J. Soc. Cosmetic Chemists, 16, 777-782 (1965) The Reaction Ketones with of a-Hydroxymethyl Skin and Amino Acids* KARL LADEN, Ph.D.,** and R. ZIELINSKI, Ph.D. Synopsis--The reaction of dihydroxyacetone and various a-hydroxymethyl ketones with callus, amino acids, and bovine serum albumin has been investigated. The reaction of callus and amino acids with a-hydroxymethyl ketones to produce colored products appears to be a general one. In addition, there is a suggestion that the reaction is enhanced if electron with- drawing groups are attachcd to the a-hydroxymethyl ketone. The failure of various ana- lytical schemes to detect the presence of these ketones in callus suggests that although in some cases relatively intense color is produced very little material has actually reacted with the callus. INTRODUCTION Dihydroxyacetone (DHA) has been used in recent years in order to produce a simulated suntan on skin. This tanning effect has been attributed to the reaction of DHA with the amino acids in the skin and with the keratin itself (1-5). Other compounds have also been shown to be capable of producing a dark product when placed on skin or re- acted with amino acids. Goldman et al. (1) have shown that glyoxal reacts in a manner similar to DHA. Wittgenstein and Berry (2) com- pared the reactions of solutions of DHA and solutions of fructose with various amino acids. It was found that, in some cases, the fructose also gave colored products. A similar type of "browning reaction" has been observed in the reaction of amino acids with sugars (6-11). The purposes of this study were to determine if the reaction of a-hy- droxymethyl ketones with skin is a general one and also to obtain some additional information concerning the nature of the reaction. * A contribution from The Toni Company, a Division of The Gillette Company, Chicago, Ill. ** Gillette Medical Research Institute, 6221 North Capitol St., N. E., Washington, D.C. 20011. 777
778 JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS EXPERIMENTAL AND RESULTS Initial experiments involved study of the reaction of several a-hy- droxymethy] ketones with amino acids. The tests were run by placing two drops of a 1% solution of various amino acids on a piece of filter paper and, after drying, placing a drop of a 1% solution of the a-hydroxy- methyl ketone on the spot where the amino acid solution had been placed. The filter paper was allowed to dry at room temperature and the color TABLE I The Reaction of Amino Acids with a-Hydroxymethyl Ketones on Filter Paper Proline Norvaline Threonine Isoleucine a-Alanine Glycine Dihydroxyacetone 1 day 4 days no color lt. brown v. lt. lt. brown lt. brown brown brown no color dk. brown dk. dk. dk. brown brown brown brown Phenacyl alcohol 1 day no color lt. yellow 4 days no color yellow p-Bromophenacyl alcohol I day no color trace golden 4 days no color gold-ydlow no color yellow no color no color no color yellow yellow yellow no color no color no color no color gold- gold- gold- gold- yellow yellow yellow yellow Itydroxyacetone 1 day no color lt. tan no color no color no color no color 4 days no color tan tan tan tan tan Reactions performed as described in the text, using IS solutions of amino acids and 1% solutions of a-hydroxymethyl ketones. development observed. The results are presented in Table I. To show the effects of concentration of reagents similar trials were made with 10% concentrations rather than 1%. Some impressions as to the rate of reac- tion were also obtained by noting the time required for the first color to appear on the filter paper. Amino acids were selected so as to assess the role of structure of the amino acid on the reactivity. The results are presented in Table II. In a second type of experiment 5 ml. of a 1% solution of the a-hy- droxymethyl ketone in ethanol was added to 0.05 g. of each of the various amino acids, and the mixtures were allowed to stand overnight. The alcohol was evaporated on a steam bath, and the color produced was ob- served. While the end products were deeply colored, the color was not formed until the samples were heated. The results are presented in Table III.
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J. Soc. Cosmetic Chemists, 16, 777-782 (1965) The Reaction Ketones with of a-Hydroxymethyl Skin and Amino Acids* KARL LADEN, Ph.D.,** and R. ZIELINSKI, Ph.D. Synopsis--The reaction of dihydroxyacetone and various a-hydroxymethyl ketones with callus, amino acids, and bovine serum albumin has been investigated. The reaction of callus and amino acids with a-hydroxymethyl ketones to produce colored products appears to be a general one. In addition, there is a suggestion that the reaction is enhanced if electron with- drawing groups are attachcd to the a-hydroxymethyl ketone. The failure of various ana- lytical schemes to detect the presence of these ketones in callus suggests that although in some cases relatively intense color is produced very little material has actually reacted with the callus. INTRODUCTION Dihydroxyacetone (DHA) has been used in recent years in order to produce a simulated suntan on skin. This tanning effect has been attributed to the reaction of DHA with the amino acids in the skin and with the keratin itself (1-5). Other compounds have also been shown to be capable of producing a dark product when placed on skin or re- acted with amino acids. Goldman et al. (1) have shown that glyoxal reacts in a manner similar to DHA. Wittgenstein and Berry (2) com- pared the reactions of solutions of DHA and solutions of fructose with various amino acids. It was found that, in some cases, the fructose also gave colored products. A similar type of "browning reaction" has been observed in the reaction of amino acids with sugars (6-11). The purposes of this study were to determine if the reaction of a-hy- droxymethyl ketones with skin is a general one and also to obtain some additional information concerning the nature of the reaction. * A contribution from The Toni Company, a Division of The Gillette Company, Chicago, Ill. ** Gillette Medical Research Institute, 6221 North Capitol St., N. E., Washington, D.C. 20011. 777
778 JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS EXPERIMENTAL AND RESULTS Initial experiments involved study of the reaction of several a-hy- droxymethy] ketones with amino acids. The tests were run by placing two drops of a 1% solution of various amino acids on a piece of filter paper and, after drying, placing a drop of a 1% solution of the a-hydroxy- methyl ketone on the spot where the amino acid solution had been placed. The filter paper was allowed to dry at room temperature and the color TABLE I The Reaction of Amino Acids with a-Hydroxymethyl Ketones on Filter Paper Proline Norvaline Threonine Isoleucine a-Alanine Glycine Dihydroxyacetone 1 day 4 days no color lt. brown v. lt. lt. brown lt. brown brown brown no color dk. brown dk. dk. dk. brown brown brown brown Phenacyl alcohol 1 day no color lt. yellow 4 days no color yellow p-Bromophenacyl alcohol I day no color trace golden 4 days no color gold-ydlow no color yellow no color no color no color yellow yellow yellow no color no color no color no color gold- gold- gold- gold- yellow yellow yellow yellow Itydroxyacetone 1 day no color lt. tan no color no color no color no color 4 days no color tan tan tan tan tan Reactions performed as described in the text, using IS solutions of amino acids and 1% solutions of a-hydroxymethyl ketones. development observed. The results are presented in Table I. To show the effects of concentration of reagents similar trials were made with 10% concentrations rather than 1%. Some impressions as to the rate of reac- tion were also obtained by noting the time required for the first color to appear on the filter paper. Amino acids were selected so as to assess the role of structure of the amino acid on the reactivity. The results are presented in Table II. In a second type of experiment 5 ml. of a 1% solution of the a-hy- droxymethyl ketone in ethanol was added to 0.05 g. of each of the various amino acids, and the mixtures were allowed to stand overnight. The alcohol was evaporated on a steam bath, and the color produced was ob- served. While the end products were deeply colored, the color was not formed until the samples were heated. The results are presented in Table III.

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