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21.
O. B. Ryabova E. Yu. Khmel’nitskaya V. A. Makarov L. M. Alekseeva N. B. Grigor’ev V. G. Granik 《Russian Chemical Bulletin》2005,54(12):2873-2879
On heating at pH 6.86, 4-(N,N-dialkylthiocarbamoylthio)-5-nitropyrimidines are transformed into dithiolopyrimidines, which are either oxidized to bis(4-dialkylthiocarbamoylpyrimidin-5-yl)
disulfides or converted into 4,6-diamino-5-nitropyrimidine derivatives with carbon disulfide elimination. The direction of
the reaction is determined by the nature of a substituent in position 2 of pyrimidine and the bulk of the thiocarbamate substituent.
Mechanistic schemes for these processes were proposed.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2777–2783, December, 2005. 相似文献
22.
Multiphoton IR dissociation of SF6 (in a mixture with CH4) under nonequilibrium conditions of a compression shock formed by an intense, gas dynamically cooled, pulsed molecular beam impacting a solid surface was studied using the HF* luminescence detection ( 2.5 m) technique. The dependences of the HF* luminescence intensity on the distance x between the region in which molecules were excited and the surface and on the laser radiation frequency at different values of x were obtained. It was shown that, as the distance x decreased from 4 to 1.5 mm, the HF* luminescence intensity increased by more than an order of magnitude as compared to the case of excitation of molecules in an undisturbed flow, whereas the frequency dependences of luminescence intensity (SF6 dissociation yield) were broadened only insignificantly. 相似文献
23.
Single-molecule experiments in which proteins are unfolded by applying mechanical stretching forces generally force unfolding to proceed along a reaction coordinate that is different from that in chemical or thermal denaturation. Here we simulate the mechanical unfolding and refolding of a minimalist off-lattice model of the protein ubiquitin to explore in detail the slice of the multidimensional free-energy landscape that is accessible via mechanical pulling experiments. We find that while the free-energy profile along typical "chemical" reaction coordinates may exhibit two minima, corresponding to the native and denatured states, the free energy G(z) is typically a monotonic function of the mechanical coordinate z equal to the protein extension. Application of a stretching force along z tilts the free-energy landscape resulting in a bistable (or multistable) free energy G(z)-fz probed in mechanical unfolding experiments. We construct a two-dimensional free-energy surface as a function of both chemical and mechanical reaction coordinates and examine the coupling between the two. We further study the refolding trajectories after the protein has been prestretched by a large force, as well as the mechanical unfolding trajectories in the presence of a large stretching force. We demonstrate that the stretching forces required to destabilize the native state thermodynamically are larger than those expected on the basis of previous experimental estimates of G(z). This finding is consistent with the recent experimental studies, indicating that proteins may refold even in the presence of a substantial stretching force. Finally, we show that for certain temperatures the free energy of a polyprotein chain consisting of multiple domains is a linear function of the chain extension. We propose that the recently observed "slow phase" in the refolding of proteins under mechanical tension may be viewed as downhill diffusion in such a linear potential. 相似文献
24.
Yu. A. Simonov É. V. Ganin V. E. Zavodnik V. F. Makarov 《Chemistry of Heterocyclic Compounds》1987,23(10):1056-1059
It was demonstrated by x-ray diffraction investigation of the product of the reaction of 1,2-diaminoethane with phthalic acid dichloride that the resulting compound has the 1,2-diisophthalimidoethane structure. An improved method for its synthesis is proposed.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1320–1323, October, 1987. 相似文献
25.
V. I. Makarov G. I. Skubnevskaya N. M. Bazhin 《Reaction Kinetics and Catalysis Letters》1978,9(2):217-220
The spectrum of an intermediate, ascribed to nitrosopentane, has been detected in the photolysis of SO2-pentane-NO mixtures. This may be explained by a radical photolysis mechanism involving an initial H-atom abstraction from the pentane molecule by SO2.
SO2--NO , . , H .相似文献
26.
F. A. Shmidt N. M. Ryntina V. V. Saraev V. A. Gruznykh V. A. Makarov 《Reaction Kinetics and Catalysis Letters》1976,5(2):101-106
The reaction of tributylphosphine with the catalytic system (C5H5)2 TiCl2–LiC4H9 prepared in an atmosphere of H2 has been investigated in toluene solution. By using the ESR technique, a hydride complex Cp2Ti(H) (PBu3) has been detected. The proportionality between the rate of cyclohexene hydrogenation and the complex concentration has been established. The kinetics of cyclohexene hydrogenation has been investigated and a reaction mechanism is proposed.
Cp2TiCl2–LiC4H9 (Cp–C5H5), H2, Cp2Ti(H) (PBu3). Ti (III). .相似文献
27.
Interactions of zero radius with an additional inner channel are considered. The corresponding generalized Krein resolvents in a functional sector are approximated in the weak sense with the aid of interactions of rank 1. The cut-off procedure of the interaction is explicitly described in prepresentation.Translated from Zapiski Nauchnykh Seminarov Leningradskogo Otdeleniya Matematicheskogo Instituta im. V. A. Steklova Akademii Nauk SSSR, Vol. 182, pp. 113–122, 1990. 相似文献
28.
V. I. Makarov N. L. Lavrik G. I. Skubnevskaya N. M. Bazhin 《Reaction Kinetics and Catalysis Letters》1979,12(3):225-227
Sulfur dioxide fluorescence and phosphorescence are quenched by a magnetic field. A model is suggested for the qualitative interpretation of the results.
. , - .相似文献
29.
A. A. Makarov 《Applied physics. B, Lasers and optics》1982,29(4):287-290
For the detection of the rare radioactive isotope41Ca, the possibilities of the earlier-proposed initial-state enrichment by continuous-wave laser radiation are examined. It is shown that the enrichment 1014 of 3d-states of the ion Ca II can be reached. As the method of enriched-state detection, the process of resonant charge exchange is analysed. For a further increase of the selectivity, the repetition of the cycle initial state enrichment plus resonant charge exchange is discussed. 相似文献
30.
AbstractThe reaction between glutathionylcobalamin (GSCbl), a complex of Co(III)-cobalamin with glutathione, and selenocysteine (Sec) was investigated using ultraviolet-visible (UV–vis) spectroscopy. The interaction results in the formation of cob(II)alamin and proceeds via two pathways: (i) a rapid formation of complex between GSCbl and Sec followed by the rate-determining substitution of glutathionyl-ligand by Sec and rapid electron-transfer from Se-atom to Co(III)-ion and (ii) a nucleophilic attack of Co(III)-S bond by Sec. 相似文献