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Objective: To study the effects of addition of a redox metal, copper, antioxidants and metal chelators on the formation of free radicals in natural white Caucasian hair subsequently exposed to UV light. Three different methods, electron paramagnetic resonance (EPR), a fluorescent probe for hydroxyl radical formation (terephthalate) and free radical photoyellowing, were used. These methods utilized different UV sources and reaction conditions, and so can give insights into the different mechanisms of action occurring during UV oxidation of hair. In addition, this study demonstrates how antioxidants and chelators can be screened to determine whether they can protect hair from UV damage. Results: The three methods gave somewhat different results, illustrating the importance of reaction conditions and wavelength on the photochemical mechanisms, and the efficacy of additives to influence these reactions. EPR results showed that N‐acetylcysteine (NAC) pre‐treatment eliminated the intensity of the signal because of sulphur and carbon free radicals in white hair both before and after exposure to UVB radiation. Doping the hair with copper ions had no effect on the intensity of the EPR signal under dry conditions. Terephthalate fluorescent probe data showed that under wet conditions, irradiation of white hair with UVA produced significant amounts of hydroxyl radicals. Pre‐treatment of hair with NAC reduced the number of •OH radicals produced by natural white hair compared to an untreated control. In contrast to the EPR result, white hair doped with copper ions produced significantly higher levels of •OH radicals under wet conditions. It appears that the ability of copper ions to catalyse the photogeneration free radicals in hair is highly dependent on water content. Photoyellowing data showed a benefit for oxalic acid but no difference for NAC and an increase in yellowing for EDTA. Conclusion: The micro‐EPR and terephthalate fluorescent probe methods are both effective techniques to study production of free radicals by hair exposed to UV light under wet and dry conditions, respectively. Both assays are simple methods for determining the effectiveness of potential protective hair treatments against UV damage, but because they assess free radical damage under dry vs wet conditions, the chemistry created on UV exposure is different. This gives insights into mechanism of action, but results may not be consistent between the two methods for actives added for reduction of UV damage. NAC pre‐treatment did reduce free radical generation in UV‐exposed hair under both wet and dry conditions. Photoyellowing data are more complicated as it is a less direct measure of UV damage and is highly dependent on irradiation source. Using UVB irradiation is experimentally convenient but may not be appropriate, because UVB wavelengths comprise only 0.3% of terrestrial sunlight. The photochemistry of hair exposed to sunlight involves concurrent photobleaching and photoyellowing processes and is far more complex. Under UVB irradiation conditions, oxalic acid showed a yellowing benefit. [ABSTRACT FROM AUTHOR]

Synopsis The catalytic formation of hydroxyl radicals in oxidative hair colourant systems in the presence of added copper ions was measured and quantified using a colorimetric probe N, N′-(5-nitro-1,3-phenylene)bisglutaramide. Also monitored in the same experiments was the decomposition of hydrogen peroxide. The first set of experiments was performed using aqueous model solutions containing the key oxidant actives in a hair colourant, ammonium hydroxide and hydrogen peroxide at p H 10, with added copper and calcium ions. The second set of experiments was performed in the presence of hair containing different levels of copper in conditions very close to those found during hair colouring. Both sets of experiments demonstrate the ability of copper ions to trigger the formation of hydroxyl radicals and catalyse the decomposition of hydrogen peroxide. The ability of chelants ethylenediamine tetraacetic acid (EDTA) and N, N′-ethylenediamine disuccinic acid ( EDDS) to moderate the flux of hydroxyl radicals formed in solution systems was demonstrated in the presence of copper ions alone. However, only EDDS was successful in the presence of both calcium and copper ions. This was confirmed in the hair experiments where again only EDDS was successful at preventing hydroxyl radical formation where hair is added as the source of copper and calcium ions. These results are explained using metal speciation modelling and demonstrate the importance of the chelant to be able to specifically bind and prevent the one-electron redox chemistry of copper in the presence of high levels of calcium ions as found in hair. The formation of hydroxyl radicals during the colouring process was shown to lead to hair structure damage as measured by protein loss. EDDS was demonstrated to significantly reduce cuticle damage by suppressing the formation of the hydroxyl radicals in systems with realistic concentrations of calcium and copper. [ABSTRACT FROM AUTHOR]

Synthesis of sulphated proteoglycans by cell lines derived from explants of 7 rheumatoid and 9 normal specimens of synovial tissue, as well as by 7 lines of skin fibroblasts from non-rheumatoid patients, was examined. Cells of all 3 types were cultured as monolayers. They were then disaggregated and their capacity to synthesise proteoglycan estimated in cell suspensions by the incorporation of [35S]-sulphate into CPC-precipitable material during 2 hours of incubation. Cell suspensions incorporated somewhat more [35S]-sulphate than corresponding duplicate monolayers. Synovial cells from rheumatoid patients incorporated 2 to 3 times as much [35S]-sulphate as synovial cells from normals. Skin fibroblasts, however, incorporated less [35S]-sulphate than rheumatoid or normal synovial cells up to the fifth passage. Thereafter their incorporation gradually increased to overtake that of synovial cells. About one-half to one-third of the total [35S]-sulphate labelled material was closely associated with cells from synovial tissues and fibroblasts respectively. [ABSTRACT FROM PUBLISHER]

J. Cosmet. Sci., 60, 337–345 (May/June 2009) Accepted for publication December 29, 2008. Synopsis During hair coloring a number of disulfide bonds in cystine are oxidized (1) to create cysteic acid, forming binding sites for metal ions such as Ca2+ and Cu2+ from tap water (2). The increased uptake of these metals can have a detrimental impact on fiber properties—for example, reducing shine and causing a poor wet and dry feel (3). In addition, the increased uptake of copper can also contribute to further fiber damage during subsequent coloring due to its ability to take part in metal-induced radical chemistry (4). It is important to know where in the fibers these metals are located in order to either effectively remove these metals or control their chemistry. Nanoscale secondary ion mass spectrometry (NanoSIMS) has been used to locate the calcium and copper within hair that has been treated with a colorant and washed multiple times in tap water containing these ions. Untreated hair is used as a baseline standard material. Images with up to 50-nm spatial resolution of the preferential locations of calcium uptake were obtained, showing a high concentration of calcium in the cuticle region of colored hair, specifically in the sulfur-rich regions (A-layer and exocuticle). [ABSTRACT FROM AUTHOR]

Accepted for publication July 16, 2007 Synopsis High-pressure differential scanning calorimetry (HPDSC) can be used to gain information on both the degree of crystallinity in the intermediate filaments (IFs) and the structural rigidity of the surrounding matrix or intermediate filament associated proteins (IFAP) of the hair cortex (1–3). We have used HPDSC to measure changes in the denaturation temperature (TD) and enthalpy (ΔHD) of the crystalline components after multiple treatments with permanent hair colorant products. We have observed that after three repeat treatments both the denaturation enthalpy and peak temperature are significantly decreased vs. the untreated starting substrate. However, on dialysis of the fibers in deionized water this decrease is shown to be completely reversible, returning the enthalpy and temperature to that of the untreated hair. It is proposed that the decrease is due to the incorporation of formulation components such as the alkalizer and surfactants etc. and metal ions such as calcium and magnesium from the tap wash water. These components are predicted to have a non-permanent effect on the salt bridges and hydrogen bonds and hence the rigidity or viscosity of the matrix. We have compared the denaturation temperature with the tensile properties of the fiber after treatment both before and after removal of actives from the fiber. [ABSTRACT FROM AUTHOR]