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M. Di Valentin A. Bisol G. Agostini G. Giacometti D. Carbonera 《Applied magnetic resonance》2006,30(3-4):555-576
A comparative electron paramagnetic resonance (EPR) study has been performed on a series of structurally related molecular triads which undergo photoinduced electron transfer and differ one from the other in terms of the acceptor or donor moieties. The molecular triads, C-P-C60, TTF-P-C60 and C-P-PF, share the same free-base, tetraarylporphyrin (P) as the primary electron donor, which after light excitation initiates the electron transfer process, but differ either in terms of the electron acceptor (fullerene derivative, C60, versus fluorinated free-base porphyrin, PF), or in terms of the final electron donor (carotenoid polyene, C, versus tetrathiafulvalene, TTF). All these molecular triads can be considered artificial photosynthetic reaction centers in their ability to mimic several key properties of the reaction center primary photochemistry. Photoinduced charge separation and recombination have been followed by time-resolved EPR in a glass of 2-methyltetrahydrofuran and in the nematic phase of the uniaxial liquid crystal E-7. All the triads undergo photoinduced electron transfer, with the generation of charge-separated states in both the low-dielectric environment of the 2-methyl-tetrahydrofuran glass and in anisotropic E-7 medium. Different photochemical pathways have been recognized depending on the specific donor and acceptor moieties constituting the molecular triads. In the presence of the tetrathiafulvalene electron donor singlet- and triplet-initiated electron transfer routes are concurrently active. Recombination to the low-lying carotenoid triplet state occurs in the carotene-based triads, while singlet recombination is the only active route for the TTF-P-C60 triad, where a low-lying triplet state is lacking. Long-lived charge separation has been observed in the case of TTF-P-C60: about 8 μs for the singlet-born radical pair in the glassy isotropic matrix and about 7 μs for the triplet-born radical pair in the nematic phase of E-7. For all the molecular triads, a weak exchange interaction (J?1 G) between the electrons in the final spin-correlated radical pair has been evaluated by simulation of the EPR spectra, providing evidence for superexchange electronic interactions mediated by the tetraarylporphyrin bridge. 相似文献
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Employing a cleavable carbohydrate–peptide linker, a new strategy for single-bead analysis of multivalent cyclic neoglycopeptides based on Edman degradation is described. Edman degradation of glycopeptides is hampered by the acid lability of the glycosidic bond and potential incompatibilities of phenylthiohydantoin (PTH) derivatives of glycosylated amino acids with PTH derivatives of the proteinogenic amino acids. To overcome this problem, carbohydrates are detached from the cyclopeptide templates before single-bead analysis, allowing for micro sequencing under routine conditions. With this strategy, application of multivalent cyclic neoglycopeptides in split-mix libraries with a subsequent screening process becomes possible for the first time. 相似文献
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Valentin Brimkov 《Discrete Applied Mathematics》2007,155(14):1812-1825
We consider the problem of computing the Lovász theta function for circulant graphs Cn,J of degree four with n vertices and chord length J, 2?J?n. We present an algorithm that takes O(J) operations if J is an odd number, and O(n/J) operations if J is even. On the considered class of graphs our algorithm strongly outperforms the known algorithms for theta function computation. We also provide explicit formulas for the important special cases J=2 and J=3. 相似文献
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A.D. Bykov V.N. Saveliev C. Camy-Peyret A. Valentin 《Journal of Molecular Spectroscopy》2004,224(2):164-175
Forty-seven N2 broadened water vapor line-widths have been measured in the 1845-2140 cm−1 spectral range with a Fourier Transform spectrometer in the 258-330 K temperature range at a spectral resolution of 0.005 cm−1 for the lines with upper state rotational quantum number up to 16. The measured exponents of the temperature dependence of the width exhibit a large range of values from 1.60 to −0.86. Theoretical calculations were made using a semi-empirical technique based on the Anderson theory. The calculated broadening coefficients as well as the temperature exponents for the half-width agree satisfactory with measured values. 相似文献
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Lyudmila Kondakova Victor Yanishpolskii Valentin Tertykh Tat'yana Buglova 《Analytical sciences》2007,23(1):97-101
Galactose oxidase from Fusarium graminearum IMV-1060 adsorbed on, and covalently bound to, silica carriers has been used for analytical determinations of D-galactose and galactose-containing sugars. Using a flowing oxygen electrode of the Clark-type, sensor system for enzymatic analysis of water solutions of galactose-containing carbohydrates was made. Measurements were taken both in the pulse and continuous modes of a substrate flowing through a column with an immobilized biocatalyst. The linear measurement ranges for galactose-containing carbohydrates concentrations were determined. 相似文献
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