Study of dyeing properties of semipermanent dyestuffs for hair

In this article we have evaluated some of the factors (pH, solvent composition and dye structure) that influence the dyeing of hair with dyes from direct semipermanent categories. These dyes, in fact, have been used more and more in cosmetic industry over the last years, due to their lesser aggressiveness vs. hair fibres. Two different dye classes are investigated: phenylene diamine (HC), well known for their low molecular weight and their small size, and a series of Basic dyes, characterized by the same ionic charge (positive) but with different sizes and different polar groups in the molecule. pH and dyebath composition result critical factors controlling the diffusion and adsorption process.     

Application of TLC and HPTLC in the analysis of semipermanent hair dyes

Semipermanent or direct colouring includes any product capable of affecting to some extent a change in the natural hair colour that will last through at least five shampoo washings. Semipermanent dyes are simple and easy to use, as opposed to oxidation dyes, and are normally formulated for application on nonbleached hair. Following increases in supply of such formulations, we have started an analysis for quality control purposes of 21 commonly marketed dyestuffs (nitroaminobenzenes, anthraquinone and Arianor dyes) and 20 colouring products manufactured by four leading companies. By using TLC (silica gel and reversed phase) and HPTLC (silica gel) procedures we have determined relative retention values to 1,3-diamino-4-nitrobenzene of standards and dyes found in the commercial products. All the values reported (standards and samples) are the average of five analytical results (+/-SD).     

Dyeing behaviours of amino heterocyclic compounds as blue oxidative hair dye precursors applied to keratin fibres

Several novel heterocyclic compounds based on 1,2,3,4-tetrahydroquinoline and 2,3-dihydroindole have been investigated for their application of colour keratin fibres as blue oxidative dye precursors, especially to human hair. The colourants we studied contained anyone of these dyes (concentration range from 0.005% to 6%), and some common oxidative hair dyes, such as p-phenylenediamine, toluene-2,5-diamine sulphate. Experiments were carried out on the method of mixing hair colourants with H(2)O(2) gel at the ratio of 1 : 1, accompanied by pH = 8～11. It is demonstrated that 1,2,3,4-tetrahydroquinoline derivatives could be considered as an excellent candidate for blue dyes, and N-methyl-7-amino-1,2,3,4-tetrahydroquinoline is the most outstanding one among this kind of compounds. They own significant advantages of colour purity, stability and fastness. On the other hand, 2,3-dihydroindoles show the similar colours but not stable and brilliant enough.     

Application of high-performance liquid chromatography in the analysis of direct dyes in semipermanent hair colouring cosmetics

A method for the identification and the quantification of direct dyes in semipermanent hair colouring cosmetics by using a reversed phase high-performance liquid chromatography (HPLC) with gradient elution and diode array detector (DAD) detection is presented. A standard mixture of 18 commonly marketed dyestuffs (11 nitroderivatives, two anthraquinones and five Arianor dyes) was studied. The major problems in the analysis of the mixture of direct dyes is the different chemical structure and especially the wide range of polarities. However we succeeded in the complete separation of the standard dyes. A qualitative analysis of eight colouring commercial products selected from different shades and a quantitative analysis of three of them was carried out. Materials, methods and results are reported.     

Determination of impurities in oxidation hair dyes as raw materials by liquid chromatography (HPLC)

Oxidation hair dyes as raw materials may present toxic impurities from synthesis or degradation pathways, which are responsible for allergic phenomena. In the present study selective and sensitive HPLC methods are proposed for the determination of Bandrowski base, 4-chloroaniline, 1,2-phenylenediamine and 4,4'-diaminoazobenzene in 1,4-phenylenediamine as well as 2,4-diaminoanisole in N-hydroxyethyl-4-methoxy-1,3-phenylenediamine. The proposed methods, based on reversed phase mode separation using 1,8-diaminooctane as amine modifier and photodiode array detection, proved to be suitable for the purity assessment of these widely used hair dyes; in particular the cited potential impurities were determined at ppm level.     

Significance of hair‐dye base‐induced sensory irritation

Oxidation hair ‐ dyes, which are the principal hair ‐ dyes, sometimes induce painful sensory irritation of the scalp caused by the combination of highly reactive substances, such as hydrogen peroxide and alkali agents. Although many cases of severe facial and scalp dermatitis have been reported following the use of hair ‐ dyes, sensory irritation caused by contact of the hair ‐ dye with the skin has not been reported clearly. In this study, we used a self‐assessment questionnaire to measure the sensory irritation in various regions of the body caused by two model hair‐dye bases that contained different amounts of alkali agents without dyes. Moreover, the occipital region was found as an alternative region of the scalp to test for sensory irritation of the hair‐dye bases. We used this region to evaluate the relationship of sensitivity with skin properties, such as trans‐epidermal water loss (TEWL), stratum corneum water content, sebum amount, surface temperature, current perception threshold (CPT), catalase activities in tape‐stripped skin and sensory irritation score with the model hair‐dye bases. The hair‐dye sensitive group showed higher TEWL, a lower sebum amount, a lower surface temperature and higher catalase activity than the insensitive group, and was similar to that of damaged skin. These results suggest that sensory irritation caused by hair ‐ dye could occur easily on the damaged dry scalp, as that caused by skin cosmetics reported previously.     

Effect of cationic charge and hydrophobic index of cellulose‐based polymers on the semipermanent dyestuff process for hair

In this work, the effects of a new class of polymers generally used in hair and skin cleansing products, the SoftCAT (SofCAT SL and SoftCAT SX), on the dye uptake on the hair fibre and the fading effects has been studied. These polymers, based on quaternary ammonium salts of hydroxyethylcellulose, are cationic products that differ in viscosity, hydrophobic substitution index (HS) and/or cationic substitution (CS, % N). UV–Vis spectroscopy has been used to analyse the extracted dyes from the hair cuticle and the cortex. The results indicate that the presence of polymers in the dye bath improve both the quality of the dyeing process and the anti‐fading effect during the washing cycles. This phenomenon is postulated to be attributable to the polymers hydrophobically bonding with the dyes and so facilitating their increased penetration into the hair.     

How different is human hair? A critical appraisal of the reported differences in global hair fibre characteristics and properties towards defining a more relevant framework for hair type classification

This review critically appraises the reported differences in human hair fibre within three related domains of research: hair classification approaches, fibre characteristics and properties. The most common hair classification approach is based on geo-racial origin, defining three main groups: African, Asian and Caucasian hair. This classification does not account sufficiently for the worldwide hair diversity and intergroups variability in curl, shape, size and colour. A global classification into eight curl types has been proposed but may be too complex for reproducibility. Beyond that, hair cross-sectional shape and area have been found to have an inverse relation to curl: straighter fibres are circular with larger cross-sectional area, whilst the curlier fibres are elliptical with smaller cross-sectional area. These geometrical differences have been associated with bilateral vs homogenous distribution of cortical cell in curly vs straight hair respectively. However, there is no sufficient data demonstrating significant differences in hair amino composition, but proteomic studies are reporting associations of some proteins with curly hair. Eumelanin’s relative abundance has been reported in all hair colours except for red hair which has a high pheomelanin content. Higher tensile and fatigue strength of straight hair are reported, however, curly hair fragility is attributed to knotting, and crack and flow formations rather than the structural variations. African hair has been found to have the highest level of lipids, whilst the water sorption of Caucasian hair is the highest, and that of Asian hair the lowest. Not all comparative studies clearly report their hair sampling approaches. Therefore, to strengthen the robustness of comparative studies and to facilitate cross-study data comparisons, it is recommended that the following hair defining characteristics are reported in studies: hair cross sectional diameter/area, curl type, hair assembly colour, as well as where possible donor data (age/gender) and sample pooling approach.     

Evaluation of an in vitro percutaneous permeation model with two oxidative hair dyes

The percutaneous permeation of two oxidative hair dyes was measured by means of pig skin in a flow-through diffusion cell system entirely constructed from Teflon. Pig skin membranes were prepared by reducing full thickness skin with a dermatome to a more in vivo -like barrier layer and their integrity was checked by measuring the steady-state permeation of tritiated water. Initially, the inter- and intraindividual variability of percutaneous permeation was determined with an aqueous solution of 1-(2'-hydroxyethyl)-amino-3,4-methylenedioxybenzene-hydrochloride, an oxidative hair dye component. In the same way the proper flow rate of elution fluid through the receptor cell was found to be most favourable at 10 ml h^-1, the thickness of permeation membranes was fixed at 1 mm, and it was shown that storage of the skin at −20°C for up to 35 days did not change the permeability. The percutaneous permeation of the same hair dye component and of 4-amino-2-hydroxymethylphenol-hydrochloride was determined after application to pig skin membranes under practical conditions of hair dyeing. The in vitro skin permeation was in the same order of magnitude as results from comparable in vivo skin absorption studies in rats.
Perméation percutanée in vitro de colorants d'oxydation pour cheveux     

Some challenges in modern hair colour formulations

Formulation of hair coloring product involves two stages, first a development of product base followed by formulation of desired shade. During that process a special consideration needs to be given to a whole range of product characteristics such as dye stability in the product medium, colour wearability on hair, light fading and finally rheology of the product. This paper reviews improvement in permanent coloring products as it relates to dye and base composition. Examples are shown where a reduction or elimination of certain dyes, m-phenylenediamine or sodium picramate, improves long term stability and product performance on hair. In cases when only reduction of the dyes was carried out, improvement in stability was achieved through their use as secondary colour contributors and not as primary ones. There are also other composition aspects that impact colour performance of the final product. For example, pH of the coloring mixture has a pronounced effect on the final colour developed in hair. It is shown that a shift in tonality caused by pH change can be predicted for finished product using a simple system composed of the main coupler-intermediate pair employed in the product. The colour response to pH change of this simple system was found to mirror that of the product. This predictability can be used as a formulation tool to develop more efficient dye systems. Effects of some functional materials on colour result such as propylene glycol, ascorbic acid or silicone are also shown.     

The biology of hair diversity

Hair diversity, its style, colour, shape and growth pattern is one of our most defining characteristics. The natural versus temporary style is influenced by what happens to our hair during our lifetime, such as genetic hair loss, sudden hair shedding, greying and pathological hair loss in the various forms of alopecia because of genetics, illness or medication. Despite the size and global value of the hair care market, our knowledge of what controls the innate and within‐lifetime characteristics of hair diversity remains poorly understood. In the last decade, drivers of knowledge have moved into the arena of genetics where hair traits are obvious and measurable and genetic polymorphisms are being found that raise valuable questions about the biology of hair growth. The recent discovery that the gene for trichohyalin contributes to hair shape comes as no surprise to the hair biologists who have believed for 100 years that hair shape is linked to the structure and function of the inner root sheath. Further conundrums awaiting elucidation include the polymorphisms in the androgen receptor (AR) described in male pattern alopecia whose location on the X chromosome places this genetic contributor into the female line. The genetics of female hair loss is less clear with polymorphisms in the AR not associated with female pattern hair loss. Lifestyle choices are also implicated in hair diversity. Greying, which also has a strong genetic component, is often suggested to have a lifestyle (stress) influence and hair follicle melanocytes show declining antioxidant protection with age and lowered resistance to stress. It is likely that hair research will undergo a renaissance on the back of the rising information from genetic studies as well as the latest contributions from the field of epigenetics.     

Toxicity,mutagenicity and transport in Saccharomyces cerevisiae of three popular DNA intercalating fluorescent dyes

We have compared the toxicity, mutagenicity and transport in Saccharomyces cerevisiae of three DNA‐intercalating fluorescent dyes widely used to stain DNA in gels. Safety data about ethidium bromide (EtBr) are contradictory, and two compounds of undisclosed structure (Redsafe and Gelred) have been proposed as safe alternatives. Our results indicate that all three compounds inhibit yeast growth, with Gelred being the most inhibitory and also the only one causing cell death. EtBr and Gelred, but not Redsafe, induce massive formation of petite (non‐respiratory) mutants, but only EtBr induces massive loss of mitochondrial DNA. All three compounds increase reversion of a chromosomal point mutation (lys2‐801^amber), with Gelred being the most mutagenic and Redsafe the least. These dyes are all cationic and are probably taken by cells through non‐selective cation channels. We could measure the glucose‐energized transport of EtBr and Gelred inside the cells, while uptake of Redsafe was below our detection limit. We conclude that although all three compounds are toxic and mutagenic in the yeast system, Redsafe is the safest for yeast, probably because of very limited uptake by these cells. Copyright © 2015 John Wiley & Sons, Ltd.     

Grey hair: clinical investigation into changes in hair fibres with loss of pigmentation in a photoprotected population

Loss of pigmentation in hair fibres is one of the most obvious phenotypic changes with ageing and has been a topic of increasing interest in the study of follicle biology. The onset of greying brings cosmetic complaints that grey fibres are wild or difficult to manage. Of course, these perceptions may be the consequence of visual obviousness rather than underlying physical or chemical differences. Although several studies have compared pigmented and unpigmented fibres, few have tried to control genetic and ethnic difference as well as extrinsic factors such as photoexposure and chemical treatment. We have recruited subjects with salt-and-pepper hair from a population of Old Order Mennonites who, for cultural reasons, are not only prohibited from chemically treating their hair but also limit their exposure to sunlight. Hair samples were examined for elemental composition, surface energy, Young's modulus, break stress, bending modulus, shear modulus and water sorption/desorption isotherm. The parameters were evaluated statistically for global differences, individual differences and typical individual differences. Consistent with previous published literature, few global differences were found between pigmented and unpigmented hair across the population. We do find that many individual subjects had differences between pigmented and unpigmented fibres. These differences tend to be more pronounced in bulk than in surface properties. The small differences in mechanical properties and moisture uptake and loss lend support to the perception by consumers that grey hair is wilder, drier and less manageable.     

Function of surfactants in hair dyeing by oxidation dyes 2. Effect on formation of oxidation dyes by p-aminophenol and 5-amino-o-cresol in dye bath(1)

The effect of surfactants on an oxidation-hair-dye-formation reaction in a dye bath was studied in order to learn the mechanism of the effect of surfactants on the dyeability of hair by the oxidation dye. The dye-formation behaviours for the p-aminophenol and 5-amino-o-cresol system with the surfactants, of which the hydrophilic parts have different charges, were compared changing the concentration of surfactants. It was found that the same dyes are produced, regardless of the charge of surfactants added, and the rate of dye produced in the dyebath is increased in the presence of surfactants. The order of the production rate is, with an anionic surfactant > with non-ionic surfactant > with cationic surfactant > without surfactant. The relation between the dyeability of hair and the rate of dye produced in the dyebath in the presence of surfactants is not found. The major factor governing the dyeability of hair is different from the mechanism of the increased dye in the solution. It was also found that the dye-formation rate is increased by immersing hair into the reaction solution, and hair works as an accelerator for the dye-formation reaction.     

Can plant‐derived phytochemicals provide symptom relief for hair loss? A critical review

It is known that hair growth disorders and hair loss can cause personal distress and affect well‐being. Whilst clinical conditions remain a target for medical research, current research on hair follicle biology and hair growth control mechanisms also provides opportunities for a range of non‐medical and cosmetic interventions that have a modulating effect on the scalp and follicle function. Furthermore, an improvement of the hair fibre characteristics (cuticle structure, cortex size and integrity) could add to the overall positive visual effect of the hair array. Since phytochemicals are a popular choice because of their traditional appeal, this review provides a critical evaluation of the available evidence of their activity for hair benefit, excluding data obtained from animal tests, and offers recommendations on improving study validity and the robustness of data collection in pre‐clinical and clinical studies.     

食品中色素检测的研究进展

文章详细介绍了食用色素和违禁染料的定义、分类、特点,以及国内外对于色素类检测技术的研究现状,提出了未来色素类检测技术的重点、难点和发展趋势。     

ESR study of photoinduced free radicals by visible light in hair and the effects of ascorbic acid (vitamin C)

The ESR spectra of melanin's free radicals in natural black and red hair have been investigated. It is shown that the ESR spectrum of black hair is slightly asymmetric singlet with g=2.0037 and ΔH=0.5 mTl. The ESR spectrum of red hair with g=2.0053 differs from the spectrum of black hair. Using the method of saturation was shown that ESR spectrum of red hair represents a superposition of two signals: a singlet, relating to the black hair, and a triplet from red hair's pheomelanin. Under the influence of visible light (blue with λ(max) =450 nm, green with λ(max) =510 nm and red with λ(max) =650 nm) in both types of hair (black and red), the photoinduced free radicals appear, which indicates an increase in the intensity of already existing ESR spectrum of hair. It should be noted that the ESR spectra of red hair from various donors are different. The antioxidant ascorbic acid (vitamin C) has the different effect on the photoinduced free radicals. In particular, in the case of black hair, the concentration of photoinduced free radicals is slightly reduced, whereas in red hair, the disappearance of the triplet in the spectrum is observed, and at the same time, the spectrum becomes a singlet, the intensity of which increases sharply. It is assumed that the antioxidants, effective for black hair, may be ineffective for red hair and vice versa. Therefore, in each, specific case is necessary to investigate the effectiveness of an antioxidant separately.     

In vivo procedures for assessment of hair greasiness

Greasy hair is a common problem in Europe. The first step in developing anti-grease hair products must be to establish a sensitive protocol for measuring any changes in perceived hair greasiness.
Sensitive clinical trials and in vivo evaluation methods of determining hair greasiness have been developed that show significant differences in the perceived hair greasiness following the use of different shampoos.
Products tested in two clinical trials for efficacy as anti-grease shampoos were an anti-grease shampoo containing 2% 3,4-thiolanediol as the active ingredient, and a baby shampoo based on mild surfactants. The same placebo shampoo based on ether sulphates used in typical European shampoo formulations was used in both tests. A shampoo containing 2% zinc pyrithione was included in the trials as a control, since there were indications that this would increase the amount of hair greasiness.
Neither of the test products were shown to be effective anti-grease shampoos. The shampoo containing 2% zinc pyrithione was shown to produce significantly more greasiness than both the placebo and the test shampoos.
Since significant differences could be shown between the different shampoos, the protocol and in vivo evaluation techniques used in these clinical trials are considered to be validated.
Méthodes in vivo d'évaluation du graissage des cheveux     

Some simple theoretical considerations on the bending stiffness of human hair

Factors affecting the cantilever bending of human hair have been investigated by theoretical structural mechanics in which the hair was treated as if it was of isotropic structure and internal mechanical property. Despite the simplicity of the model it is a valuable one for assessing the major geometric factors affecting a hair's bending behaviour in relation to perceptions of coarseness and fineness. Simple equations have been used for predicting relative bending stiffness between hairs of different racial types using published fibre cross-sectional information and these accord with existing perceptions of behaviour. Strikingly it is the hair's minor elliptic diameter which has a dominant effect upon bending resistance and it is shown that the hair's cuticle could be making a very high proportional contribution. It is shown that triangular hairs of the uncombable hair syndrome will be stiffer than normal elliptical hairs of the same cross-sectional area and that this goes some way to explaining the condition.     

6-O glucose linoleate supports in vitro human hair growth and lipid synthesis

The hair follicle is a very active organ with a complex structure, which produces a hair fibre at a rate of 0.3 mm a day. Accordingly, the hair follicle is highly demanding in energy source, as the hair bulb matrix cells are endowed with one of the highest rates of proliferation in the human body. Moreover, recent data have shown the involvement of lipids in hair follicle function. As in vitro-grown hair follicle keeps producing a hair fibre that closely resembles the natural hair fibre, we decided to use this model to investigate the role of a new of glucose linoleate derivative (6-O-linoleyl-d-glucose: 6-O-GL) as a lipid precursor and energy provider. Our results demonstrated that 6-O-GL was (i) quite stable and surprisingly resistant to oxidative degradation, and (ii) readily taken up and metabolized by the hair follicle into various lipids, namely neutral lipids, ceramides and polar lipids. Moreover, it supported hair follicle growth and survival in a glucose- and linoleic-acid free medium. 6-O-GL thus appeared to be a bi-functional nutrient, ensuring both proper fibre quality and production by the hair follicle.