64 JOURNAL OF COSMETIC SCIENCE oil- and water-continuous microstructure, showing affinity for both aqueous and oily substances. This bicontinuous phase was applied to the development of a novel makeup remover. Determination of remover cap-ability and fresh skin feel revealed that the makeup could be completely removed and that the amount of oil remaining on skin surface after wash­ off was much less than with previous oil-based removers. The results of the sensory test also supported the finding that the remover was far superior to conventional products. This makeup remover is the first example of the application of the bicontinuous phase technology to a cosmetic product and clearly seems to provide the best conditions for subsequent skin care, meaning that it is suitable for the first step in the skincare process. Change in Surface Chemistry of the Cuticle of Human Hair by Chemical and Photochemical Oxidation Sigrid B. Ruetsch and Yash K. Karnath TRI/Princeton, 601 Prospect Ave., Princeton, NJ 08542, USA This is a multifaceted study on the characterization and quantification of damage to the hair fiber surface caused by photochemical and cosmetic chemical oxidative processes. Unique techniques were used, including a microfluorometric method that had been adapted to characterize and quantify the delipidation and acidification of the human hair surface during light exposure and cosmetic chemical grooming processes such as bleaching. During photochemical and chemical oxidation, breakdown of the lipid domains (also called the »F-layer«) of the outer b-layer occurs on the exposed scale faces [ 1] and cysteic acid groups are generated on the cuticle cell surface. The newly formed acid functionalities can be tagged with the cationic fluorochrome Rhodamine B, allowing not only quantification of the level of progressive acidification but also localization of the newly formed acid functionalities. On the other hand, the negative charges generated on the hair surface by oxidation can also bind low molecular weight quaternary cationic conditioning compounds such as cetyltrimethylammonium bromide. This process can be considered a »relipidation by adsorption«. We have shown that the entire process of »delipidation/acid formation« and subsequent »relipidation by adsorption« on the scale faces can be quantified by X-ray photoelectron spectroscopy. Since X-ray photoelectron spectroscopy analysis is highly sensitive [2] and able to detect atomic species at the very surface of the hair fibers, receiving signals from an escape depth as shallow as 25 A, it appeared ideal for the characterization of treatment-induced changes in the hair surface. However, X-ray photoelectron spectroscopy provides an average elemental composition of the hair surface including scale faces and scale edges. The microfluorometric technique, on the other hand, can distinguish progressive delipidation of the scale faces from changes occurring at the broken scale edges. This distinction was shown and characterized in detail by slow speed microfluorometric scanning of the hair surface. Chemical and photochemical oxidative processes at the hair surface result in certain collateral effects. Particularly changes in surface wettability and fiber friction are of significance to the cosmetic chemist because they affect the spreading and wicking of products in hair as well as the managability and the »body« of hair assemblies. Methods of characterizing these effects are discussed briefly. Cutaneous Restructuration by Apple Seed Phytosterols: From DNA Chip Analysis to Morphological Alterations Thomas Doering, Olaf Holtkotter, Kordula Schlotmann, Claudia Jassoy, Dirk Petersohn, Armin Wadle, and Marianne Waldmann-Laue Henkel KGaA, Henkelstrasse 67, 40191 Diisseldorf, Germany Plant secondary metabolites such as flavonoids, isoflavones and phytosterols have been proposed as cosmetic ingredients displaying anti-aging effects. On the cellular level, however, , the activity profiles of these ingredients are only partially understood. In this study we analyzed the effects of apple seed phytosterols on age-related structural and functional parameters using cell biochemicaL molecular biological and bioengineering techniques. The expression of age-related genes was studied using skin equivalents and cDNA microarrays. Incubation of skin equivalents with apple seed phytosterols had significant consequences: (i) differential regulation of a set of genes associated with keratinocyte proliferation and differentiation, (ii) stimulation ofhyaluronic acid synthesis, and (iii) increase of epidermal thickness. In vivo studies revealed that apple seed phytosterols improve skin elasticity and decrease skin roughness. In conclusion, apple seed phytosterols display distinct biological effects and significantly improve the structure and function of mature skin. Free Internal Lipids in Hair from Pre- and Post-Menopausal Women Jennifer Wills, Susan Dolphin, Louise Albiston, Presh Parmar, Gillian E. Westgate, and Godfrey J. Harrap Unilever R&D Port Sunlight, Bebington, CH63 3JW, UK Unilever R&D Colworth, Bedford, MK 44 lLQ, UK Little is known about changes in hair lipids during life and their effects on hair properties. Our objectives were to study for the first time the effects of the female menopause on hair lipids, the contribution of sebum, and hair quality using pre­ menopausal and post-menopausal subjects with and without hormone replacement therapy. Extracted hair lipids were quantified by high performance thin layer chromatography, forehead sebum output measured by sebumeter and hair greasiness, shine, softness and smoothness evaluated by expert assessment Pre-menopausal free internal lipids contained free fatty acids, wax or cholesteryl esters, cholesterol, ceramides, triglycerides and squalene. The composition was distinct from scalp surface lipids collected at the same time and from hair follicles from facelift patients, with no wax or cholesteryl esters and squalene in follicles and no ceramides in the surface lipids. Wax or cholesteryl esters and squalene were decreased (p0.05) and cholesterol and ceramides increased (p0.05) in post-menopausal hair. The changes for squalene, wax or cholesteryl esters and cholesterol were reduced when hormone replacement therapy was taken. Sebum output and hair greasiness, shine, softness and smoothness fell significantly (p0.05) fter menopause. Hormone replacement therapy increased (p0.05) results after menopause. It is concluded that hair free internal lipids derive from both the hair follicle and sebum. Sebum output falls after menopause and contributes less to hair lipids. The hair condition also changes. Understanding hair changes during life should improve matching of hair products to consumer needs.

J. Cosmet. Sci., 56, 65-77 CTanuary/February 2005) Electron spectroscopy and microscopy applied to chemical and structural analysis of hair B. C. BEARD, A. JOHNSON, F. M. CAMBRIA, and P. N. TRINH, Akzo Nobel Surfactants America, Akzo Nobel Chemicals, 1 Livingstone Ave., Dobbs Ferry, NY 10522. Synopsis The application of surface specific x-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) will be shown to be an effective means for the elucidation of hair fiber surface chemistry and structure. Example studies of bleaching and fiber conditioning treatments are discussed. The bleached fiber surface is found to become more hydrophilic due to the loss of the naturally occurring hydrocarbon overlayer and oxidation of surface functional groups as a result of bleaching. Comparison between generic bleaching regimens illustrates the importance of increased pH and the presence of surfactant for effective treatment. Adsorption of conditioning diester quat and dimethicone molecules reintroduces a hydrophobic like surface layer on the hair fiber. Spectroscopic data indicates a segregated adsorption structure of the chemically different conditioning molecules. Electron microscope Images of the conditioned hair shows a smooth uniform surface. INTRODUCTION Human hair is a complex and variable material, composed of an inner spindle overlaid with 5-10 layers of cuticle arranged like roofing shingles. Comprised of proteins, hair contains C, 0, N and S in proportion to the amino acids present. The terminal hair surface, therefore is a mix of all the possible organic functionalities present in the amino acids, (carboxylate, sulfonate, hydroxyl, amine, disulfide, thio ether, aromatic, alkyl, etc.). Cross links at the exterior, cuticle portion of the hair fiber, are substantially more numerous than in the whole hair due to the concentration of sulfur containing cystine amino acid. Upon aging or chemical treatment of the hair, some of the disulfide cross links of cystine are oxidized, resulting in the formation of sulfonate groups at the surface (1). The carboxylate and sulfonate groups play a primary role in surface treatment interactions owing to their charge at near neutral pH. The isoelectric point for hair has been found to be around 3.7 (2). Through an oversight, this paper was omitted from "Proceedings of the First International Conference on Applied Hair Science, Princeton, New Jersey,June 9-10, 2004," sponsored by TRI/Princeton and published by the journal of Cosmetic Science in a 2004 supplement to Volume 55. As with the other papers in the supplement, this paper has been only minimally edited (for conformity to journal format) by the Society of Cosmetic Chemists. * Address all correspondence to B. C. Beard. 65