characterised by the presence of the methyl esters of 1,2-benzenedicarboxylic acid (dimethyl- o-phthalate) and benzoic acid. In addition, thermochemolysis of alizarin and quinizarin afforded 1,2-dimethoxyanthraquinone and 1,4-dimethoxyanthraquinone, respectively. Carminic acid produced a series of methylated fragments deriving from both the substituted anthraquinoid moiety and the glycosidically-C-linked glucose. Finally, the principal thermochemolysis products of indigo were the N-methylated derivatives of 2-amino benzoic acid methyl ester followed by methylated aniline and indoles. The potential of THM as a rapid technique for the identification of dyes in real samples was illustrated by the analysis of madder lake, cochineal lake, and natural indigo dispersed in a binder.

Konstitution und Farbe von Alizarin‐ und Purpurin‐Farblacken

Constitution and Colour of Alizarin and Purpurin DyesThe colour of madder dyes used as pigment in antiquity and in the last centuries is produced mainly by metal complexes of alizarin (1) and purpurin (2). Single crystals of aluminium calcium alizarinate and purpurinate are obtained by two‐phase crystallization. X‐ray structure determinations show tetranuclear complex molecules with four alizarins which are different from formerly proposed structures. Solutions of 17 metal complexes of alizarin in DMF/Water exhibit UV‐Vis spectra the maxima of absorption of which strongly depend on the electronegativity of the metals. A classical explanation for this is given.

Competition Between the Aniline and Madder Dyes

Competition Between the Aniline and Madder Dyes