We report on the optical characterization and measurement of oxygen singlet quantum yield of Chlorophyll and Chlorin e6 in water-ethanol mixtures by direct observation of thermal relaxation using time resolved thermal lens method. The analysis of the time-resolved curve allows the determination of the quantum yield of singlet oxygen formation. The quantum yield is deduced from the relative magnitudes of the fast and slow components.
Recently new photosensitizers, chlorophyll "a and b" derivatives, for photodynamic therapy (PDT) have been presented. It already passed complete pre-clinical investigations. This prompted us to carry out an extensive study of photophysical properties of chlorine derivatives, important both for optimization of their clinic applications and for study of mechanisms of chlorine PDT&. The fresh leaves of Bauhinia megalandra (Caesalpinaceae) were extracted with methanol by percolation, and re-extract with a mixture of methanol-water (1:1), the insoluble fraction was then separated by column chromatography [RP18/hexane-ethylacetate (9:1)] to obtain four fractions named 1 to 4. These compounds were identified by NMR data. We found that 3 and 4 efficiently generates singlet oxygen when irradiated with visible light. Detection of the singlet oxygen was fulfilled by its reaction with histidine and detected by bleaching p-nitrosodimethylaniline under 440 nm irradiation. The quantum yields of singlet oxygen determined by us were 0.088 (1), 0.151 (2), 0.219 (3) and 0.301 (4). We measured absorption and fluorescence spectra of compounds 1 to 4 (Mg-chlorophyll-a, Pheophytin, Mg-chlorophyll-b and chlorophyll-b respectively) in different media and in aqueous solutions of human serum albumin. The association constant of the compounds 1, 2, 3 and 4 in the presence of HSA were estimated. The binding and quenching studies suggest that only 1 and 3 may serve as a useful fluorescence probe for structure/function studies of different chlorophyll binding proteins. No photoinduced binding was observed after irradiation by all the studied compounds in presence of human serum albumin.
We report on a new source of coherent red-light with perspective applications in laser photodynamic therapy. The red light is generated through stimulated Raman scattering (SRS) process by acetone of a frequency-doubled Nd:YAG nanosecond laser radiation (532 nm). The Stokes transition is found at 630 nm and with spectral line narrowing similar to the pump one. When pumping using the radiation from a Rhodamine-6G Dye laser (560 - 575 nm), tuning between 640 and 670 nm is demonstrated. Conversion efficiencies up to 50% are reported.
A comparative study of the second harmonic generation at the M(H2,Ni(II),V=O)-porphyrin/glass interface in a total reflection geometry is presented. The state of polarization of the incident pulses was changed by a computer controlled rotation of a quarter wave plate. The rotation patterns obtained from the experimental data were fit to a Fourier series based upon theoretical Fourier coefficients. Complex valued components of the superficial susceptibility tensor are showed. From these values, average tilt angles concentration dependent were obtained. A different behavior for each Metalloporphyrin was observed.
Resonant molecular optical second harmonic generation (SHG) has been obtained from [2, 3, 7, 8, 12, 13, 17, 18- Octaethyl-porphinato] vanadyl, (OEP)V=O, adsorbed on the hypotenuse face of a glass prism. Rotational intensity patterns are showed by plotting the second harmonic intensity as a function of the incident polarization angle of the fundamental wave, at a fixed angle of incidence. Evaluation of these patterns by Fourier analysis allowed the determination of the second order susceptibilities components of the adsorbed layers. Assuming a delta distribution function, the mean orientation angles from normal to the surface plane, were obtained for different solution concentrations. Our results indicate an abrupt change in the angle for two concentration ranges.
Resonant molecular optical second harmonic generation (SHG) was obtained from(2, 3, 7, 8, 12, 13, 17, 18-Octaethyl- porphinato)M, with M equals none, vanadyl and Ni(II), adsorbed onto fused silica substrates. The polarization dependence of the SHG signals at 1064 nm allowed the determination of average molecular orientations. For the vanadium porphyrin the average angle between the long axis molecules and the surface normal was 38 degrees, while, for the Nickel porphyrin, and the non-metal porphyrin the angle was close to 0 degrees. These results can be understood in terms of the different symmetries of the molecules.
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