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1.
2.
The thermal and photochemical fragmentations of a few bisazoalkenes have been investigated. 2-Phenyl-4,5-disubstituted-1, 2,3-triazoles were obtained both in the thermolysis and photolysis of 1, 2-bisphenylazo-(4, 4′-dichloro) stilbene, 1, 2-bisphenylazo(4, 4′-dimethoxy)stilbene, 1, 2-bisphenylazocyclohexene and o-(phenylazo) phenyldiazocyanide. Both 2, 3-bisphenylazo-2-butene and 1, 2-bisphenylazoethylene failed to undergo either photolysis or thermolysis in the expected manner. However, 2, 3-bisphenylazo-2-butene underwent an acid-catalysed valence isomerisation to anhydro 1-phenylimino-2-phenyl-4, 5-dimethyl-1, 2, 3-trizolium hydroxide, which on photolysis gave 2-phenyl-4, 5-dimethyl-1, 2, 3-triazole. The same iminotriazolium intermediate gave a cycloadduct, 2, 6-diphenyl-3, 3a-dimethyl-4, 5-dicarbomethoxypyrazolino [2.3.c][1.2.3] triazole, on treatment with dimethyl acetylenedicarboxylate, whereas treatment with carbon disulphide gave 2-phenyl-4, 5-dimethyl-1, 2, 3-triazole. Both photolysis and thermolysis of C-biphenylene-Nα(4-chlorophenyl)-Nβ-cyanoazomethine imine gave 9-fluorenone-N- (4-chlorophenyl) anil. Photolysis of 1, 2-bisphenylazoacenaphthylene in methanol gave acenaphthenequinone monophenylhydrazone. 相似文献
3.
Santhosh P Gopalan A Vasudevan T 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2003,59(7):1427-1439
UV-visible spectroelectrochemical studies on copolymerization of diphenylamine (DPA) with ortho-methoxy aniline (OMA) were carried out for different feed ratios of DPA and OMA using indium tin oxide (ITO)-coated glass as working electrode. The UV-visible spectra show clear dependencies on the molar feed composition of DPA or OMA used in electropolymerization. Derivative cyclic voltabsorptogram (DCVA) was deduced at the wavelengths corresponding to the absorption by the intermediate species and used to confirm the intermediates generated during the electropolymerization. The composition of DPA and OMA in the copolymer for the copolymers synthesized with different molar feed ratios of DPA and OMA was determined by UV-visible spectroscopy. Reactivity ratios of DPA and OMA were deduced by using Fineman-Ross and Kelen-Tudos methods and correlated with spectroelectrochemical results. 相似文献
4.
Non-empirical SCF and CI calculations are reported for the HN2, free radical in various low-lying electronic states. The nature of the angular and N-N and N-H stretching potential curves of each of these species is investigated, including a study of the dissociative behavior of such states. The ground state is found to be only very slightly bound with respect to NH stretch, in contrast to what is observed for isoelectronic HCO, The vertical electronic spectrum of HN2, appears to be marked by a single long wavelength transition (1.95 eV) from the bent (124°) ‘A’ ground state to the linear 2Π excited species, but at least four other intra-valence and an additional n → 3s Rydberg species are indicated in the 5.5–8.0 eV absorbing region. 相似文献
5.
Cytochrome P-450 isozymes represent a critical component of nature’s spectrum of detoxification catalysts that could be exploited
for bioremediation. The ethanol-inducible human cytochrome P-450 2E1 serves as a model eukaryotic P-450 that complements the
bacterial P-450 cam in dehalogenation and detoxification of environmental pollutants. We explored the construction of novel
chimeric P-450s using cytochrome P-450 camC and 2E1 genes. For construction of chimera 1 (478 amino acids, 55.14 kDa), 145 amino acids from the N-terminus of P-450 2E1 protein
(493 amino acids, 56.84 kDa) were replaced with 130 amino acids from the N-terminus of P-450 camC protein (415 amino acids,
46.66 kDa). In chimera 2 (525 amino acids, 60.24 kDa) the strategy involves replacement of 28 amino acids in the C-terminus
of chimera 1 with 75 amino acids from the C-terminus of P-450 camC gene. Homology models of both the chimeric proteins were
developed using SWISS-MODEL based on the known crystal structure of cytochrome P-450 camC, BM-3, 1DT6A, and 2C17A. The models
indicated that the proposed heme-binding site was intact, which is inevitable for catalytic activity of cytochrome P-450s.
The expression of chimera 1 and 2 genes in Escherichia coli DH5α was evident from light-pink cell pellets, protein band in sodium dodecyl sulfate polyacrylamide gel electrophoresis,
and diagnostic carbon monoxide-difference spectra. Our studies show that strategies can be developed to exploit the natural
diversity of the P-450 superfamily to generate chimeric biocatalysts that would provide new templates amenable to directed
evolution. 相似文献
6.
Numerical results for the ground state of the HN
2
+
and HCO+ molecular ions at their near equilibrium geometry, obtained by the complex molecular orbitals (CMO) method in the extended basis set, are reported. The CMO wavefunction of the HN
2
+
ion is compared with the CI wavefunction obtained in the same basis set. This reveals the nature of approximations inherent in the CMO method. A peculiar feature of the occupation numbers of the CMO natural orbitals is also explained.Alexander von Humboldt Fellow. On leave from the Institute Rudjer Bokovi, Zagreb, Croatia, Yugoslavia. 相似文献
7.
Cyclodextrin cavities have been intercalated in a layered metal hydroxide to create hydrophobic nanopockets within the galleries of the layered solid. Anthracene molecules have been included in the anchored cavities by partitioning from a polar solvent. The excitation-emission fluorescence spectra of the included anthracene show a total absence of Stokes shift. The orientational dynamics of the isolated, solvent-free anthracene molecules in the anchored cyclodextrin cavities have been probed by fluorescence anisotropy decay measurements. The results have been compared with those for anthracene included in cyclodextrin cavities in aqueous solutions. 相似文献
8.
9.
Adsorption of n-hexane in zeolite-5A: a temperature-programmed desorption and IR-spectroscopic study
The adsorption and desorption of n-hexane over Zeolite-5A has been investigated as a function of loading using simultaneous Fourier transform infrared (FTIR)-temperature-programmed desorption (TPD) measurements. The TPD profiles show a second peak developing at lower temperatures when loading exceeds 16 hexane molecules per Zeolite-5A unit cell or two molecules per alpha-cavity of the Zeolite-5A structure. The infrared spectra rule out two types of adsorption sites as the origin of the two peaks in the TPD. Changes in the conformation of the adsorbed hexane as a function of loading and temperature were followed by monitoring the position of the methylene stretching modes in the infrared spectra. With increasing loading, the adsorbed hexane adopts a stretched trans conformation. These changes occur at loading levels below 12 hexane molecules per Zeolite-5A unit cell. No change is observed above this loading, ruling out any conformational change at loadings where the second peak is seen in the TPD. The second peak in the TPD arises, therefore, from a combination of steric repulsion and loss of translational entropy. 相似文献
10.
K. Suryakala K. R. Marikkannu G. Paruthimal Kalaignan T. Vasudevan 《Journal of Solid State Electrochemistry》2007,11(12):1671-1677
LiMn2O4-based spinels are of great interest as positive electrode materials for lithium ion batteries. LiCo
x
Mn2−x
O4 (x = 0.0, 0.1, 0.2, 0.3, and 0.4) spinel phases have been synthesized by novel citric acid-modified microwave-assisted sol–gel
method. The structural properties of the synthesized products have been investigated by X-ray powder diffraction and scanning
electron microscopy. To improve the recharge capacity of Li/LiCo
x
Mn2−x
O4 cells, the electrochemical features of LiCo
x
Mn2−x
O4 compounds have been evaluated as positive electrode materials. The structural properties of Co-doped oxides are very similar
to LiMn2O4 electrode. Techniques like cyclic voltammetry, charge–discharge and cycle life are also used to characterize the LiCo
x
Mn2−x
O4 (x = 0.0, 0.1, 0.2, 0.3, and 0.4) electrodes. 相似文献