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31.
Summary The kinetics of reduction of [MnIII(cydta)]– (where H4cydta=trans-cyclohexane-1,2-diamine-N N N' N'-tetraacetic acid) by some thiourea reductants have been studied in aqueous solution by stopped-flow techniques in the pH ranges 2.5–4.5 and 9.2–10.2. An initial increase in absorbance followed by a steady decrease indicated the formation of a precursor complex prior to the electron transfer step. The reactions are first order in both oxidant and reductant. The observed increase in rate in going from low to high pH is attributed to the difference in reactivities of the aqua and hydroxo species of the MnIII complex; the higher reactivity of the latter is consistent with the formation of a ligand-bridged activated species prior to electron transfer. The reactivity order for the thiourea derivatives follows the order of their reported substituent effects. 相似文献
32.
Mukul Biswas Madhusudan Banerjee Mrinal M. Maiti 《Journal of polymer science. Part A, Polymer chemistry》1984,22(9):1997-2004
Copper(II)-exchanged-13X molecular sieves, prepared from four copper(II) salts, namely, sulfate, nitrate, chloride, and acetate, and their activities in the polymerization of N-vinylcarbazole at a fixed copper ion exchange level were studied. From the kinetic characteristics of polymerization it was established that the variation in activities of the Cu-exchanged sieves is due primarily to the difference in the pH of the original salt solution, which is responsible for the varying degree of proton exchange with the zeolite during copper ion exchange. A first-order dependence of the rate of polymerization was observed with respect to H+ ion concentration of the original copper-salt solution. It was further established that the rate of polymerization of exchanged copper ion, at a hypothetical zero proton concentration, is low. A mechanism of polymerization of NVC on copper-exchanged-13X zeolite was suggested on the basis of the results obtained. 相似文献
33.
U. Pandey S. Banerjee A. Mukherjee H. D. Sarma M. Venkatesh 《Journal of Radioanalytical and Nuclear Chemistry》2007,273(3):719-723
Several human tumors such as neuroendocrine tumors, medullary thyroid carcinoma, etc., express somatostatin receptors which
specifically bind somatostatin and its analogues such as lanreotide, octreotide, etc. In order to prepare a therapeutic agent
for targeting such tumors, attempts were made to prepare 90Y-DOTA-Lanreotide. Lanreotide could be successfully conjugated with the macrocyclic chelating agent DOTA (1,4,7,10-tetraaza
cyclododecane tetracetic acid) which forms stable complexes with 90Y. 90Y-DOTA-Lanreotide could be prepared in >98% radiochemical purity and remained stable for 72 hours at room temperature. The
tracer showed specific binding to A431 cells. Biodistribution studies in C57BL6 mice bearing melanoma showed ∼1.3% uptake
pergram of tumor at 24-hour p.i. 相似文献
34.
Arijit BanerjeeSamir Kumar Maji Michael G.B. DrewDebasish Haldar Arindam Banerjee 《Tetrahedron letters》2003,44(4):699-702
A single-crystal X-ray diffraction study of the terminally protected tetrapeptide Boc-β-Ala-Aib-Leu-Aib-OMe 1 (Aib: α-aminoisobutyric acid; β-Ala: β-Alanine) reveals that it adopts a new type of double turn structure which self-associates to form a unique supramolecular helix through intermolecular hydrogen bonds. Scanning electron microscopic studies show that peptide 1 exhibits amyloid-like fibrillar morphology in the solid state. 相似文献
35.
A new method for the preparation of the synthon (±)-2,6,7,7a-tetrahydro-1β-hydroxy-4-formyl-7aβ-methylindene (1,a) for the
total synthesis of steroids in both (±) and (+) forms, starting from the known β-ketoester, (±)-methyl 1β-t-butoxy-5,6,7,7a-tetrahydro-7aβ-methyl-5-keto-4-indancarboxylate (2,a) has been described. An alternative route to (1,a) has
been investigated. Although the compound, (±)-1β-hydroxy-5,6,7,7a-tetrahydro-7aβ-methyl-5-keto-4-methoxymethylindan (2,b)
could not be prepared, interesting pathways leading to two unexpected products, (±)-5,6,7,7a-tetrahydro-4,7a-dimethyl-5H-indene-1,5-dione
and (±)-2,6-diketo-3-methyltricyclo-(5,2,1,0)decan-8-ol (3 and 4), were encountered during an attempted annelation reaction
of the ketone, N-diethylamino-5-methoxypentan-3-one (6), with 2-methylcyclopentan-1,3-dione (5). Trapping of the intermediate,
(±)-3a,4,5,6,7,7a-hexahydro-3a-hydroxy-4-methylene-7a-methylindene-1,5-dione (7), through the formation of the adduct, (±)-3a,4,5,6,7,7a-hexahydro-3a-hydroxy-4-(1′,
3′-diketo-2′-methylcyclopentano-2′-methylene)-7a-methylindene-1,5-dione (8), established the mechanism of the formation of
the products (3 and 4). 相似文献
36.
Rupendranath Banerjee 《Transition Metal Chemistry》1985,10(4):147-148
Summary In low acid (0.02 M HClO4) media, Pb2+ ion strongly catalyses the aquation of Cr(ox)
3
3–
to givecis-Cr(ox)2(OH2)
2
–
ion. The catalytic efficiency of Pb2+ as represented by the second order rate constant, kpb (3.76 × 10–4 M–1 s–1 at 25 °C; I, 1.0 M perchlorate), for the Pb2+ catalysed path is remarkably higher than might be expected on the basis of Kpb-ox, the first formation constant for the lead-oxalate complex. This catalytic superiority of Pb2+ has been found to result mainly from a comparatively much lower H (65.2 ±0.8 kJ mol–1) value which more than compensates for the relatively unfavourable S value (–93.2 ±2.4 JK–1mol–1) for this catalysed path. This low S value is, however, in line with the entropy of hydration of Pb2+ ion. These facts, together with the different LFER plots, have been utilised to propose a plausible mechanism for such catalysed reactions. 相似文献
37.
Premamoy Ghosh Partha Sarathi Mitra Amar Nath Banerjee 《Journal of polymer science. Part A, Polymer chemistry》1973,11(8):2021-2030
Low concentrations of bromine (0.008–0.06M) were used to initiate photopolymerization of MMA in bulk and in diluted (near bulk) systems, the diluents or solvents used being benzene, toluene, dioxane, tetrahydrofuran, carbon tetrachloride, chloroform, methylene chloride, and methanol. Polymerization in bulk follows usual free-radical kinetics. Inert solvents (benzene, toluene) as well as the other solvents used enhance the rate of polymerization MMA even when used in the range of catalytic concentrations (0.04–0.4M). An initiation mechanism involving solvent molecules appears to be predominant in diluted systems. 相似文献
38.
The structure and stereochemistry of crotocaudin, a new norditerpene occurring as a minor constituent in Crotoncaudatus Geisel (Euphorbiaceae) have been established as ent-8S,10S-15,16-epoxy-19-norcleroda-4,11,13(16), 14-tetraene 18,6S: 20,12-diolactone 7 from the detailed studies of 1H NMR spectra using lanthanide shift reagents, decoupling experiments and chemical reactions. The congener, teucvidin, ent-10S-15,16-epoxy-19-norcleroda-4,13(16), 14-triene-18,6S: 20,12R-diolactone 1 was obtained as a major component besides several triterpenoids viz taraxerone 2, taraxerol 3 and taraxeryl acetate 4. 13C NMR and 1H NMR spectra and a few novel reactions of teucvidin and its conversion to teucvin, ent-(6R,12R)-15,16-epoxy-19-nor-9,4-friedolabda-4,13(16),14-triene-18,6:20, 12-diolactone 6 are also reported. 相似文献
39.
The coupled-cluster approach to obtaining the bond-state wave functions of many-electron systems is extended, with a set of physically reasonable approximations, to admit a multiconfiguration reference state. This extension permits electronic structure calculations to be performed on correlated closed- or open-shell systems with potentially uniform precision for all molecular geometries. Explicit coupled cluster working equations are derived using a multiconfiguration reference state for the case in which the so-called cluster operator is approximated by its one- and two-particle components. The evaluation of the requisite matrix elements is facilitated by use of the unitary group generators which have recently received wide attention and use in the quantum chemistry community. 相似文献
40.
C. K. Das A. K. Ghosh S. Banerjee 《Journal of polymer science. Part A, Polymer chemistry》1977,15(9):2255-2268
The salient features of nonelemental sulfur vulcanization by tetramethylthiuram disulfide (TMTD) and elemental sulfur vulcanization promoted by TMTD both in presence and absence of ZnO and stearic acid have been studied. In stock containing TMTD, a higher rate constant value for dicumyl peroxide (DCP) decomposition was observed. TMTD decreases the crosslinking density due to DCP depending on its concentration. An entirely radical mechanism has been advanced in the absence of ZnO. ZnO or ZnO–stearic acid seems to alter the entire course of reaction. The rate of crosslinking increases in the presence of ZnO or ZnO–stearic acid. Moreover, crosslinks are formed additively (further supported from the activation energy data), and mixed crosslink formation has been confirmed by the methyl iodide test of the vulcanizates. Stearic acid has no effect on crosslink formation. An ionic chain mechanism has been postulated in the presence of ZnO, as suggested by British authors. 相似文献