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191.
Houghton J Dyson G Douthwaite RE Whitwood AC Kariuki BM 《Dalton transactions (Cambridge, England : 2003)》2007,(28):3065-3073
A series of palladium(II) complexes incorporating di-NHC-amine ligands has been prepared and their structural, dynamic and catalytic behaviour investigated. The complexes [trans-(kappa(2)-(tBu)CN(Bn)C(tBu))PdCl(2)] (12) and [trans-(kappa(2)-(Mes)CN(H)C(Mes))PdCl(2)] (13) do not exhibit interaction between the amine nitrogen and palladium atom respectively. NMR spectroscopy between -40 and 25 degrees C shows that the di-NHC-amine ligand is flexible expressing C(s) symmetry and for 13 rotation of the mesityl groups is prevented. In the related C(1) complex [(kappa(3)-(tBu)CN(H)C(tBu))PdCl][Cl] (14) coordination of NHC moieties and amine nitrogen atom is observed between -40 and 25 degrees C. Reaction between 12-14 and two equivalents of AgBF(4) in acetonitrile gives the analogous complexes [trans-(kappa(2)-(tBu)CN(Bn)C(tBu))Pd(MeCN)(2)][BF(4)](2) (15), [trans-(kappa(2)-(Mes)CN(H)C(Mes))Pd(MeCN)(2)][BF(4)](2) (16) and [(kappa(3)-(tBu)CN(H)C(tBu))Pd(MeCN)][BF(4)](2) (17) indicating that ligand structure determines amine coordination. The single crystal X-ray structures of 12, 17 and two ligand imidazolium salt precursors (tBu)C(H)N(Bn)C(H)(tBu)][Cl](2) (2) and [(tBu)C(H)N(H)C(H)(tBu)][BPh(4)](2) (4) have been determined. Complexes 12-14 and 15-17 have been shown to be active precatalysts for Heck and hydroamination reactions respectively. 相似文献
192.
Coolen-Schrijner Pauline Pollett Phil 《Methodology and Computing in Applied Probability》1999,1(1):81-96
We consider a discrete-time Markov chain on the non-negative integers with drift to infinity and study the limiting behavior of the state probabilities conditioned on not having left state 0 for the last time. Using a transformation, we obtain a dual Markov chain with an absorbing state such that absorption occurs with probability 1. We prove that the state probabilities of the original chain conditioned on not having left state 0 for the last time are equal to the state probabilities of its dual conditioned on non-absorption. This allows us to establish the simultaneous existence, and then equivalence, of their limiting conditional distributions. Although a limiting conditional distribution for the dual chain is always a quasi-stationary distribution in the usual sense, a similar statement is not possible for the original chain. 相似文献
193.
Manenkov A.B. Benson T.M. Sewell P.D. Kendall P.C. 《Optical and Quantum Electronics》2000,32(11):1245-1255
A novel scalar (i.e. paraxial) free space radiation mode method is presented for calculating the normal incidence facet reflectivity of the main guided mode of a step-index optical fibre with generally shaped smooth core. Numerical results are presented and discussed for several cases of the Nth order super-elliptical core shape, including the circular, elliptical, rectangular-type and slab limiting cases. 相似文献
194.
建立了微波等离子体原子发射光谱法(MP-AES)测定地质样品中的常量和微量元素的方法,四酸(盐酸+硝酸+高氯酸+氢佛酸)消解样品,得出了使用4200 MP-AES仪分析地化认证参考物质中常规金属元素(Ag,Cu,Ni,Pb和Zn)的结果,测定样品结果的相对标准偏差落在±10%范围内,另外,IEC和FLIC模型可成功校正光谱干扰。MP-AES仪无需使用乙炔等危险气体,极大提高了实验室安全性并显著降低了运行成本。MP-AES仪已成功应用于地化样品的分析中,结果准确可靠。 相似文献
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199.
Benson M. Kariuki Patrizia Calcagno Kenneth D. M. Harris Douglas Philp Roy L. Johnston 《Angewandte Chemie (International ed. in English)》1999,38(6):831-835
The genetic algorithm approach , in which a population of trial structures is allowed to evolve subject to well-defined procedures for mating, mutation, and natural selection, was employed to solve the complex molecular crystal structure of Ph2P(O)(CH2)7P(O)Ph2 directly from powder diffraction data. The structure solution reveals an interesting (perhaps unexpected) molecular conformation (see picture), which emphasizes the importance of allowing complete conformational flexibility of the molecule in the structure solution calculation. 相似文献
200.
K. C. Nicolaou Phil S. Baran Rolf Jautelat Yun He Kin Chiu Fong Ha‐Soon Choi Won Hyung Yoon Yong‐Li Zhong 《Angewandte Chemie (International ed. in English)》1999,38(4):549-552
A seven‐step cascade reaction —in which selective mesylation, epoxide formation, epoxide lysis, cyclization, reiterative oxidation, and nitrogen–oxygen exchange occur sequentially—facilitates the construction of the maleic anhydride moiety of CP molecules 1 and 2 (>93% yield per step). Unstable intermediates of this reaction sequence were detected, providing evidence for the proposed mechanism and resulting in the discovery of a new chemical entity. 相似文献