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41.
The kinetics of oxidation of four vicinal diols, four nonvicinal diols, and one of their monoethers by pyridinium bromochromate (PBC) have been studied in dimethyl sulfoxide. The main product of oxidation is the corresponding hydroxyaldehyde. The reaction is first-order with respect to each the diol and PBC. The reaction is acid-catalyzed and the acid dependence has the form: kobs=a+b[H+]. The oxidation of [1,1,2,2-2H4]ethanediol exhibited a primary kinetic isotope effect (kH/k D=6.70 at 298 K). The reaction has been studied in 19 organic solvents including dimethyl sulfoxide and the solvent effect has been analyzed using multiparametric equations. The temperature dependence of the kinetic isotope effect indicates the presence of a symmetrical transition state in the rate-determining step. A suitable mechanism has been proposed. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 285–290, 1998. 相似文献
42.
Lszl Ktai KalyanK. Banerji Istvn Saj Jnos Kristf B. Sreedhar Sndor Holly Gbor Keresztury Antal Rockenbauer 《Helvetica chimica acta》2002,85(8):2316-2327
Tetraamminecopper(2+) bis(permanganate) ([Cu(NH3)4](MnO4)2; 1 ) was prepared, and its properties were studied in both aqueous solution and the solid phase. The presence of H‐bond interactions between the ammonia ligand of the complex cation and an O‐atom of the permanganate ion was detected by IR and Raman methods. The solid‐phase thermal deammoniation of 1 led to an unusual intramolecular redox reaction between the Mn O⋅⋅⋅H N linkage with formation of NH4NO3 and CuMn2O4‐type mixed oxides instead of stepwise deammoniation, even below 100°. The thermal deammoniation of 1 in aqueous solution led, instead of to hydrated copper(2+) bis(permanganate), to the formation of NH4MnO4 ( 2 ). Since the temperature of the thermal deammoniation of 1 is lower than the decomposition temperature of the permanganate ion, the regulated solid‐phase decomposition of 1 allowed preparation of CuMn2O4‐type oxides with mixing of copper and manganese at the atomic level. 相似文献
43.
There are quantum states of light that can be expressed as finite superpositions of Fock states (FSFS). We demonstrate the nonclassicality of an arbitrary FSFS by means of its phase space distributions such as the Wigner function and the Q-function. The decoherence of the FSFS is studied by considering the time evolution of its Wigner function in amplitude decay and phase damping channels. As examples, we determine the nonclassicality and decoherence of generalized and reciprocal binomial states. 相似文献
44.
Pal P Saha A Mukherjee AK Mukherjee DC 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2004,60(1-2):167-171
Menadione (vitamin K(3)) has been shown to form charge transfer complexes with N,N-dimethyl aniline, N,N-dimethyl p-toluidine and N,N-dimethyl m-toluidine in CCl(4) medium. The CT transition energies are well correlated with the ionisation potentials of the anilines. The formation constants of the complexes have been determined at a number of temperatures from which the enthalpies and entropies of formation have been obtained. The formation constants exhibit a very good linear free energy relationship (Hammett) at all the temperatures studied. 相似文献
45.
Gantait A Maji A Barman T Banerji P Venkatesh P Mukherjee PK 《Natural product research》2012,26(3):216-222
Capsicum annuum L. (family: Solanaceae) possesses therapeutic benefits for the treatment of rheumatism, neuropathy, psoriasis, flatulence and so on. In this study fruits of four different varieties of C. annuum from four different geographical regions in India were evaluated based on their total content of capsaicin. Ethanol extracts of the fruits were used. HPTLC plates were developed in a mobile phase containing benzene, ethyl acetate and methanol (75:20:5). Densitometric scanning was performed at a wavelength of 283 nm in the absorbance mode. The calibration curve was described by the equation Y=393.587+3.836*X with a correlation coefficient (r) of 0.99890. The content of capsaicin in Nagaland, Manipur, West Bengal and Shimla varieties was found to be 3.71%, 1.78%, 0.54% and 0.06%, respectively. The developed densitometric method was found to be specific, accurate and precise. A recovery study and precision showed low levels of %RSD values. The linearity range of the curve for capsaicin was found to be 300-900 ng per spot. The limit of detection and the limit of quantification values were determined to be 31 and 94 ng, respectively, proving the sensitivity of the method. Thus the method can be used to control the total content of capsaicin on an industrial scale. 相似文献
46.
The synthesis, spectroscopic, and electrochemical properties of seven new P(V)-meso-triarylcorroles (1-7) are reported. Compounds 1-7 were prepared by heating the corresponding free-base corroles with POCl(3) at reflux in pyridine. Hexacoordinate P(V) complexes of meso-triarylcorroles were isolated that contained two axial hydroxy groups, unlike the P(V) complex of 8,12-diethyl-2,3,7,13,17,18-hexamethylcorrole, which was pentacoordinate, or the P(V) complex of meso-tetraphenylporphyrin, which was hexacoordinate with two axial chloro groups. (1)H and (31)P?NMR spectroscopy in CDCl(3) indicated that the hexacoordinated P(V)-meso-triarylcorroles were prone to axial-ligand dissociation to form pentacoordinated P(V)-meso-triarylcorroles. However, in the presence of strongly coordinating solvents, such as CH(3)OH, THF, and DMSO, the P(V)-meso-triarylcorroles preferred to exist in a hexacoordinated geometry in which the corresponding solvent molecules acted as axial ligands. X-ray diffraction of two complexes confirmed the hexacoordination environment for P(V)-meso-triarylcorroles. Their absorption spectra in two coordinating solvents revealed that P(V)-meso-triarylcorroles showed a strong band at about 600?nm together with other bands, in contrast to P(V)-porphyrins, which showed weak bands in the visible region. These compounds were easier to oxidize and more difficult to reduce compared to P(V)-porphyrins. These compounds were brightly fluorescent, unlike the weakly fluorescent P(V)-porphyrins, and the quantum yields for selected P(V)-corroles were as high as Al(III) and Ga(III) corroles, which are the best known fluorescent compounds among oligopyrrolic macrocycles. 相似文献
47.
Avijit Ghosh Prof. Mangalampalli Ravikanth 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(20):6386-6396
The synthesis, spectroscopic, and electrochemical properties of seven new PV–meso‐triarylcorroles ( 1 – 7 ) are reported. Compounds 1 – 7 were prepared by heating the corresponding free‐base corroles with POCl3 at reflux in pyridine. Hexacoordinate PV complexes of meso‐triarylcorroles were isolated that contained two axial hydroxy groups, unlike the PV complex of 8,12‐diethyl‐2,3,7,13,17,18‐hexamethylcorrole, which was pentacoordinate, or the PV complex of meso‐tetraphenylporphyrin, which was hexacoordinate with two axial chloro groups. 1H and 31P NMR spectroscopy in CDCl3 indicated that the hexacoordinated PV–meso‐triarylcorroles were prone to axial‐ligand dissociation to form pentacoordinated PV–meso‐triarylcorroles. However, in the presence of strongly coordinating solvents, such as CH3OH, THF, and DMSO, the PV–meso‐triarylcorroles preferred to exist in a hexacoordinated geometry in which the corresponding solvent molecules acted as axial ligands. X‐ray diffraction of two complexes confirmed the hexacoordination environment for PV–meso‐triarylcorroles. Their absorption spectra in two coordinating solvents revealed that PV–meso‐triarylcorroles showed a strong band at about 600 nm together with other bands, in contrast to PV–porphyrins, which showed weak bands in the visible region. These compounds were easier to oxidize and more difficult to reduce compared to PV–porphyrins. These compounds were brightly fluorescent, unlike the weakly fluorescent PV–porphyrins, and the quantum yields for selected PV–corroles were as high as AlIII and GaIII corroles, which are the best known fluorescent compounds among oligopyrrolic macrocycles. 相似文献
48.
Avijit Banerji Kaustabh Kumar Maiti Sunanda Haldar Chaitali Mukhopadhyay Julie Banerji Thierry Prangé Alain Neuman 《Monatshefte für Chemie / Chemical Monthly》2000,131(8):901-911
Summary. Studies on cycloadditions of C,N-diarylnitrones to cinnamic acid amides were carried out. The diastereoisomeric (I, II) and (in some cases) regioisomeric (III) cycloadducts obtained were characterized by spectroscopic and X-ray data. Conformational studies were carried out by molecular
modelling.
Received February 8, 2000. Accepted February 18, 2000 相似文献
49.
This problem deals with the determination of thermo-elastic interaction due to step input of temperature on the boundaries of a functionally graded orthotropic hollow sphere in the context of linear theories of generalized thermo-elasticity. Using the Laplace transformation the fundamental equations have been expressed in the form of vector–matrix differential equation which is then solved by eigenvalue approach. The inverse of the transformed solution is carried out by applying a method of Bellman et al. Stresses, displacement and temperature distributions have been computed numerically and presented graphically in a number of figures. A comparison of the results for different theories (TEWOED(GN-II), TEWED(GN-III) and three-phase-lag model) is presented. When the material is homogeneous, isotropic and outer radius of the hollow sphere tends to infinity, the corresponding results agree with that of existing literature for GN-III model. 相似文献
50.
Qian Wu Avijit Roy Elisabeth Irran Zheng‐Wang Qu Stefan Grimme Hendrik F. T. Klare Martin Oestreich 《Angewandte Chemie (International ed. in English)》2019,58(48):17307-17311
A metal‐free, intermolecular syn‐addition of hexamethyldisilane across simple alkenes is reported. The catalytic cycle is initiated and propagated by the transfer of a methyl group from the disilane to a silylium‐ion‐like intermediate, corresponding to the (re)generation of the silylium‐ion catalyst. The key feature of the reaction sequence is the cleavage of the Si?Si bond in a 1,3‐silyl shift from silicon to carbon. A central intermediate of the catalysis was structurally characterized by X‐ray diffraction, and the computed reaction mechanism is fully consistent with the experimental findings. 相似文献