Synergistic effects of binary oil mixtures on the solubility of sunscreen UV absorbers.

Sunscreens for the photoprotection of human skin often are prepared as emulsions, containing organic UV-absorber molecules dissolved in the oil phase. The solubility of such oil-soluble UV-absorbers can be a limiting factor when aiming for high protection against UV-radiation. Possible synergistic effects of combinations of oil components toward UV-absorber solubility are therefore of great interest. Since a multitude of different combinations of oil components are possible, it would be desirable to predict synergistic effects by computational methods. As a model system, the solubility of a hydroxyphenyl triazine type UV-absorber was studied in several binary oil mixtures, experimentally and also by using a computational procedure based on density functional theory (DFT) and the continuum solvation model COSMO-RS. We have found good agreement of experimental and computational results. Computational methods may thus be employed to predict synergistic behaviour of solubility for systems containing two or more solvents.

Analysis of photokinetics of 2'-ethylhexyl-4-methoxycinnamate in sunscreens.

2'-Ethylhexyl-4-Methoxycinnamate (EHMC), also designated as octinoxate, is an oily UV-absorber used in sunscreens for the protection of human skin against solar UV-radiation and represents one of the most employed UVB absorbers for that application. In water-in-oil emulsions EHMC was adjusted at a constant overall concentration, while changing the EHMC concentration in the oil droplets by adding a non-absorbing oil. In that way the EHMC concentration could be varied at constant optical thickness. Here we show that the kinetics of the photoreaction follows a second-order rate law, in line with the UV-induced [2 + 2]-cycloaddition reaction mechanism known for this UV absorber. The second-order rate constant decreased with higher overall EHMC concentration. This can be explained by the fact, that at higher overall concentration of the UV absorber not every EHMC molecule will absorb a photon due to the increased optical density, so that on average less photons are absorbed per molecule. On the other hand, the rate constant increases with decreasing polarity of the surrounding oil. Since the molar fraction of the trans-isomer of EHMC is augmented at lower polarity, more photons are absorbed in this case, as the strength of the absorption band of the trans-isomer is significantly higher than that of the cis-isomer. In conclusion, our experiments show that a high polarity of the oil phase and a high concentration of EHMC are advantageous for the photostability of this compound.

Photostability of UV absorber systems in sunscreens.

Sunscreens are used to protect the human skin against harmful UV radiation. Today there is a trend toward higher sun protection factors (SPF) and better UVA protection. Methods for the assessment of SPF and UVA protection involve irradiation of the product, and the photostability properties of the sunscreen have an influence on its performance. Sunscreens often contain more than one UV filter. Thus it is important to understand the photostability properties of the complete system. The filter combinations used may exhibit destabilizing, stabilizing or inert interactions. For that reason, besides assessment of the properties of the single filters, photostabilities of binary filter combinations are investigated. Destabilization occurs when two UV absorbers undergo a chemical reaction after absorption of UV radiation. Stabilization may be achieved when the optical density of the system is very high, giving rise to a self-protection effect of the sunscreen film. Photounstable UV absorbers may be additionally stabilized by employing triplet quenchers. Being aware of these mechanisms and applying them for specific UV filter combinations can help in designing efficient sunscreens.

Physical properties of organic particulate UV absorbers used in sunscreens II. UV-attenuating efficiency as function of particle size.

In this study the UV-attenuating properties of microparticles consisting of a benzotriazole derivative were investigated, which are used as absorbers for UV radiation in cosmetic sunscreens. The particles were micronized in presence of a dispersing agent by means of a ball milling process. According to the energy input different particle sizes were produced in the range of 0.16 to 4 microm. In order to study even smaller particles, the sample with particle size 0.16 microm was fractionated further by centrifugation. Particle sizes were measured using fiberoptic quasi-elastic light scattering (FOQELS) and laser diffractometry. The UV-attenuating properties of the dispersions with different particle sizes were assessed using UV spectroscopy. With decreasing particle size the efficiency of the UV extinction of the dispersion increases up to a particle size of 80 nm. For particles smaller than 80 nm the UV extinction decreases again indicating an optimum at 80 nm. From reflection spectroscopic measurements it was found that scattering makes about 10%, and absorption 90%, of the UV-attenuating effect of the particles, which are obtained at the end of the milling process.

Prediction of sun protection factors and UVA parameters of sunscreens by using a calibrated step film model.

At the stage of screening of new sun protection formulations, quick and inexpensive methods for estimation of the ultraviolet (UV) screening performance are highly desirable. It has been shown recently that apart from measurements of sun protection factors in vitro, calculations using a calibrated step film model are also a possibility. In the present investigation, further evidence for the usefulness of the step film model in terms of prediction of the sun protection factor is shown. In addition, it is demonstrated that parameters, which characterize the protection in the UVA range such as the UVA/UVB ratio and the critical wavelength can be calculated in good accordance with experimental data. Although with less accuracy, the estimation of UVA protection factors is also possible, if the photodegradation some filters undergo upon irradiation is taken into consideration.

Physical properties of organic particulate UV-absorbers used in sunscreens. I. Determination of particle size with fiber-optic quasi-elastic light scattering (FOQELS), disc centrifugation, and laser diffractometry.

In this study microparticles consisting of a benzotriazole derivative, which are used as absorbers for UV radiation in cosmetic sunscreens, were investigated. The particles were micronized in presence of a dispersing agent by means of a ball milling process. According to the energy input different particle sizes were produced in the range of 0.16 to 4 microm. The particle sizes obtained after different stages of the micronization process were measured using fiber-optic quasi-elastic light scattering (FOQELS), disc centrifugation, and laser diffractometry. All methods showed satisfactory agreement over the whole range of sizes. With the FOQELS technique the particle size distribution could be resolved to sizes well below 0.1 microm.