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Surfactants form the core of all shampoo formulations, and contribute to a wide range of different benefits, including cleansing, foaming, rheology control, skin mildness and the deposition of benefit agents to the hair and scalp. The purpose of this review was to assist the design of effective, modern, shampoo surfactant technologies. The mechanisms through which surfactants help deliver their effects are presented, along with the appraisal techniques through which surfactant options can be tested and screened for product development. The steps that should be taken to select the most appropriate blend of surfactants are described, and useful information on the most widely used surfactants is provided. The review concludes with an examination of recent developments in 'greener' surfactants, 'sulphate-free' technologies and structured liquid phases for novel sensory properties and for suspending benefit agents.R esum e Les agents tensioactifs sont les ingr edients de base de la plupart des shampooings, et contribuent de nombreuses mani eres a leurs performances et sp ecificit es : qualit e nettoyante, onctuosit e de la mousse, control de la rh eologie, sensation cutan ee ou bien d eposition d'actifs sur les cheveux ou le cuire chevelue. Le but de cette revue est d'apporter une assistance pour l' elaboration de surfactants innovants pour le d eveloppement de nouveaux produits capillaires. Les m ecanismes par lesquels les agents tensioactifs d elivrent leurs b en efices sont discut es, ainsi que les diff erentes techniques disponibles pour les tester et les s electionner dans le cadre de l' elaboration de nouveaux produits. Les diff erentes etapes qui devraientêtre prises en consid erations pour s electionner les agents tensioactifs les plus appropri es y sont d ecrites ainsi qu'une section r esumant les informations relatives aux agents tensioactifs les plus utilis es actuellement. En conclusion, la revue pr esente les d eveloppements r ecents autour de nouveaux agents ecologiques (ou « vert »), des technologies « sans sulfate » et des technologies « structured liquid phases » qui procurent de nouvelles propri et es sensorielles ou de suspensions.

Twelve sesquiterpene compounds, derived from natural volatile oils, were investigated as putative skin penetration enhancers for human skin. Pretreatment of epidermal membranes with sesquiterpene oils, or solid sesquiterpenes saturated in dimethyl isosorbide, increased the rate of absorption of the model hydrophilic permeant, 5-fluorouracil (5-FU). Enhancers with polar functional groups were generally more potent than pure hydrocarbons. Furthermore, enhancers with the least bunched structures were the most active. The largest effect was observed following pretreatment with nerolidol, which increased pseudo-steady-state 5-FU flux over 20-fold. Molecular modelling suggested that terpenes with structures suitable for alignment within lipid lamellae were the most potent enhancers. Sesquiterpene enhancers had long durations of action implying that they did not wash out of the skin easily. This study attempted to improve enhancer clearance by replacing the aqueous donor and receptor phases by ethanol:water (1:1) solutions. Ethanol increased the permeability coefficient for 5-FU 13-fold, demonstrating that, in aqueous solution, it is a moderately potent penetration enhancer. Sesquiterpene and ethanol enhancement effects were approximately additive. Sesquiterpene effects were almost fully maintained for at least 4.5 days following pretreatment, illustrating poor reversibility. Stratum corneum/water drug partitioning studies suggested that an important mechanism of action of the enhancers was to increase the apparent drug diffusivity in the stratum corneum. Increases in drug partitioning into the entire stratum corneum following enhancer pretreatment were relatively small. Diffusivity increases were directly related to overall rises in permeability. This study has shown that sesquiterpene compounds, which are of low toxicity and cutaneous irritancy, can promote 5-FU absorption across human skin. Sesquiterpene compounds, therefore, show promise as clinically-acceptable skin penetration enhancers.

Wide-angle X-ray-diffraction experiments were used to investigate the molecular organization of barrier components of human stratum corneum. Diffraction lines related to the side-by-side lipid packing arrangements in the intercellular bilayers were identified as were patterns arising from secondary protein structures in intracellular keratin. Reflections were also identified which may be produced by proteins in the corneocyte envelopes. The effects of hydration on stratum corneum structure were monitored using 0, 20-40, 40-60, 60-80 and approximately 300% hydrated samples. The packing arrangements in the intercellular lipid bilayers remained the same over the entire hydration range, as did keratin structures. A new diffraction ring, attributable to liquid water, was produced by 300% hydrated samples with a repeat spacing of 0.35 to 0.30-0.29 nm. The effects of three terpene enhancers, (+)-limonene, nerolidol and 1,8-cineole, on stratum corneum structure were monitored. Treatment with each of the terpenes produced additional reflections which were attributed to the presence of the respective liquid enhancers within the stratum corneum. (+)-Limonene produced an additional reflection at 0.503-0.489 nm, nerolidol, an additional reflection at 0.486-0.471 nm and 1,8-cineole, an intense reflection at 0.583-0.578 nm. Reflections characteristic of gel-phase lipids and crystalline lipids also remained after all terpene treatments. These results provide no clear evidence of lipid bilayer disruption by the terpenes and suggest that areas of liquid terpene exist within the stratum corneum. The mechanisms underlying propylene glycol synergy with terpene enhancers were investigated. Treatment of stratum corneum with each terpene mixed with propylene glycol gave rise to two additional reflections. One reflection, always positioned at 0.452-0.448 nm, had been observed in control studies following propylene glycol treatment and may have been associated with bilayer structures disrupted by propylene glycol or altered keratin structures. The second reflection was developed by the respective terpene enhancer. For example, treatment with a 1,8-cineole/propylene glycol mixture produced reflections at 0.457-0.451 nm (propylene glycol-disrupted lipids or altered keratin) and 0.591-0.578 nm (liquid 1,8-cineole). Since the reflection at 0.452-0.448 nm was unaffected by co-application of propylene glycol with terpene enhancers, this study offers no evidence to support the theory that propylene glycol synergy with the terpenes occurs through enhanced lipid disruption.

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