High pressure Raman investigation on trans-urocanic acid.

Trans-urocanic acid (t-UCA) is an important epidermal UV protector predominantly found in human skin. Exposure of UV radiation triggers photoisomerization of t-UCA into its other conformer, cis-urocanic acid (cis-UCA), which has been shown to be a mediator of UV-induced immune-suppression leading to skin cancer. In this report, we present the investigation of molecular changes of t-UCA under high pressures by in-situ high pressure Raman spectroscopy. The study indicates onset of ring opening polymerization of t-UCA at pressure above 1.4 GPa. At pressures beyond 5 GPa, a well discernible characteristic vibrational mode (CC stretch) accompanied by several other spectral features such as δ CO2- and δ NH modes of cis-UCA point towards the isomerization of residual t-UCA monomers into cis-UCA. The content of cis-UCA gradually increased with increase in pressure. On release to ambient conditions, the spectrum of the quenched sample showed Raman modes of polymer and cis-UCA indicating that the changes are irreversible.