Dye Components Research Articles

Hydrogen peroxide and monoethanolamine are the key causative ingredients for hair dye-induced dermatitis and hair loss

Hair dyes are being commonly used to change the color of hair for cosmetic reason. However, concern is growing over the dermatitis and subsequent hair loss associated with the repeated use of hair dye products, yet the causative ingredients have not been elucidated. Here we investigated hair dye-induced dermatitis and hair loss using in vivo mouse model to uncover the causative ingredients. Commercially available hair dye products or combination of the ingredients of hair dye product were applied topically for 3 days on the dorsum of the female C57BL/6 mice and, dermatitis and hair loss were examined. The mice treated with hair dye products exhibited unequivocal signs of hair loss and dermatitis. To find out causative ingredients, combinations of the representative components of hair dye including reducing agents, the mixture of dye and monoethanolamine (MEA), ammonia, and hydrogen peroxide (H(2)O(2)) were applied and thereafter, hair loss and dermatitis were evaluated. All the groups treated with the combinations containing H(2)O(2) and neutralized dye mixture manifested hair loss and dermatitis. Subsequent experiments revealed that H(2)O(2) and MEA synergistically induced hair loss and dermatitis. Histological examination showed that oxidative stress may be the mechanism underlying hair-dye induced dermatitis. Consistently, H(2)O(2) and MEA synergistically induced oxidative stress and cytotoxicity in human keratinocytes. These results suggest that H(2)O(2) and MEA may be the key causative ingredients for hair dye-associated dermatitis and hair loss.

In vivo quantitative evaluation of the transport kinetics of gold nanocages in a lymphatic system by noninvasive photoacoustic tomography.

Sentinel lymph node (SLN) biopsy has emerged as a preferred method for axillary lymph node staging of breast cancer, and imaging the SLN in three-dimensional space is a prerequisite for the biopsy. Conventional SLN mapping techniques based on the injection of an organic dye or a suspension of radioactive colloids suffer from invasive surgical operation for visual detection of the dye or hazardous radioactive components and low spatial resolution of Geiger counters in detecting the radioactive colloids. This work systematically investigates the use of gold nanocages (AuNCs) as a novel class of optical tracers for noninvasive SLN imaging by photoacoustic (PA) tomography in a rat model. The transport of AuNCs in a lymphatic system and uptake by the SLN were evaluated by PA tomography on the axillary region of a rat. Quantification of AuNCs accumulated in the lymph node was achieved by correlating the data from PA imaging with the results from inductively coupled plasma mass spectrometry. Several parameters were systematically evaluated and optimized, including the concentration, size, and surface charge of the AuNCs. These results are critical to the further development of this AuNC-based PA tomography system for noninvasive SLN imaging, providing valuable information for metastatic cancer staging.

Ultra-Performance Liquid Chromatographic Determination of Manufacturing Intermediates and Subsidiary Colors in D&C Red No. 34 and Its Lakes

An ultra-performance liquid chromatography (UPLC) method was developed to determine the manufacturing intermediates and subsidiary colors in the monosulfo monoazo color additive D&C Red No. 34 and its lakes. This method is currently used for batch certification of the color additives by the U.S. Food and Drug Administration to ensure that each lot meets published specifications for coloring drugs and cosmetics. The new UPLC method has replaced an HPLC method for determining the intermediates and a TLC method for determining the subsidiary colors. The intermediates are 2-amino-1-naphthalenesulfonic acid (Tobias acid) and 3-hydroxy-2-naphthalenecarboxylic acid (3-hydroxy-2-naphthoic acid). Subsidiary colors are positional isomers of the major dye component or related compounds containing lower numbers of substituent groups. The analytes are identified by comparison of their UPLC retention times and UV or visible absorption spectra with those of standards. Validation studies showed that peak area calibrations for the analytes were generally linear (R > 0.999), and recoveries were 98-103%. The LODs were 0.002-0.02%, and the RSDs at the specification levels were 0.7-2.2%. Survey analyses of 12 samples of certified D&C Red No. 34 straight colors and lakes from six domestic and foreign manufacturers yielded results for the intermediates by UPLC and HPLC that were consistent within experimental error. The UPLC analyses yielded results for the subsidiary colors that were consistently lower than results previously obtained by TLC, which we attribute to limitations of the TLC method. The new UPLC method provides sharper peaks, better peak separation, and faster analysis times than the formerly used HPLC method and is more accurate, much faster, and much less labor-intensive than the formerly used TLC method.

Ultra-Performance Liquid Chromatographic Determination of Manufacturing Intermediates and Subsidiary Colors in D&C Red No. 34 and Its Lakes

Abstract An ultra-performance liquid chromatography (UPLC) method was developed to determine the manufacturing intermediates and subsidiary colors in the monosulfo monoazo color additive D&C Red No. 34 and its lakes. This method is currently used for batch certification of the color additives by the U.S. Food and Drug Administration to ensure that each lot meets published specifications for coloring drugs and cosmetics. The new UPLC method has replaced an HPLC method for determining the intermediates and a TLC method for determining the subsidiary colors. The intermediates are 2-amino-1-naphthalenesulfonic acid (Tobias acid) and 3-hydroxy-2-naphthalenecarboxylic acid (3-hydroxy-2-naphthoic acid). Subsidiary colors are positional isomers of the major dye component or related compounds containing lower numbers of substituent groups. The analytes are identified by comparison of their UPLC retention times and UV or visible absorption spectra with those of standards. Validation studies showed that peak area calibrations for the analytes were generally linear (R >0.999), and recoveries were 98–103%. The LODs were 0.002–0.02%, and the RSDs at the specification levels were 0.7–2.2%. Survey analyses of 12 samples of certified D&C Red No. 34 straight colors and lakes from six domestic and foreign manufacturers yielded results for the intermediates by UPLC and HPLC that were consistent within experimental error. The UPLC analyses yielded results for the subsidiary colors that were consistently lower than results previously obtained by TLC, which we attribute to limitations of the TLC method. The new UPLC method provides sharper peaks, better peak separation, and faster analysis times than the formerly used HPLC method and is more accurate, much faster, and much less labor-intensive than the formerly used TLC method.

Identification and partial characterization of C-glycosylflavone markers in Asian plant dyes using liquid chromatography–tandem mass spectrometry

Flavonoids in the grasses (Poaceae family), Arthraxon hispidus (Thunb.) Makino and Miscanthus tinctorius (Steudel) Hackel have long histories of use for producing yellow dyes in Japan and China, but up to now there have been no analytical procedures for characterizing the dye components in textiles dyed with these materials. LC–MS analysis of plant material and of silk dyed with extracts of these plants shows the presence, primarily, of flavonoid C-glycosides, three of which have been tentatively identified as luteolin 8- C-rhamnoside, apigenin 8- C-rhamnoside and luteolin 8- C-(4-ketorhamnoside). Two of these compounds, luteolin 8- C-rhamnoside ( M = 432), apigenin 8- C-rhamnoside ( M = 416), along with the previously known tricin ( M = 330) and several other flavonoids that appear in varying amounts, serve as unique markers for identifying A. hispidus and M. tinctorius as the source of yellow dyes in textiles. Using this information, we have been able to identify grass-derived dyes in Japanese textiles dated to the Nara and Heian periods. However, due to the high variability in the amounts of various flavonoid components, our goal of distinguishing between the two plant sources remains elusive.

A facile route to the new triazene dyes based on substituted pyrazolidin-3,5-dione derivatives

Several substituted triazenes dyes were synthesized by coupling functionalized pyrazolidin-3,5-dione derivatives, to various heteroarene azides in excellent yields (98%). Electron delocalization between the two coupled components of these triazene dyes was studied using UV–vis spectra and NMR spectroscopy. Their thermolysis was investigated and by using an isotopically labeled triazene, the mechanism decomposition reaction was also identified. The protolysis of these triazenes was evaluated and showed that they are highly stable and even in strongly acidic medium.

A detachable SERS active cellulose film: a minimally invasive approach to the study of painting lakes

AbstractThe design and synthesis of a tailor‐made surface‐enhanced Raman scattering (SERS) active film that is fabricated to be removable from the surface of an artwork under study following effective measurements is detailed. It is shown that silver nanoparticles prepared by green chemical reduction with glucose can be effectively doped into a methylcellulose (MC) matrix for the formation of a gel, which can be subsequently applied to a minute area (ca 1–1.5 mm) of an artwork without posing a threat to its integrity. Studies have been aimed at characterizing this film's chemical and physical properties, with regard to the stability of the nanoparticles dispersed within the MC, the ease of application of the viscous gel, its speed of drying and the transparency of the dry film for SERS measurements. Importantly, results have led to reproducible SERS enhancements of the order 103–104 for studies carried out on reference laboratory dye components and unvarnished mock‐paintings. Techniques including optical and scanning electron microscopy were used to monitor the drying of the film and its resulting morphology, as well as to map the distribution of silver nanoparticles in the film so as to account for any visual modification to the underlying surface upon film removal. Copyright © 2011 John Wiley & Sons, Ltd.

Extracting natural dyes from wool—an evaluation of extraction methods

The efficiency of eight different procedures used for the extraction of natural dyes was evaluated using contemporary wool samples dyed with cochineal, madder, woad, weld, brazilwood and logwood. Comparison was made based on the LC-DAD peak areas of the natural dye's main components which had been extracted from the wool samples. Among the tested methods, an extraction procedure with Na(2)EDTA in water/DMF (1:1, v/v) proved to be the most suitable for the extraction of the studied dyes, which presented a wide range of chemical structures. The identification of the natural dyes used in the making of an eighteenth century Arraiolos carpet was possible using the Na(2)EDTA/DMF extraction of the wool embroidery samples and an LC-DAD-MS methodology. The effectiveness of the Na(2)EDTA/DMF extraction method was particularly observed in the extraction of weld dye components. Nine flavone derivatives previously identified in weld extracts could be identified in a single historical sample, confirming the use of this natural dye in the making of Arraiolos carpets. Indigo and brazilwood were also identified in the samples, and despite the fact that these natural dyes were referred in the historical recipes of Arraiolos dyeing, it is the first time that the use of brazilwood is confirmed. Mordant analysis by ICP-MS identified the widespread use of alum in the dyeing process, but in some samples with darker hues, high amounts of iron were found instead.

Simultaneous determination of p-phenylenediamines and aminophenols in hair dye products: interlaboratory study.

An isocratic HPLC method routinely used in the National Laboratory for Food and Drug Analysis of Taiwan was validated for the simultaneous determination of six aminophenols and phenylenediamines in commercial hair dyes. After extraction of the commercial hair dye product, the dye intermediates were determined by HPLC. Recoveries from the extraction were between 91.6 and 96.5%. The method was then evaluated in an interlaboratory collaborative study according to AOAC guidelines. Five laboratories in Taiwan participated in the study that analyzed the test product, which was preanalyzed by two laboratories to ensure acceptable homogeneity. The RSD(r) and RSD(R) values of the measurements obtained for the dye intermediates in the product were < or = 3.75 and < or = 5.95%, respectively. The method demonstrated acceptable reproducibility, as evidenced by HorRat values of 0.82- 0.97. The applicability of the method to the determination of oxidative hair dye components was further demonstrated in analyses of two different products. The method is thus proposed to be used by manufacturers and laboratories to evaluate the quality of commercial hair dyes containing the six aminophenols and phenylenediamines.

Production of textile reddish brown dyes by fungi

Eleven fungal strains were tested for their ability to produce brown and reddish brown textile dyes using H-acid (1naphthol-8-amino-3, 6-disulfonic acid) as a dye precursor in the fermentation medium. All tested fungal strains exhibited high ability to produce dyes varying in both dye color (brown to reddish brown) and fastness properties to washing, perspiration and UV light. The produced dyes were subjected to further analysis for quantitative determination of dye components for investigation of their inter-relations as well as their role in dye color and stability.

Application of sulphanilamides disazo dyes with Tropaeolin O for simple, rapid and sensitive spectrophotometric assay of medicines

A rapid, simple and sensitive spectrophotometric method for the determination of some sulphanilamides is described. The method is based on the formation of blue coloured disazo dyes by the diazotization of sulphonamides viz. sulphanilamide (SA), sulphamerazine (SMR), sulphamethazine (SMZ), sulphadimethoxine (SDM), sulphamethoxazole (SMX), sulphadiazine (SDA), sulfathiazole (STZ), sulphaguanidine (SGN), sulphamonomethoxine (SMM), sulphamethoxypyridazine (SMP) in 0.5 M hydrochloric acid media at ice bath followed by the azocoupling reaction with acid monoazo dye Tropaeolin O (TrO) at pH = 10.5. Formed products are stable for 10 h at room temperature. Effective molar absorptivities at absorbance maxima 595 nm for disazo dyes were ∼10 4 M −1 cm −1. Stoichiometric ratios of the components of disazo dyes were determined by means of mole ratio and continuous variations methods. Linear ranges for sulphanilamides determination were 0.4–14.0 μg ml −1. The methods were successfully approved at suphanilamides determination in model solutions and commercial pharmaceutical preparations.

HPLC–DAD–MS analysis of dyes identified in textiles from Mount Athos

Organic colorants contained in 30 textiles (16th to early 20th century) from the monastery of Simonos Petra (Mount Athos) have been investigated using high-performance liquid chromatography equipped with diode-array detection and mass spectrometry (HPLC-DAD-MS). The components of natural dyes identified in samples treated by the standard HCl dyestuff extraction method were: alizarin, apigenin, butein, carminic acid, chrysoeriol, dcII, dcIV, dcVII, ellagic acid, emodin, fisetin, flavokermesic acid, fustin, genistein, haematein derivative (Hae'), indigotin, indirubin, isoliquiritigenin, isorhamnetin, kaempferide, kaempferol, kermesic acid, luteolin, naringenin, purpurin, quercetin, rhamnazin, rhamnetin, sulfuretin, and type B and type C compounds (last two are markers for Caesalpinia trees). Early, semi-synthetic dyes, for example indigo carmine, fuchsin components, and rhodamine B were identified in objects dated late 19th to early 20th century. A dyestuff extraction method which involves use of TFA, instead of HCl, was applied to selected historical samples, showing that the mild method enables efficient extraction of weld (Reseda luteola L.) and dyer's broom (Genista tinctoria L.) glycosides. The marker compound (Hae') for logwood (Haematoxylum campechianum L.) identification after treatment with HCl was investigated by liquid chromatography coupled to mass spectrometry (LC-MS) in negative electrospray ionization (LC-MS-ESI(-)) mode. LC-MS in negative atmospheric pressure chemical ionization (LC-MS-APCI(-)) mode was used, probably for the first time, to investigate cochineal (Dactylopius coccus Costa) samples. Positive electrospray ionization (LC-MS-ESI(+)) mode was used for identification of fuchsin components. Detailed HPLC-DAD studies were performed on young fustic (Cotinus coggygria Scop.) and Persian berries (Rhamnus trees).

INVESTIGATION OF THE COLOURING MATERIALS OF FUSTAT CARPET FRAGMENTS

The Benaki Museum (Athens, Greece) possesses 50 fragments that, according to its archives, are recorded as having a provenance in the Fustat area. The objects are divided into three groups on the basis of the techniques employed. Most (eight) of the objects included in the present study belong to group A (8th–11th centuries). A few (five) fragments belong to groups B and C, which include objects dated up to the 18th century. The goal is to identify the colouring compounds contained in microsamples removed from the selected Fustat carpet fragments. Identifications are achieved using high-performance liquid chromatography (HPLC) with photodiode array detection (PDA). The following compounds are identified repeatedly in many samples: laccaic acid A and other laccaic acids (components of Kerria lacca, Kerr), alizarin, purpurin and rubiadin (madder components), luteolin, apigenin and chrysoeriol (components of Reseda luteola L.), and indigotin and indirubin (components of indigoid dyes). In one sample, the type C compound (marker compound for the identification of soluble redwoods, Caesalpinia trees) is identified. The HPLC profiles collected for the samples in which madder components are detected suggest that most probably Rubia tinctorum L. (and not Rubia peregrina L.) was used during dyeing.

Separation, Purification, and Characterization of Analogues Components of a Commercial Sample of New Fuchsin

New Fuchsin (NF), also known as Magenta III, has potential applications in photodynamic therapy. The commercial product labeled NF contains two other dye components in different proportions, Magenta II and Magenta I (Rosaniline). The proportions of NF, Magenta II, and Magenta I determined by reversed-phase high-performance liquid chromatography (RP-HPLC) in the commercial sample used were 71.6 +/- 0.4%, 25.2 +/- 0.2%, and 2.8 +/- 0.1% (n = 7), respectively. The isolation, purification, and characterization of commercial NF dye components were carried out applying different techniques, such as preparative column liquid chromatography (PCLC), thin layer chromatography (TLC), RP-HPLC, absorption spectrophotometry, nuclear magnetic resonance spectroscopy (NMR), electrospray ionization mass spectrometry (ESI-MS), and tandem electrospray ionization mass spectrometry (ESI-MS-MS). After separation and isolation, the degree of purity obtained for NF compound was higher than 95% and 92% for Magenta II and Magenta I compounds, respectively. Therefore, it is essential to ensure a high degree of purity of these dyes as raw material to obtain new drugs intended for therapeutic treatments.

Selective Detection of p‐Phenylenediamine in Hair Dyes Based on a Special CE Mechanism Using MnO2 Nanowires

AbstractWe report a novel approach for selective determination of p‐phenylenediamine in hair dyes using β‐MnO2 nanowires modified glassy carbon (GC) electrodes through an electrochemical co‐deposition process with chitosan hydrogel. A special CE (chemical reaction and electron transfer) process on the surface of β‐MnO2 nanowires modified GC electrode is proposed and proved by cyclic voltammetry and UV‐Vis spectroscopy in the presence of p‐phenylenediamine. p‐Phenylenediamine can react with MnO2 nanowires to produce diimine and the equilibrium of the two‐electron and two‐proton redox process of p‐phenylenediamine on the electrode is changed, and consequently the reductive current is enhanced significantly. At a constant potential of 0 V vs. SCE, other main components of hair dyes including o‐, m‐phenylenediamine, catechol, resorcinol, and p‐dihydroxybenzene do not interfere in the determination of p‐phenylenediamine in the amperometric measurement because of their much lower chemical reaction activities with MnO2 nanowires. It shows a determination range of 0.2–150 μM and a low detection limit of 50 nM to response p‐phenylenediamine. This modified electrode is successfully used to analyze the amount of p‐phenylenediamine in hair dyes without preseparation procedures.

A new concept for titanium oxo-alkoxo-carboxylates’ encapsulated biocompatible time temperature food indicators based on arising, not fading color

New insight into the factors determining formation and stability of oxo-alkoxide carboxylates of titanium permits to design biocompatible systems for encapsulation of binary food quality inorganic dyes, such as Preussian blue, in a temperature-sensitive shell. The shells are formed spontaneously on hydrolysis of carboxylic acid-modified titanium alkoxides on the surface of water droplets containing the dye components. The complete dye is then prepared through mixing of pre-frozen encapsulated droplets which can be activated by heating to room temperature and also influenced by the storage time. The stable shells are obtained from longer chain carboxylates providing the micellar self-assembly derived constructions with increased colloid stability. The factors influencing the formation of individual crystalline oxo-alkoxide carboxylates—a process competing with the micellar self-assembly and decreasing the stability of the oxo-alkoxide carboxylate shells are discussed with the starting point in the molecular structures of the known compounds and also the new complexes Ti6O6(OAc)6(OiPr)6 · C6H14 (1) and Ti12O12(OAc)6(OnPr)18 (2).

Abstract 4959: Multispectral imaging of chromogenic multiplex IHC assays as an alternative to fluorescent methods

Abstract Detection and analysis of two or more co-localized antigens by light microscopy has been hindered by the difficulty in discerning and quantifying overlaying chromogens. Performing multi-analyte immunohistochemistry has many potential benefits and applications in the field of drug target evaluation and patient screening, including: 1) determination and quantification of immunoreactivity co-localization; 2) evaluation of spatial relationships between immunoreactive cell types; 3) signal transduction pathway activation studies; 4) reduction in tissue depletion; and 5) decreased reagent utilization. Multiplex immunofluorescence is not widely used as an analytical technique for clinical samples due to its lower sensitivity than chromogenic methods and concerns about autofluorescence in formalin-fixed tissue. Through the use of multispectral imaging, the absorption pattern of overlapping chromogens can be spectrally unmixed into quantitative individual dye components. This process works accurately when chromogens are developed to a lower intensity than typical for most standard pathology laboratories. The chromogens must be developed to a point where they do not scatter light or block subsequent chromogenic development. The current study was performed to define the accuracy of spectral unmixing of chromogens and evaluate whether interference existed between chromogens. Stained samples were imaged using multispectral imaging, and quantitative grayscale images for each analyte were created by spectral unmixing. The grayscale images were analyzed using image analysis software to determine the overall expression levels of each analyte. Development with Vulcan Red followed by DAB produced little interference, while high density development with DAB decreased the subsequent Vulcan Red staining intensity. Vulcan Red, DAB and hematoxylin unmixed properly and quantitatively. In summary, when multiplexed chromogenic IHC assays were developed using methods optimized for multispectral imaging, the technique demonstrated excellence performance characteristics without suffering from drawbacks commonly associated with fluorescence-based techniques. Citation Format: {Authors}. {Abstract title} [abstract]. In: Proceedings of the 101st Annual Meeting of the American Association for Cancer Research; 2010 Apr 17-21; Washington, DC. Philadelphia (PA): AACR; Cancer Res 2010;70(8 Suppl):Abstract nr 4959.

Para-phenylenediamine induced DNA damage and apoptosis through oxidative stress and enhanced caspase-8 and -9 activities in Mardin–Darby canine kidney cells

Para-phenylenediamine (p-PD), a suspected carcinogen, is a component of permanent hair dyes. In this study we examined the mechanism of cytotoxicity and genotoxicity in Mardin–Darby canine kidney cells (MDCK)-treated with p-PD. Our results showed that p-PD decreased cell viability in a dose- and time-dependent manner. In addition, p-PD induced DNA damage was confirmed by the comet and TUNEL assays. Pre-treatment of MDCK cells with antioxidants vitamin C or E significantly inhibited p-PD induced cytotoxicity and reactive oxygen species (ROS) generation. Furthermore, p-PD induced apoptosis through activated initiator caspase-8 and -9, and effector caspase-3/7. Based on these results, we suggested that p-PD induce apoptosis which was mediated with caspase-8, caspase-9 and caspase-3/7 activation via the involvement of ROS.

DYESTUFF AND COLOUR ANALYSES OF THE SELJUK CARPETS IN KONYA ETHNOGRAPHY MUSEUM

Reversed-phase high performance liquid chromatography with diodearray ultraviolet–visible spectrophotometric detection was used to identify dyestuffs in carpets of the Seljuk period. The objects that were examined originate from the thirteenth century and belong to the collection of the Konya Ethnography Museum in Konya, Turkey. Extraction from fibres was carried out with a 2:1:1 solution of hydrochloric acid, methanol and water. The study identified the main individual chemical components of natural anthraquinone, flavonoid and other dyes, including alizarin, purpurin, indigotin and ellagic acid, indicating that the most important classes of natural red and yellow dyes were used in these historical carpets. Colour measurements were made on the pile of the carpets and are reported as CIELAB L*, a* and b* values. The data from the dyestuff analyses and colour measurements were used to inform conservation and restoration.

Isolation and characterization of the organic components of a black indigenous mineral hair dye

Isolation and characterization of the main organic component of a black indigenous mineral dye; Yombotumtum (YT) was carried out. The methods employed include physicochemical characterization using solubility test, melting point, combustion test, organic and inorganic (ash) contents, functional group tests, IR and UV- VIS spectroscopic analysis and preparation of derivatives. The results obtained were compared with similar results when a synthetic organic compound reference was used. Keywords: Indigenous, mineral dye, organic components, physicochemical characterization and Spectroscopic analysis.