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排序方式: 共有369条查询结果,搜索用时 15 毫秒
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2.
Francine Vinette Jiri Cizek Edward R. Vrscay 《International journal of quantum chemistry》1987,32(6):663-667
The upper and lower bounds of a harmonic oscillator with an octic perturbation are studied with the use of renormalized inner projection. It is shown that this relatively simple technique works even in the infinite coupling constant limit. Symbolic computation is very convenient and useful in these types of problems, where only a finite number of operations are required. 相似文献
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Fernandes SA Nachtigall FF Lazzarotto M Fujiwara FY Marsaioli AJ 《Magnetic resonance in chemistry : MRC》2005,43(5):398-404
'Non-covalent synthesis' of novel chiral hosts (calix[6]arene-chiral amine complexes) and its application to enantiomeric discrimination was investigated by (1)H NMR spectroscopy. The topology of a ternary complex was proposed for the calix[6]arene-amine-sulfoxide to rationalize the chiral recognition. 相似文献
5.
Yara De M. Gomes AndrÉ F. Furtado Luana B. B. Coelho 《Applied biochemistry and biotechnology》1991,31(1):97-107
Hemagglutinating activity was studied in homogenates of three embryonic stages, and in the hemolymph of most instar larvae and in adult insects of Panstrongylus megistus, an important Chagas' disease vector in Brazil. A hemolymph lectin from the 5th instar larvae of P. megistus was purified through a biospecific adsorption by using formaldehyde-treated erythrocytes. The lectin fraction was desorbed with 0.2M D-galactose in 0.15M NaCl. The lectin fraction activity was inhibited by L-rhamnose, D-lactose, raffinose, D-galactose, and D-fucose. The electrophoretic pattern to native and acidic proteins resolved lectin fraction in two main bands with lectin activity. These bands were considered as multiple molecular forms or isoforms of P. megistus lectin. Under denaturating conditions, isoform 1 showed one band with apparent mol wt (MW) of 64 kDa while isoform 2 was resolved in two bands with MW of 64 and 33 kDa. 相似文献
6.
Palmer FN Lach F Poriel C Pepper AG Bagley MC Slawin AM Moody CJ 《Organic & biomolecular chemistry》2005,3(20):3805-3811
Various approaches to the tyrosine-derived fragment of the marine secondary metabolite diazonamide A are described. Initial efforts were focused on the originally proposed structure of the natural product, and a feasibility study established that a model 4-aryltryptamine could be readily prepared. Protected 4-bromotryptamine underwent Pd0-catalyzed coupling with the boronic acid derived from 2-bromophenyl allyl ether by Claisen rearrangement, O-methylation and lithiation-boration. The resulting biaryl was elaborated into an alpha-diazo-beta-ketoester, dirhodium(II)-catalyzed reaction of which with N-Z-valinamide gave the desired tryptamine-oxazole following cyclodehydration of the intermediate ketoamide. A potential precursor to the benzofuran ring of the original structure of diazonamide A was prepared in eight steps from N-Z-tyrosine tert-butyl ester. Iodination, O-protection and Stille coupling gave the cinnamyl alcohol 25, converted via the bromide into the allyl aryl ether 27. Subsequent Claisen rearrangement and oxidative cleavage of the alkene gave the lactol 29, converted into the desired benzofuranone 31. The revision in the structure of diazonamide A to 2 resulted in the targeting of an alternative tyrosine-derived model benzofuranone 41 synthesized in four steps from N-Z-tyrosine methyl ester 36 by a route involving Claisen rearrangement of cinnamyl ether 37. Poor yields in this sequence prompted an investigation into the intramolecular Heck reaction as a route to benzofuranone 50. Coupling of 3-iodotyrosine 44 with 2-phenylbutenoic acid 48 gave ester 49 that readily underwent intramolecular Heck reaction to give benzofuranone 50, albeit with poor stereocontrol. 相似文献
7.
Christian NP Reilly JP Mokler VR Wincott FE Ellington AD 《Journal of the American Society for Mass Spectrometry》2001,12(6):744-753
To probe the mechanism of gas-phase oligonucleotide ion fragmentation, modified oligonucleotides were studied using matrix-assisted laser desorption/ionization. The oligonucleotides were of the form 5'-TTTTXTTTTT, where X was a modified nucleotide. Modifications included substitution of hydroxy, methoxy, amino, and allyl groups at the 2'-position of the deoxyribose. The modified ribose contained adenine, guanine, cytosine, or uracil bases. For comparison, we studied oligomers where X was an unmodified adenosine, guanosine, cytidine, thymidine, or uridine deoxyribonucleotide. We found a very strong dependence of the matrix-to-analyte ratio on fragmentation for these oligomers. Analysis of these modifications suggests that the initial fragmentation step in MALDI-MS involves a two-step (E1) elimination of the base. 相似文献
8.
Monique Nanot Francine Queyroux Jean-Claude Gilles 《Journal of solid state chemistry》1979,28(2):137-147
The homologous phases corresponding to the formula AnBnO3n+2 observed in the systems: La2Ti2O7CaTiO3, Nd2Ti2O7CaTiO3 and Ca2Nb2O7CaTiO3, have a structure derived from the structure of perovskite by periodic crystallographic shears, which delimitate n octahedra thick sheets. In the [0 1 0]1 direction, the sheets are following each other with two types of arrangement.Crystals of terms n = 4,5, 5 and 6 were investigated by X-ray diffraction. According to the type of arrangement of the sheets, the phases studied have either an orthorhombic symmetry or a monoclinic symmetry, this last one giving rise to merohedral twins. 相似文献
9.
Bludský O Silhan M Nachtigall P Bucko T Benco L Hafner J 《The journal of physical chemistry. B》2005,109(19):9631-9638
Periodic DFT and combined quantum mechanics/interatomic potential function (QM-pot) models were used to describe the interaction of CO with the Cu+ sites in FER. The CO stretching frequencies were calculated using omega(CO)(CCSD(T))/r(CO)(DFT) scaling method relating frequencies determined using a high-level quantum-chemical (coupled clusters) method for simple model carbonyls to CO bond lengths calculated using periodic DFT and QM-pot methods for the Cu+-zeolite system. Both periodic DFT and QM-pot models together with omega(CO)/r(CO) scaling describe the CO stretching dynamics with the "near spectroscopic accuracy", giving nu(CO) = 2156 cm(-1) in excellent agreement with experimental data. Calculations for various Cu+ sites in FER show that both types of Cu+ sites in FER (channel-wall sites and intersection sites) have the same CO stretching frequencies. Thus, the CO stretching frequencies are not site-specific in the CO/Cu+/FER system. The convergence of the results with respect to the model size was analyzed. When the same exchange-correlation functional is used the adsorption energies from periodic DFT and QM-pot are in good agreement (about 2 kcal/mol difference) but substantially larger than those of the experiment. The adsorption energy calculated with the B3LYP functional agrees with available experimental data. The overestimation of the adsorption energy in DFT calculations (periodic or QM-pot) is related to a red-shift of the CO stretching mode, both result from an underestimation of the HOMO(5sigma)-LUMO(2pi) gap of CO and the consequent overestimation of the Cu(+)(d)-CO(2pi*) back-donation. For the adsorption energy, this can be overcome by the use of hybrid B3LYP exchange-correlation functional. For the frequency calculations, the DFT problem can be overcome by the use of the omega(CO)(CCSD(T))/r(CO)(DFT) correlation. 相似文献
10.