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A chemical mapping with high lateral resolution using an atomic force microscope in the pulsed force mode with chemically modified tips, introduced as "dynamic chemical force microscopy" (dCFM), was carried out to investigate the chemical properties of the cuticle of human hair and its changes following an oxidative treatment. Chemically modified atomic force microscopy (AFM) tips, CH3- and NH2-terminated, were applied to achieve a defined chemical contrast (hydrophobic and ionic) in aqueous medium. A comparative Fourier transform infrared spectroscopy-attenuated total reflection identified the dominant chemical groups of the surface vicinity of the hair fiber resulting from the bleaching process. The combined experimental results lead to the conclusion that the hydrophobic top layer is partially removed after bleaching, resulting mostly in hydrophilic SO3(-) end groups at the top of the surface of the hair, with a mean surface density "δ(mean)" of negatively charged groups of approximately 2.2 molecules/nm(2), corresponding to ∼600 μg/m(2) cysteic acid. This indicates that thioester bonds are disrupted and fatty acids are removed as a result of cysteine oxidation. At the molecular level, our results indicate a clustered "self-assembled monolayer" alignment of cysteic acid with a crystal-like structuring, reminiscent of the "fluid mosaic model of cell membranes", with a surface energy of approximately 0.04 N/m. Despite previous extensive works of AFM on human hair, this is, to our knowledge, the first time that the hydrophobic and ionic sites at the top surface of hair have been imaged at the nanoscale with dCFM.

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The adsorption processes of polymers that belong to two different families (neutral hydrophilic polymers and cationic polysaccharide polymers) onto solid surfaces with different charge density have been studied using dissipative quartz crystal microbalance (D-QCM) and ellipsometry. The polymers studied are very frequently used in the cosmetic industry as conditioning agents. The adsorption kinetics of the polymers involves at least two steps. The total adsorbed amount depends on the charge density of the surface for both types of polymers. The comparison of the adsorbed mass on each layer obtained from D-QCM and from ellipsometry has allowed calculating the water content of the layers that reaches high values for the polymers studied. The analysis of D-QCM results also provided information about the shear modulus of the layers, whose values have been found to be typical of a rubber-like polymer system. The main driving force of the adsorption was found to be the energy of the interactions between chains and surface.

Polymer-surfactant mixtures are found in many industrial formulations, and hence there is a significant interest in understanding, at a molecular level, how the self-assembly of surfactant is affected by oppositely-charged polyelectrolytes (PEs). We use self-consistent field modeling and show that the modes of interaction of PEs strongly depend on the architecture of the PE on the segmental level. Hydrophilic cationic PEs with their charge proximal to the linear backbone are expected to bind electrostatically to the outsides of the coronas of the spherical micelles of anionic surfactants, such as sodium laureth sulphate (SLES). As a result, the surfactant aggregation number increases, but at the same time the colloidal stability deteriorates, due to bridging of the PEs between micelles. PEs with their charge somewhat displaced from the backbone by way of short hydrophobic spacers, are expected to be present inside a micelle at the core-corona boundary. In this case the aggregation number decreases, yet the colloidal stability is retained. Hence, SLES tends to remove hydrophilic PEs from an aqueous solution, whereas it solubilizes more hydrophobic ones. The binding isotherm shows that the uptake of PEs remains typically below charge compensation and in this case the spherical micelle topology remains the preferred state.

Examination of very long hair (length > 2.4 m) using a large range of evaluation methods including physical, chemical, biochemical and microscopic techniques has enabled to attain a detailed understanding of natural ageing of human hair keratin fibres. Scrutinizing hair that has undergone little or no oxidative aggression--because of the absence of action of chemical agents such as bleaching or dyeing--from the root to the tip shows the deterioration process, which gradually takes place from the outside to the inside of the hair shaft: first, a progressive abrasion of the cuticle, whilst the cortex structure remains unaltered, is evidenced along a length of roughly 1 m onwards together with constant shine, hydrophobicity and friction characteristics. Further along the fibre, a significant damage to cuticle scales occurs, which correlates well with ceramides and 18-Methyl Eicosanoic Acid (18-MEA) decline, and progressive decrease in keratin-associated protein content. Most physical descriptors of mechanical and optical properties decay significantly. This detailed description of natural ageing of human hair fibres by a fine analysis of hair components and physical parameters in relationship with cosmetic characteristics provides a time-dependent 'damage scale' of human hair, which may help in designing new targeted hair care formulations.

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