Polyurethane (PUR) nanofabrics based on nanofibers of average diameters in the range of 250-110 nm with different meso-tetraphenylporphyrin (TPP) loading (0.01-5 wt %) were prepared by an electrospinning process. The oxygen quenching of excited states and singlet oxygen-sensitized delayed fluorescence (SODF) of TPP were studied at different oxygen pressures. We found that TPP in PUR matrix is present in monomeric state, and it is easily accessed by oxygen. Analysis of the kinetics of the TPP triplet, singlet oxygen, and SODF indicates that repopulation of TPP fluorescent state includes reaction of singlet oxygen with TPP triplets. The integrated SODF achieved more than 20% of the prompt fluorescence for nanofabric loaded with 5 wt % TPP. The dependence of SODF intensity on the TPP concentration in nanofibers is nearly quadratic.
Low pressure pyrolysis at 600 K of bis(fluoroformyl) peroxide, FC(O)OOC(O)F, yields the fluorocarboxyl radical, FCO2, in a concentration high enough to allow its detection by millimeter wave and infrared spectroscopy. The radical was first identified from its high resolution infrared spectrum obtained using a Fourier transform infrared interferometer. Observation and identification of its millimeter wave (MMW) spectrum were made possible by reliable ab initio calculations at the level of open-shell coupled cluster theory using large basis sets. The excellent agreement between the experimental and theoretical results confirms the structure of the FCO2 radical and the efficiency of the synthesis. The analysis of the MMW spectrum has given a set of ground state parameters including rotational, quartic centrifugal distortion, fine and hyperfine constants.
More than 160 new hyperfine components of rotational transitions of the free fluoroformyloxyl radical FCO(2) have been measured using the Prague millimeter wave high resolution spectrometer. The frequencies of these transitions together with the previously measured data were analyzed in detail and precise values of magnetic hyperfine and fine parameters were obtained. These new parameters significantly improve the values of previously determined hyperfine parameters which were rather unreliable. The new fine and hyperfine parameters obtained in this study are compatible with those of the simultaneously electron paramagnetic resonance study. Besides that, significantly improved ground state rotational and centrifugal distortion constants of the fluoroformyloxyl radical were derived.
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