Investigation of the Formation of Squalene Oligomers Exposed to Ultraviolet Light and Changes in the Exposed Squalene as a Potential Skin Model.

UV-induced oligomerisation of squalene was undertaken to indicate the potential for squalene-containing biological systems to exhibit rheology changes. DOSY NMR enabled the determination of the molecular weight (MW) range using Stokes-Einstein Gierer-Wirtz Estimation (SEGWE Calculator, University of Manchester). This approach was validated by Atmospheric Solids Analysis Probe Time of Flight Mass Spectrometry (ASAP TOF MS). To demonstrate the principle, both benzoyl peroxide and AIBN were used, separately, to initiate rapid, radical oligomerisation. Subsequent experiments in the absence of initiators compared the influence of UV wavelength and time on the resulting oligomer formation. To further model a relevant biological implication of this potentially chaotic UV oligomerisation, both saturated and unsaturated free fatty acids were added to squalene and exposed to UV at 285 nm and 300 nm to determine if cross oligomerisation could be observed. This representation of sebum evidenced the formation of a distribution of higher MW oligomers. Internal viscosity was normalised using the DMSO solvent, but to confirm that changes in rheology did not affect diffusion, a final experiment where fresh squalene was added to our oligomer mixture, representative of sebum, showed that unchanged squalene possessed the anticipated monomeric diffusion coefficient and hence MW. This work suggests, at least qualitatively, that UV-induced squalene oligomerisation can occur over time and that this may have a role in the behaviour of squalene on the skin.

Near-infrared spectroscopy combined with chemometrics to classify cosmetic foundations from a crime scene.

Cosmetic smears are a form of trace evidence that can link the crime scene, suspects, and victims. Foundation and lipstick are the most common sources of cosmetics that can easily smear, with most current research focused on the evidential analysis of lipsticks. This research aims to create a database of cosmetic foundations on different materials and to access the robustness of using Near-infrared with chemometrics as a non-destructive technique to identify unknown samples collected from a crime scene. Small amounts of six shades of three brands of foundations were smeared on clothing materials, which were then analysed with a combination of Near-infrared with chemometric analysis. Principle component analysis (PCA) was used to reduce data dimensionality and explore potential patterns in sample separation and Linear Discriminant Analysis (LDA) was utilised to assign unknown samples to one of the established classes. The selected techniques proved to be promising for database construction and as a preliminary method of analysis, with 93% of the spectra being correctly classified. Notably, darker foundation shades were less likely to be correctly classified (90% classified correctly) compared to lighter ones (96.7% classified correctly). This could not be improved with Standard Normal Variate (SNV) data pre-treatment or selecting specific NIR regions. This finding is of particular importance; according to the Crime Survey for England and Wales (year ending March 2020) police recorded sexual offences demonstrated that those in Mixed and Black or Black British ethnic groups were significantly more likely to be a victim of sexual assault compared to White, Asian or Other ethnic groups. It is, therefore, crucial to add a wide range of foundation shades, particularly of darker tones, to the future database.