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61.
The Yule–Simon distribution is usually employed in the analysis of frequency data. As the Bayesian literature, so far, has ignored this distribution, here we show the derivation of two objective priors for the parameter of the Yule–Simon distribution. In particular, we discuss the Jeffreys prior and a loss-based prior, which has recently appeared in the literature. We illustrate the performance of the derived priors through a simulation study and the analysis of real datasets. 相似文献
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The interaction of 8-methoxypsoralen (8-MOP) with synthetic eumelanin was investigated using static and time-resolved fluoresence and pulsed photoacoustic calorimetry. Spectroscopic data indicate the absence of interaction in the ground state, whereas the singlet excited state of 8-MOP is quenched by the pigment; the average fluorescence lifetimes are independent of the melanin concentration, thus indicating a static mechanism. Photoacoustic data show that the quenching process involves an increased intersystem crossing probability, which is almost unaffected by the presence of oxygen, as expected for a molecule essentially acting as a type I photosensitizing agent. 相似文献
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Abbruzzetti S Grandi E Viappiani C Bologna S Campanini B Raboni S Bettati S Mozzarelli A 《Journal of the American Chemical Society》2005,127(2):626-635
We have used a nanosecond pH-jump technique, coupled with simultaneous transient absorption and fluorescence emission detection, to characterize the dynamics of the acid-induced spectral changes in the GFPmut2 chromophore. Disappearance of the absorbance at 488 nm and the green fluorescence emission occurs with a thermally activated, double exponential relaxation. To understand the source of the two transients we have introduced mutations in amino acid residues that interact with the chromophore (H148G, T203V, and E222Q). Results indicate that the faster transient is associated with proton binding from the solution, while the second process, smaller in amplitude, is attributed to structural rearrangement of the amino acids surrounding the chromophore. The protonation rate shows a 3-fold increase for the H148G mutant, demonstrating that His148 plays a key role in protecting the chromophore from the solvent. The deprotonation rate for T203V is an order of magnitude smaller, showing that the hydrogen bond with the hydroxyl of Thr203 is important in stabilizing the deprotonated form of the chromophore. A kinetic model suggests that, in addition to protecting the chromophore from the solvent, His148 may act as the primary acceptor for the protons on the way to the chromophore. 相似文献
66.
Gómez-Zavaglia A Reva ID Frija L Cristiano ML Fausto R 《The journal of physical chemistry. A》2005,109(35):7967-7976
In this work, the molecular structure, infrared spectrum and UV photochemistry of 2-methyl-2H-tetrazol-5-amine (2MTA) isolated in solid argon (10 K) were investigated. The experimental studies were supported by extensive DFT(B3LYP)/6-311++G(d,p) calculations. The infrared spectrum of matrix-isolated 2MTA was fully assigned and correlated with structural properties. Taking into consideration the observed frequency of the NH2 wagging mode, it is suggested that, in the matrixes, the amine group becomes slightly more planar than in the gas phase, due to matrix-packing effects. In situ UV irradiation (lambda > 235 nm) of the matrix-isolated 2MTA monomer is shown to induce three main primary photochemical processes: (1) tautomerization to mesoionic 3-methyl-1H-tetrazol-3-ium-5-aminide; (2) nitrogen elimination, with production of 1-methyl-1H-diazirene-3-amine; (3) ring cleavage leading to production of methyl azide and cyanamide. Following the primary photoproducts, secondary reactions were observed, leading to spectroscopic observation of methylenimine and isocyanidric acid. 相似文献
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Summary: Dynamic light scattering (DLS) and fluorescence experiments were carried out to study PCL44-b-PEO114 biocompatible micelles used as nanocarriers in drug delivery. Micelles prepared by a simple procedure (THF removal under nitrogen flow) exhibited a narrow size distribution with an average diameter of 100 nm. For micelles containing a hydrophobic model compound (pyrene) within the PCL core, a smaller average micellar size of 80 nm was observed, with a simultaneous broadening in the size distribution profile. In parallel to DLS results, fluorescence experiments showed evidence of pyrene encapsulation, and that the onset of the micellization process occurs at approximately 10/90 (v/v) THF/water mixtures in the case of PCL44-b-PEO114 polymer. 相似文献
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Cristiano Raminelli 《Tetrahedron》2005,61(2):409-415
tert-Butyldimethylsilyl ethers of propargylic alcohols are hydrotellurated regioselectively to give 1,2-Z-vinylic tellurides. Enantiomerically pure propargylic alcohols give enantiomerically pure vinylic tellurides, which are coupled with alkynes under Pd catalysis to give enantiomerically pure allylic enynols. 相似文献
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