A spectroscopic study of sunscreens

Abstract

Exposure to UV radiation is known to result in the development of skin cancer and the use of protectants m the form of topically applied sunscreens is becoming widespread. The compounds used within sunscreen formulations are subject to stringent tests and must be approved for use by such bodies as COLIPA (EC), or the FDA (U.S.). Despite these testing procedures the photochemical and photophysical properties of many of the active ingredients are poorly understood and not well documented. This study presents the results of detailed photophysical investigations of two sunscreen agents. Menthyl anthranilate is currently approved for use m commercially available formulations by the FDA, and N-acetyl-menthyl anthranilate has been synthesised as an analogue of N-acetyl-homomenthyl anthranilate, a compound approved for use by COLIPA until 1989. This work has highlighted some disturbing properties of these compounds. Following absorption of light both compounds fluoresce m UV-A region. Population of the triplet state also occurs to a significant extent, producing long lived species which are readily quenched by oxygen generating singlet oxygen, a potentially damaging species that has been linked to DNA damage. Furthermore, the triplet state energy of N-acetyl-menthyl anthranilate has been shown to be -315 kJmol(^-1)"', high enough to sensitise the formation of thymine dimers m the skin, another potential source of DNA damage. A thorough understanding of the behaviour of sunscreen formulations m contact with skin is vital. In vivo studies are made difficult due to restrictions in the sampling methods for currently used spectroscopic techniques such as UV and fluorescence. This work demonstrates the use of infixed spectroscopy, utilising an ATR probe and a flat ATR crystal, to analyse sunscreen formulations present on skin at normal usage levels. The technique has been used successfully to identify the individual active components within the formulations, probe the water-resistance properties and monitor changes that occur within the formulations following irradiation. A relationship between the IR absorbance values and Sun Protection Factor (SPF) values of any given formulation has been demonstrated and this has been used to test the water resistance claims of the manufacturers.