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1.
The structure and rotational barrier for the mesityl-silicon bond of 2,2-dimesityl-1,1,1,3,3,3-hexamethyltrisilane have been investigated by 1H- and 13C-variable temperature nuclear magnetic resonance (NMR) as well as by density functional theory structural calculations. The calculations show that the lowest energy structure has C2 symmetry with nonequivalent ortho methyl groups, consistent with the crystal structure and solution NMR. The nonequivalent ortho methyl groups exchange through a Cs transition state with a calculated relative free energy of 11.0 kcal mol−1. The barrier for this rotation found by dynamic NMR is 13.4 ± 0.2 kcal mol−1 at 298 K. 相似文献
2.
Thomas Wittmann Dr. Renée Siegel Nele Reimer Dr. Wolfgang Milius Prof. Dr. Norbert Stock Prof. Dr. Jürgen Senker 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(1):314-323
The resistance of metal–organic frameworks towards water is a very critical issue concerning their practical use. Recently, it was shown for microporous MOFs that the water stability could be increased by introducing hydrophobic pendant groups. Here, we demonstrate a remarkable stabilisation of the mesoporous MOF Al‐MIL‐101‐NH2 by postsynthetic modification with phenyl isocyanate. In this process 86 % of the amino groups were converted into phenylurea units. As a consequence, the long‐term stability of Al‐MIL‐101‐URPh in liquid water could be extended beyond a week. In water saturated atmospheres Al‐MIL‐101‐URPh decomposed at least 12‐times slower than the unfunctionalised analogue. To study the underlying processes both materials were characterised by Ar, N2 and H2O sorption measurements, powder X‐ray diffraction, thermogravimetric and chemical analysis as well as solid‐state NMR and IR spectroscopy. Postsynthetic modification decreased the BET equivalent surface area from 3363 to 1555 m2 g?1 for Al‐MIL‐101‐URPh and reduced the mean diameters of the mesopores by 0.6 nm without degrading the structure significantly and reducing thermal stability. In spite of similar water uptake capacities, the relative humidity‐dependent uptake of Al‐MIL‐101‐URPh is slowed and occurs at higher relative humidity values. In combination with 1H‐27Al D ‐HMQC NMR spectroscopy experiments this favours a shielding mechanism of the Al clusters by the pendant phenyl groups and rules out pore blocking. 相似文献
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4.
Maria Chudnovsky Jim Geelen Bert Gerards Luis Goddyn Michael Lohman Paul Seymour 《Combinatorica》2006,26(5):521-532
Let G=(V,E) be an oriented graph whose edges are labelled by the elements of a group Γ and let A⊂V. An A-path is a path whose ends are both in A. The weight of a path P in G is the sum of the group values on forward oriented arcs minus the sum of the backward oriented arcs in P. (If Γ is not abelian, we sum the labels in their order along the path.) We are interested in the maximum number of vertex-disjoint
A-paths each of non-zero weight. When A = V this problem is equivalent to the maximum matching problem. The general case also includes Mader's S-paths problem. We prove that for any positive integer k, either there are k vertex-disjoint A-paths each of non-zero weight, or there is a set of at most 2k −2 vertices that meets each of the non-zero A-paths. This result is obtained as a consequence of an exact min-max theorem.
These results were obtained at a workshop on Structural Graph Theory at the PIMS Institute in Vancouver, Canada. This research
was partially conducted during the period the first author served as a Clay Mathematics Institute Long-Term Prize Fellow. 相似文献
5.
We discuss some variant superfield representations which can arise by the replacement of some of the usual fields in a multiplet with p-form gauge fields. 相似文献
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8.
LauraN. Gregerson TrevorC. McMorris JayS. Siegel KimK. Baldridge 《Helvetica chimica acta》2003,86(12):4133-4151
(Hydroxymethyl)acylfulvene (HMAF, irofulven; 4 ), a third‐generation derivative of a natural product extracted from the mushroom Omphalotus illudens, is selectively toxic towards certain forms of malignant tumors. Conversion of HMAF and cognates to stable aromatic derivatives is triggered by thiol attack in vitro and in vivo. Quantum‐chemical methods predict well the structure for several functionalized derivatives of irofulven as compared to known X‐ray crystallographic structures. Computational reaction profiles for thiol attack and aromatic rearrangement of irofulven and illudin S, a toxin from which irofulven is derived, provide insight into HMAF's selectivity and toxicity. Methods used include hybrid density‐functional theory (HDFT), Hartree? Fock (HF), and Møller? Plesset second‐order perturbation theory (MP2). Solvent effects have been explored by means of the new continuum‐solvation method, COSab, presented in an accompanying paper. 相似文献
9.
Liu Yuren Lu Yanxin Xie Yali Wang Yonghai Du Youling Tan Jin Meng Bonian R. S. Seymour 《Journal of Radioanalytical and Nuclear Chemistry》1991,151(1):83-93
This paper introduces the principles, instrumentation, implementation, and industrial applications of an on-line thermal neutron prompt-gamma element analysis system (using a252Cf neutron source, Am–Be neutron source, or neutron generator). The energy resolution of the system at the H prompt-gamma full-energy photopeak (2.22325 MeV) is 3.6 keV. The concentration measurement error of Al2O3, FeO3, CaO, and SiO2 is ±0.3%, ±0.1%, ±0.4%, and ±0.4%, respectively. The system has been tested on-site at both the Shandong and the Zhengzhou Aluminium Works. Our preliminary on-site measurements confirm that the stability, reliability, measurement range, and accuracy of the system can meet the requirements of the aluminium production process. Facilitation of this measurement at aluminium plants is expected to reduce plant costs by over 3 million dollars annually through reduced energy consumption, more rapid qualification of pulps being mixed during the production process, and in reduced labor costs.Other participants of Shandong and Zhenghou Aluminium Works are: Wang Aili, Zengshen, Dei Jianguo and Lu Jinnan, Wang Deyu, Jin Hequan. 相似文献
10.
OCULAR LIGHT DAMAGE 总被引:2,自引:0,他引:2