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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]

Objective The objective of this work was to create a shampoo formula that contains a stable ordered gel network structure that delivers fatty alcohols inside hair. Methods X-ray diffraction ( SAXS and WAXS), SEM and DSC have been used to confirm formation of the ordered Lβ gel network with fatty alcohol (cetyl and stearyl alcohols) and an anionic surfactant ( SLE1S). Micro-autoradiography and extraction methods using GC- MS were used to confirm penetration of fatty alcohols into hair, and cyclic fatigue testing was used to measure hair strength. Results In this work, evidence of a stable Lβ ordered gel network structure created from cetyl and stearyl alcohols and anionic surfactant ( SLE1S) is presented, and this is confirmed via scanning electron microscopy images showing lamella layers and differential scanning calorimetry ( DSC) showing new melting peaks vs the starting fatty alcohols. Hair washed for 16 repeat cycles with this shampoo showed penetration of fatty alcohols from the gel network into hair as confirmed by a differential extraction method with GC- MS and by radiolabelling of stearyl alcohol and showing its presence inside hair cross-sections. The gel network role in delivering fatty alcohol inside hair is demonstrated by comparing with a shampoo with added fatty alcohol not in an ordered gel network structure. The hair containing fatty alcohol was measured via the Dia-stron cyclic fatigue instrument and showed a significantly higher number of cycles to break vs control. Conclusions The formation of a stable gel network was confirmed in the formulated shampoo, and it was demonstrated that this gel network is important to deliver cetyl and stearyl alcohols into hair. The presence of fatty alcohol inside hair was shown to deliver a hair strength benefit via cyclic fatigue testing. [ABSTRACT FROM AUTHOR]

Hair health is an important attribute to women globally - specifically attributes such as shine, healthy tips, frizz-free and strength. However, many women will claim to have at least moderate hair damage caused by habits and practices such as washing, combing and brushing, use of heated implements and regular use of chemical treatments. The objective of this work was to investigate two mechanisms of damage - hair colouring and UV exposure - where oxidative processes are involved. The role of copper in these oxidative processes was then investigated: its presence in hair and its consequent impact on hair damage via free radical formation. Finally, the role of chelants N, N'-ethylene diamine disuccinic acid ( EDDS) and histidine in preventing free radical formation was investigated and shown to improve hair health. [ABSTRACT FROM AUTHOR]

Synopsis Objective Damage to hair from UV exposure has been well reported in the literature and is known to be a highly complex process involving initiation via absorption of UV light followed by formation and propagation of reactive oxygen species ( ROS). The objective of this work was to understand these mechanisms, explain the role of copper in accelerating the formation of ROS and identify strategies to reduce the hair damage caused by these reactive species. Methods The location of copper in hair was measured by Transmission electron microscopy-( TEM) X-ray energy dispersive spectroscopy ( XEDS) and levels measured by ICP- OES. Protein changes were measured as total protein loss via the Lowry assay, and MALDI ToF was used to identify the biomarker protein fragments. TBARS assay was used to measure lipid peroxide formation. Sensory methods and dry combing friction were used to measure hair damage due to copper and UV exposure and to demonstrate the efficacy of N,N' ethylenediamine disuccinic acid ( EDDS) and histidine chelants to reduce this damage. Results In this work, a biomarker protein fragment formed during UV exposure is identified using mass spectrometry. This fragment originates from the calcium-binding protein S100A3. Also shown is the accelerated formation of this peptide fragment in hair containing low levels of copper absorbed from hair during washing with tap water containing copper ions. Transmission electron microscopy ( TEM) X-ray energy dispersive spectroscopy ( XEDS) studies indicate copper is located in the sulphur-poor endo-cuticle region, a region where the S100A3 protein is concentrated. A mechanism for formation of this peptide fragment is proposed in addition to the possible role of lipids in UV oxidation. A shampoo and conditioner containing chelants ( EDDS in shampoo and histidine in conditioner) is shown to reduce copper uptake from tap water and reduce protein loss and formation of S100A3 protein fragment. In addition, the long-term consequences of UV oxidation and additional damage induced by copper are illustrated in a four-month wear study where hair was treated with a consumer relevant protocol of hair colouring treatments, UV exposure and regular shampoo and conditioning. Conclusions The role of copper in accelerating UV damage to hair has been demonstrated as well as the ability of chelants such as EDDS and histidine in shampoo and conditioner products to reduce this damage. [ABSTRACT FROM AUTHOR]

Synopsis Objective The objective of this work was to identify whether low levels of redox metals such as copper will accelerate damage to hair on exposure to UV irradiation and whether this damage can be prevented. Methods The methods used were proteomics to measure the protein damage via protein loss after different periods of exposure and mass spectroscopy methods to identify specific marker peptides that are specifically created by this type of damage. Results In this work, we have developed new insights into the mechanism of UV damage using these proteomic methods. A marker fragment in the hair protein loss extract was identified (m/z = 1279) that is unique to UV exposure and increases with time of UV exposure. We have also identified for the first time in hair the role of exogenous copper in increasing UV damage both in terms of total protein degradation and also increased formation of the marker fragment and proposed a mechanism of action. It has been demonstrated that shampoo treatment containing a chelant such as N,N'-ethylenediamine disuccinic acid ( EDDS) reduced copper accumulation in hair. Conclusion This work provides evidence for the role of copper in UV-induced damage to hair and strategies to reduce copper levels in hair using a chelant such as EDDS. [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]

Synopsis Human hair can extract significant levels of calcium and magnesium, water hardness metals, from tap water immediately following chemical treatments and during hygiene practices. We have previously shown that this uptake is primarily a function of the condition of the hair. Depending on the extent of chemical damage, the hair can extract notable amounts of water hardness metals even from soft water. As water hardness metals concentrate primarily in the cuticle layers of the hair fibre, it is hypothesized that their presence will affect the structural properties that are chiefly driven by the cuticle. We examined hair mechanics and styling by technical measures of single-fibre torsional and tensile properties, combability and style retention as a function of the calcium and magnesium content of virgin and bleached hair. Our work has indicated that water hardness can affect hair properties. Fibre stiffening was induced by the presence of water hardness metals inside the fibres of both virgin and bleached hair. A reduction in combing forces was also observed, and this effect is believed to be a result of the stiffening. The style retention of virgin hair was improved by water hardness metals, whereas that of bleached hair was slightly reduced. [ABSTRACT FROM AUTHOR]

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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]

In vitro conditions affecting synthesis of sulfated proteoglycans by cell suspensions derived from monolayer cell cultures of normal and rheumatoid synovial tissue were examined. The capacity of cells to synthesize proteoglycans was estimated by the incorporation of 35S--sulfate into cetylpyridinium chloride--precipitable material. Synthesis of sulfated proteoglycans was maximal during log phase, and after 2--3 hours of recovery from disaggregation. Normal synovial cells appeared to be more sensitive to changes in serum concentration than were rheumatoid synovial cells, but rheumatoid synovial cells were more sensitive to changes in cell density. The proportion of newly synthesized extracellular proteoglycans increased with the duration of incubation in 35S--sulfate.