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Valentin A. Semenov Dmitry O. Samultsev Leonid B. Krivdin 《Magnetic resonance in chemistry : MRC》2020,58(6):532-539
The density functional theory calculation of 1H and 13C NMR chemical shifts in a series of ten 10 classically known Strychnos alkaloids with a strychnine skeleton was performed at the PBE0/pcSseg-2//pcseg-2 level. It was found that calculated 1H and 13C NMR chemical shifts provided a markedly good correlation with experiment characterized by a mean absolute error of 0.08 ppm in the range of 7 ppm for protons and 1.67 ppm in the range of 150 ppm for carbons, so that a mean absolute percentage error was as small as ~1% in both cases. 相似文献
4.
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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An analysis of events in the tunneling junction shows that the interaction of one-electron processes in a many-electron system may be a source of scale-invariant low-frequency fluctuations of conductivity (the interaction consists in that the quantum probability of an electron transition depends on fast random changes in the environment in the course of the transition, including the changes caused by analogous transitions). The theory relates flicker fluctuations in the tunneling conductivity to the discrete character of the spectrum of electron states and explains the nonlinearity of the noise-current characteristic observed in nanocomposites. 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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O. I. Kotov L. B. Liokumovich S. I. Markov A. V. Medvedev A. V. Khlybov 《Technical Physics》2004,49(1):71-75
Mechanisms of polarization modulation in a single-mode fiber that modulate the phase difference between polarization modes without affecting their amplitudes are considered. A coefficient that characterizes the efficiency of cylindrical piezoceramic modulators and is independent of their resonant properties is introduced. Analytical expressions for this coefficient for different modulation mechanisms are derived. The lateral pressure on the fiber is shown to provide the highest efficiency. For isotropic fibers, a modulator with a squeezing covering, which increases significantly its efficiency, is studied. For anisotropic fibers, the most appropriate way of phase difference modulation is longitudinal extension, in which case the birefringence axes do not have to be matched. In most cases, the measured and predicted efficiencies are in good correspondence. 相似文献
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The theory of dielectric space-charge polarization losses describes well both the model of an inhomogeneous dielectric [1]
and the polarization resulting from mosaic blocks of alkali-halide crystals [2]. The Debye frequency dependences ε*(ω) and
tan δ(ω) with non-Arrhenius relaxation time are calculated in the first approximation of perturbation theory [3, 4] with the
use of a nonlinear system of the Fokker-Planck and Poisson equations for the interlayer polarization with allowance for tunnel
transitions of relaxation oscillators. For the Maxwell mechanism of space-charge relaxation, tan δ(ω) also has the Debye form
[5]. It should be noted that in studies cited above the electric field was considered uniform, and the nonlinearity of the
initial system of equations was not investigated. This paper removes these restrictions and elaborates a theory of relaxation
mechanism.
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Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 11, pp. 28–34, November, 2006. 相似文献
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