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21.
A. K. Galwey 《Journal of Thermal Analysis and Calorimetry》2005,82(2):423-437
Summary A representational model, proposed to account for the physical changes that accompany the melting of alkali halides, was described
in Part 1 [1]. The liquid is portrayed as undergoing continual dynamic structural reorganization of its constituent ions between
individual small domains, zones of various regular, crystal-type arrays. These alternative arrangements are stabilized by
the enthalpy of melting, which, in liquids, relaxes the restriction for solids that only the single, most stable, crystal
structure can be present. The dynamic character of the melt accounts for its fluid character and the loss of long-range order
[1, 2]. This model is extended here to consider the phase diagrams of binary, common ion, alkali halide mixtures comprehensively
reviewed in [3]. Factors determining whether each of these yields a eutectic, or a solid solution, on cooling are discussed
and several trends in the 70-phase diagrams are identified. Eutectic formation, involving maintenance of the liquid state
below the melting points of the pure components, is ascribed to the participation, in an extended dynamic equilibrium, of
additional domains having the regular structures characteristic of double salts. The known crystalline double binary halides
[3], Li/Cs or Rb/F, Cl, Br or I, melt at temperatures well below those of the simpler pure component salts. It is concluded
that the set/liq model for melting, proposed in [1, 2], accounts for some important properties of the phase diagrams presented
in [3]. 相似文献
22.
23.
Guihua Huang Yipeng Huang Wei Xu Qiuhong Yao Xiaofang Liu Caifeng Ding Xi Chen 《中国化学快报》2019,30(5):1021-1023
Using cesium lead halide perovskite nanocrystals, CsPb(Cl/Br)_3, as a light absorber, we report a highly effective UV and blue light blocking film. The CsPb(Cl/Br)_3 nanocrystals are well dispersed in the ethyl cellulose(EC) matrix to compose a UV and blue light shielding film, and the absorption edge of the film is tunable by adjusting Cl to Br ratio using anion exchange. The CsPbCl_2 Br-EC film exhibits a transmittance of 5% at 459 nm, 90% at 478 nm and 95% in the range of 500–800 nm, which makes it excellent for UV and blue light shielding. In addition, the as-prepared EC-CsPb(Cl/Br)_3 film shows excellent photostability under UV irradiation. Results demonstrate that this EC-CsPb(Cl/Br)_3 based materials with sharp absorbance edges, tunable blocking wavelength, and high photostability can be useful for the applications in UV and blue light blocking and optical filters 相似文献
24.
Quaternization reactions of poly(vinylpyridines) with alkyl halides show retardation in excess of that predicted by the classical second-order kinetics. Based on the classical collision and transition state theories, a kinetic model has been developed to quantify such retardation, in which the overall reaction rate is characterized by a rate constant k0 of the intrinsic reactivity between a pyridyl group and an alkyl halide group, and by a steric hindrance effect parameter α. The latter accounts for the degree to which the rate of collisions of reactants is reduced, or to which the freedom of movement of the reactants in the transition state is restricted as the reaction proceeds. The resulting kinetic expression has been validated using experimental results reported in the literature and those of our own. The functional dependence of k0 and α values on the nature of poly(vinylpyridines) and that of alkyl halides is explained. Other factors affecting k0 and α, including changes in macromolecular dimensions and/or in the distribution of residue environment, quality of solvent, and reaction temperature, are discussed. © 1993 John Wiley & Sons, Inc. 相似文献
25.
A highly efficient Suzuki cross-coupling reaction between benzylic halides and aryl boronic acids using palladium chloride as catalyst in acetone:water (3:1) as the solvent system has been developed. High yields of products, mild reaction conditions and short reaction times in the absence of ligand are important features of this method. 相似文献
26.
27.
CHEN Wen-Tong GUO Guo-Cong ZENG Xi-Rui LI Xin-Fa FANG Xiao-Niu KUANG Han-Mao LIU Dong-Sheng LIU Li-Min 《结构化学》2007,26(10)
The title compound (4,4'-H2bipy)[CdBr4]·H2O 1 has been synthesized via hydrothermal reaction and characterized by X-ray diffraction. The crystal belongs to monoelinic,space group P21/c with a=8.260(3), b=23.926(7), c=9.774(2) (A), β=106.777(9)°,C10H12Br4CdN2O, Mr=608.26, V=1849.4(9)(A)3, Z=4, Dc=2.185 g/cm3, S=1.005, μ(MoKα)=9.814 mm-1, F(000)=1128, R=0.0646 and wR=0.0989. The crystal structure analysis of 1reveals that the title compound features an isolated structure, based on discrete 4,4'-H2bipy moieties and lattice water molecules which are linked by hydrogen bonds together with tetrahedral cadmium atoms terminally coordinated by four bromine atoms. 相似文献
28.
The reactions of 1,4-bis[2-(tributylstannyl)tetrazol-5-yl]benzene with α,ω-dibromoalkanes were carried out in order to synthesise pendant alkyl halide derivatives of the parent bis-tetrazole. This led to the formation of several alkyl halide derivatives, substituted variously at N1 or N2 on the tetrazole ring. The crystal structures of 1,4-bis[(2-(4-bromobutyl)tetrazol-5-yl)]benzene (2-N,2-N′), 1,4-bis[(2-(4-bromobutyl)tetrazol-5-yl)]benzene (1-N,2-N′) and 1,4-bis[(2-(8-bromooctyl)tetrazol-5-yl)]benzene (2-N,2-N′) are reported. Further discussion involves the structure of 1,4-bis[2-(6-bromohexyl)-2H-tetrazol-5-yl]benzene (2-N,2-N′) previously reported. 相似文献
29.
A. L. Chistyakov I. V. Stankevich N. P. Gambaryan I. A. Tikhonova V. B. Shur 《Russian Chemical Bulletin》1995,44(6):997-1004
Geometries and electronic structures of the complexes of halide anions with cyclic trimerico-phenylenemercury, (o-C6H4Hg)3, perfluoro-o-phenylenemercury, (o-C6F4Hg)3, vinylenemercury, (C2H2Hg)3, and perfluorovinylenemercury, (C2F2Hg)3, were modelled by the MNDO method. Calculations were performed for [L-X]– semisandwich complexes, [X-L-X]2– bipyramidal complexes, and [L-X-L]– sandwich complexes (where X=Hal,L is a mercury-containing macrocycle). Based on the results of calculations, we concluded that it was advantageous to describe the chemical bonding between halide anions and mercury-containing macrocycles in terms of generalized chemical bonds, which were successfully used for -complexes of transition metals. In the [L-X]– semisandwich complexes, the halide anion and the metallacycle are involved in the formation of three generalized chemical bonds: one headlight-shaped -bond and two two-lobe -bonds. In the [X-L-X]2– bipyramidal complexes, each halide anion forms three generalized chemical bonds with the macrocycle. It is possible because the macrocycleL has unoccupied molecular orbitals suitable for the formation of such bonds; these MOs consist mainly of the orbitals of mercury atoms directed toward both the upper and lower halogen atoms. In the [L-X-L]– sandwich complexes, the halide anion cannot be bonded to each ringvia three bonds, and, hence, an unsymmetrical structure is formed, in which the rings are located at different distances from the central atom: the [L-X]– semisandwich complex solvated by macrocycleL.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1035–1042, June, 1995.The authors are grateful to V. I. Faustov for valuable remarks.This work was supported by the Russian Foundation for Basic Research (Project No. 93-03-18342). 相似文献
30.
Anna Maria Zawisza 《Tetrahedron letters》2007,48(38):6738-6742
The Pd-catalyzed homocoupling of aryl halides in a basic DMF solution is often accompanied by the dehalogenation of the substrate as side reaction. When an inorganic base such as sodium bicarbonate is used, the reducing role of the solvent has been demonstrated using DMF-d7 and GC/MS analysis. 相似文献