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41.
The fine structure of experimental πl,π*-absorption bands of the α hydroxyanthraquinones originates from the prototropic anthraquinoid tautomerism. The tautomeric transformations occur both in the ground and excited states of the molecules; therewith the excited states are more sensitive to the tautomerization than the ground ones. The wavelength and intensity of the πl,π*-bands, the values of all quantum-chemical characteristics studied for the tautomers of α hydroxyanthraquinones are linearly related to the number of hydroxy groups. The effect of the isomerism of di- and trihydroxyanthraquinones on this relationship was considered.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 5, 2005, pp. 722–729.Original Russian Text Copyright © 2005 by Fain, Zaitsev, Ryabov. 相似文献
42.
Varnavski OP Ostrowski JC Sukhomlinova L Twieg RJ Bazan GC Goodson T 《Journal of the American Chemical Society》2002,124(8):1736-1743
Measurements of ultrafast fluorescence anisotropy decay in model branched dendritic molecules of different symmetry are reported. These molecules contain the fundamental branching center units of larger dendrimer macromolecules with either three (C(3))- or four (T(d), tetrahedral)-fold symmetry. The anisotropy for a tetrahedral system is found to decay on a subpicosecond time scale (880 fs). This decay can be qualitatively explained by F?rster-type incoherent energy migration between chromophores. Alternatively, for a nitrogen-centered trimer system, the fluorescence anisotropy decay time (35 fs) is found to be much shorter than that of the tetramers, and the decay cannot be attributed to an incoherent hopping mechanism. In this case, a coherent interchromophore energy transport mechanism should be considered. The mechanism of the ultrafast energy migration process in the branched systems is interpreted by use of a phenomenological quantum mechanical model, which examines the two extreme cases of incoherent and coherent interactions. 相似文献
43.
Oleg V. Mikhailov Marina A. Kazymova Tatyana A. Shumilova Galina A. Chmutova Svetlana E. Solovieva 《Transition Metal Chemistry》2005,30(3):299-304
The complexing process proceeding in the NiII–thiocarbohydrazide (H2N–H–NC(=S)–NH–NH2)–propanone triple system in EtOH solution and nickel(II)hexacyanoferrate(II) gelatin-immobilized matrix has been studied. It has been found that in the first case, template synthesis leading, as a minimum, to formation of three coordination compounds of NiII with (N,N,S,S)-donor tetradentate ligands having NiL1, NiL2 and NiL3compositions where L1 is 4,6,6-trimethyl-2,3,7,8-tetraazanonen-3-di(thiohydrazide)-1,9, L2 is 4,6,6,12-tetrametyl-1,9-dithio-2,3,7,8,10,11-hexaazatridekadien-3,11-hydrazide-1 and L3 is 2,8,10,10,16-pentamethyl-5,13-dithio-3,4,6,7,11,12,14,15-octaazaheptadekatrien-2,7,15 is observed, whereas in the gelatin-immobilized matrix, a complexing process in the system considered does not occur. 相似文献
44.
1-Hydrazino-2-propanol reacts with aliphatic carbonyl compounds to form the corresponding (2-hydroxypropyl)hydrazones. 1-(N-Alkylhydrazino)-2-propanols, on the other hand, give tautomeric mixtures of alkyl-substituted perhydro-1,3,4-oxadiazines and N-alkyl-N-(2-hydroxypropyl)hydrazones. As compared with derivatives of 2-(N-alkylhydrazino)ethanols, the position of the equilibrium in the investigated cases is shifted to favor the cyclic forms.See [1] for communication I.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 301–308, March, 1971. 相似文献
45.
V. V. Davydov B. E. Zaitsev M. G. Sarabia A. É. Aliev G. V. Sheban V. L. Savel'ev V. S. Troitskaya 《Chemistry of Heterocyclic Compounds》1990,26(11):1258-1264
The structure of the previously synthesized 1,2-dihydro-3-(2-hydroxyphenyl)-4-nitropyrazol-5(3H)-one (I) was studied by 1H and 13C NMR, IR, and electronic spectra. It was established that the NMR spectra of compound (I) do not contain signals for the H atom at position 4 and the C atoms of the carbonyl groups; in the crystalline state and in solutions the IR spectra do not contain vc=o bands, while the electronic spectra do not contain absorption in the region of 250 nm. On the basis of the foregoing it is concluded that compound (I) exists in the OH form. The distribution of -electron density in the molecule of (I) and the nature of the bands in its electronic absorption spectrum were studied by quantum-chemical methods in the PPP approximation.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1510–1516, November, 1990. 相似文献
46.
F. I. Zubkov V. P. Zaitsev A. A. Orlova A. S. Peregudov N. M. Mikhailova A. V. Varlamov 《Russian Journal of Organic Chemistry》2007,43(8):1202-1208
Dimethyl acetylenedicarboxylate reacts with 4-substituted and 3,4-fused 2-furyl-1,2,3,4-tetrahydroquinoline derivatives at the furan fragment according to the [4 + 2]-cycloaddition pattern. The reaction is not stereoselective, and it yields two diastereoisomeric 7-oxabicyclo[2.2.1]hepta-2,5-dienes whose structure was determined by X-ray analysis and NMR spectroscopy. 相似文献
47.
Oleg N. Obrezkov Andrey V. Pirogov Igor V. Pletnev Oleg A. Shpigun 《Mikrochimica acta》1991,103(5-6):293-302
A new optimization criterion for chromatography is presented. It was designed to evaluate the quality of chromatograms in a way similar to human estimation. Selectivity, efficiency, and time of analysis as well as the number of peaks were taken into account. The criterion has been tested in comparison with expert estimations and some modern criteria. A better agreement of the new criterion with human estimation of chromatographic quality compared to some literature criteria is shown. A number of successful optimization runs has been performed using the criterion together with simplex optimization. 相似文献
48.
Kostko O Wrigge G Cheshnovsky O von Issendorff B 《The Journal of chemical physics》2005,123(22):221102
We present photoelectron spectroscopy studies on Zn(n) (-) in the size range of n=3-117. We show that zinc clusters exhibit a distinct transition in their electronic structure as a function of size. At small sizes (up to n=18) the clusters follow the Bloch-Wilson picture of the development of a metal from closed-shell atoms, exhibiting a gradual decrease of the gap between the fully occupied s band and the empty p band. For large sizes (n approximately or > 32) the band overlap allows the valence electrons to fully delocalize. This leads to an almost perfect free-electron density of states, as is demonstrated by discussing the spectra in the light of standard free-electron models and by comparison to the results obtained on sodium clusters. 相似文献
49.
Constant magnetic fields affect many biological transformations, but we lack mechanistic understanding of the processes. The magnetohydrodynamic effect may account for the enhancement of bioelectrocatalytic transformations at interfaces. This is exemplified by the bioelectrocatalyzed cytochrome c-mediated reduction of oxygen and oxidation of lactate in the presence of cytochrome oxidase and lactate dehydrogenase, respectively. We observe significant magnetic field effects on the rates of bioelectrochemical transformations (ca. 3-fold increase) at the functionalized interfaces at field strengths, B, up to 1 T. We show that the limiting current is proportional to the B(1/3)C*(4/3), where C is the concentration of electroactive species. The results may have important implications on the understanding of the magnetic field effects on natural biocatalytic processes at membranes and on the enhancement of biotransformations in biotechnology. 相似文献
50.
Yu. M. Evtushenko B. E. Zaitsev V. M. Ivanov K. M. Gitis 《Chemistry of Heterocyclic Compounds》2000,36(9):1054-1057
The reaction of maleic anhydride with 2-methylimidazole in acetonitrile and DMF is accompanied by the appearance of strong absorption bands in the visible part of the spectrum due to the formation of molecular complexes. In acetonitrile the reaction proceeds by two routes via the formation of an amide and the molecular complex. Phthalic anhydride reacts with 2-methylimidazole to give amide but not to form molecular complexes. 相似文献