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Hypericin (Hyp) is a natural compound with interesting photophysical and pharmacological properties, which has been used in photodynamic therapy and photodynamic inactivation of microorganisms. Its synthesis is based on a series of chemical processes that ends with a light-drug interaction by the photoconversion of protohypericin (pHyp) to Hyp. Although this photosensitizer is used in a variety of medical applications, the photophysical and photochemical mechanisms involved in the final step related to the photo production of Hyp are not completely understood at the molecular level. Protohypericin concentration, solvents, light irradiation under different wavelengths, and a sort of variables could play an important role in predicting the yielding of this photoconversion process. Here, we used the high-sensitive and remote measurement characteristics of the time-resolved thermal lens technique to investigate the relation between the light-induced photoconversion rate of pHyp to Hyp and the initial concentration pHyp. The results show a linear dependence of the photoreaction rate with the concentration of pHyp, indicating that the overall reaction process includes steps comprising the formation of distinct intermediate species. We demonstrate the applicability of the thermal lens technique for the photochemical characterization of photosensitive drugs at low concentration levels.

Recent improvements in the modeling of photo-induced thermo-optical-mechanical effects have broadened the application of photothermal techniques to a large class of solids and fluids. During laser excitation, changes in optical reflectivity due to temperature variation may affect the photothermal signal. In this study, the influence of the reflectivity change due to heating is analyzed for two pump-probe photothermal techniques, thermal lens and thermal mirror. A linear equation for the temperature dependence of the reflectivity is derived, and the solution is tested using optical properties of semi-transparent and opaque materials. For semi-transparent materials, the influence of the reflectivity change in photothermal signals is less than 0.01%, while for opaque materials it is lower than 3%.

A theoretical model for a time-resolved photothermal mirror technique using pulsed-laser excitation was developed for low absorption samples. Analytical solutions to the temperature and thermoelastic deformation equations are found for three characteristic pulse profiles and are compared to finite element analysis methods results for finite samples. An analytical expression for the intensity of the center of a continuous probe laser at the detector plane is derived using the Fresnel diffraction theory, which allows modeling of experimental results. Experiments are performed in optical glasses, and the models are fitted to the data. The parameters of the fit are in good agreement with previous literature data for absorption, thermal diffusion, and thermal expansion of the materials tested. The combined modeling and experimental techniques are shown to be useful for quantitative determination of the physical properties of low absorption homogeneous linear elastic material samples.

A theoretical and experimental study taking sample-fluid heat coupling into account in time-resolved photothermal mirror experiments is presented. Thermoelastic equations were solved to obtain a semi-analytical solution to the phase shift induced by the sample and the surrounding fluid. The solution was used to model the thermal mirror effects and found to be in excellent agreement with the finite element method analysis and experiment. Heat transferred to the air-coupling fluid did not introduce important effects in the phase shift when compared with the solution obtained, without considering heat flux. However, when using water as the fluid, heat coupling led to a significant effect in fluid phase shift. Experimental results using stainless steel in air and water were used to demonstrate the potentiality of the thermal mirror technique to determine the thermal properties of both the sample and the fluid.