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X‐ray photoelectron spectral study was made on the complexes Ni(nmedtc)2( 1 ), [Ni(nmedtc)(PPh3)2]ClO4( 2 ), [Ni‐(nmedtc)(dppe)]BPh4( 3 ) (where nmedtc = N‐methyl, N‐ethanoldithiocarbamate, dppe = 1, 2‐bis(diphenylphosphino)ethane). The nickel 2p3/2 binding energy values for chelated and free phosphine complexes are 854.0 and 854.1 eV which are significantly different from Ni2p3/2 BE value of NiS4 chromophore, indicating the relative dearth of electron density on Ni in NiS2P2 chromophores. The presence of two phosphine groups in NiS2P2 chromophore alleviates the electron density on the metal atom. More electron density is being pulled away from the metal atom in chelates than in the PPh3 analogue. This observation is in line with solution studies by cyclic voltammetry. A one‐electron reduction potential was observed to be the minimum for NiS2P2 chromophores compared to the others. Also the crystal structure of the complex [Ni(pipdtc)(1, 4‐dppb)]ClO4 (pipdtc‐ = piperidinecarbodithioato anion, 1, 4‐dppb = bis(diphenylphosphino)butane) prepared by the reaction between Ni(pipdtc)2, NiCl2�622O, and 1, 4‐dppb in CH3CN‐CH3OH is reported. 相似文献
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(1,10-Phenanthroline)bis(piperidinecarbodithioato-S,S′)cadmium(II), [Cd(pipdtc)2(1,10-phen)] (1) and (2,2′-bipyridine)bis(piperidinecarbodithioato-S,S′)cadmium(II), [Cd(pipdtc)2(bipy)] (2) adducts were prepared and the crystal structures are reported. Cd–S and Cd–N distances and the angles subtended at cadmium are almost the same in both complexes but the Cd–S distances in the adducts are longer than those in Cd(pipdtc)2 (3) complexes due to the presence of an additional neutral ligand. Thioureide C–N distance in 1 and 2 are supported by νC–N bands observed at 1471 and 1470 cm−1, respectively. S2p binding energies for the adducts show a significant reduction in value compared to the parent dithiocarbamate indicating the weakening of the Cd–S bond on adduct formation. The observed reduction in binding energy is due to the increased electron density on the metal in the adducts. The cyclic voltammetric study on the complexes also show an increase of electron density on cadmium in the adducts compared to Cd(pipdtc)2. 相似文献
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A mixture of 9-amino-(9-deoxy)epi-dihydroquinidine and salicylic acid was able to promote the direct reaction of various cyclohexanones with dibenzoyl peroxide, thus affording the corresponding protected α-hydroxy carbonyl compounds in high yield and enantioselectivity. Interestingly the same catalytic salt was found to be active when 1-indanones derivatives were directly employed in the reaction with dibenzoyl peroxide furnishing chiral 1-oxo-2,3-dihydro-1H-inden-2-yl benzoates in high yields and enantioselectivity. Furthermore their treatment with NaBH(4) gives easy access to the corresponding enantioenriched 1,2-diols in high yields and without any loss of stereoselectivity. 相似文献
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Kinkini Bhattacharyya Tanusree Kar Pradeep Kumar Dutta Basudeb Achari Gabriele Bocelli Lara Righi 《Acta Crystallographica. Section C, Structural Chemistry》2000,56(2):e60-e61
The title compound, C34H52O4, consists of five six‐membered rings. Barring the two rings, with double bonds, all other rings are in chair conformations. Mean‐plane and ring‐puckering calculations indicate these two rings to be in distorted‐chair conformations, with distortion towards the boat conformation. There are no strong hydrogen bonds and the structure is stabilized by van der Waals interactions only. The structure is compared with those reported for other triterpenes. 相似文献
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Greci L Castagna R Carloni P Stipa P Rizzoli C Righi L Sgarabotto P 《Organic & biomolecular chemistry》2003,1(21):3768-3771
N,N-Dimethyl-p-nitrosoaniline reacts with benzoyl chloride affording a complex salt containing a cation, a hybrid between a nitrenium ion and an iminium ion. The salt reacts with nucleophiles (indoles, indolizines) yielding compounds characterized by a new carbon-nitrogen bond, derived from the nitrenium ion form. According to the type of nucleophile, the reaction, to differing extents, is in competition with an electron transfer process which leads to the formation of the dimer of the nucleophile and of the azoxy corresponding to the N,N-dimethyl-p-nitrosoaniline. In one of the reactions studied, a chlorinated azoxy derivative was also isolated, and its structure was elucidated by X-ray analysis. 相似文献
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An expeditious synthesis of three polyoxygenated flavones: mosloflavone, negletein and baicalein, starting from crysin, an easily available flavone, by a bromination/methoxylation procedure is reported. The convergent synthesis exploits a base induced Wesley-Moser type rearrangement. 相似文献