Solvent effects on the spectroscopic properties of lumichromes and lumiflavins are presented. Fluorescence yields for lumiflavins are an order of magnitude larger than those for lumichromes, due to their lower nonradiative rate constants. Solvent effects on the absorption and emission band positions are explained on the basis of hydrogen-bonding interactions. TD-DFT calculations predicted that the lowest energy states are n,π* in the case of lumichromes, but π,π* in the case of the lumiflavins. The overall consistency of the predicted singlet-singlet and triplet-triplet transitions obtained for the various compounds studied, and the good correspondence between the predicted and measured transitions, indicate that the techniques applied provide an accurate description of the spectral properties of lumiflavins and lumichromes. The measured singlet oxygen yields have shown the lumichromes to be efficient singlet oxygen sensitizers.
Unpolished specimens with a more developed surface have lower color stability. Specimens stored in water develop some changes in their visual appearance. The presently proposed methods are effective in evaluating the luminescence of dental materials. Luminescence needs to be tested in addition to color, as the two characteristics are uncorrelated. It is important to further improve the color and luminescence stability of dental materials.
Total luminescence spectroscopy was used to characterise and differentiate edible oils and additionally, to control one of the major problems in the oil quality--the effect of thermal and photo-oxidation. We studied several vegetable oils available on the Polish market, including soybean, rapeseed, corn, sunflower, linseed and olive oils. Total luminescence spectroscopy measurements were performed using two different sample geometries: front-face for pure oil samples and right-angle for transparent samples, diluted in n-hexane. All the samples studied as n-hexane solutions exhibit an intense peak, which appears at 320 nm in emission and 290 nm in excitation, attributed to tocopherols. Some of the oils exhibit a second long-wavelength peak, appearing at 670 nm in emission and 405 nm in excitation, belonging to pigments of the chlorophyll group. Additional bands were present in the intermediate range of excitation and emission wavelengths; however, the compounds responsible for this emission were not identified. The front-face spectra for pure oils included chlorophyll peaks for most samples, and some additional peaks in the intermediate range, while the tocopherol peaks were comparatively less intense. The results presented demonstrate the capability of the total luminescence techniques to characterise and differentiate vegetable oil products, and additionally, to characterize the effect of thermal and photo-oxidation on such products. In the photo-oxidation experiments, special attention was paid to possible involvement of singlet oxygen. Experiments were done to monitor the highly specific O2(1delta(g)) --> O2(3sigma(g)-) singlet oxygen emission at 1270 nm. Thus, total luminescence spectroscopy presents an interesting alternative to time-consuming and expensive techniques such as gas or liquid chromatography, mass spectrometry and other methods requiring wet chemistry steps.
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