全文获取类型
收费全文 | 42793篇 |
免费 | 4110篇 |
国内免费 | 7728篇 |
专业分类
化学 | 36314篇 |
晶体学 | 1913篇 |
力学 | 2488篇 |
综合类 | 319篇 |
数学 | 2370篇 |
物理学 | 11227篇 |
出版年
2024年 | 106篇 |
2023年 | 404篇 |
2022年 | 841篇 |
2021年 | 891篇 |
2020年 | 1232篇 |
2019年 | 1106篇 |
2018年 | 966篇 |
2017年 | 1186篇 |
2016年 | 1657篇 |
2015年 | 1573篇 |
2014年 | 1953篇 |
2013年 | 3048篇 |
2012年 | 3458篇 |
2011年 | 2477篇 |
2010年 | 2104篇 |
2009年 | 2658篇 |
2008年 | 2823篇 |
2007年 | 2917篇 |
2006年 | 2712篇 |
2005年 | 2463篇 |
2004年 | 2408篇 |
2003年 | 2061篇 |
2002年 | 2185篇 |
2001年 | 1417篇 |
2000年 | 1446篇 |
1999年 | 1151篇 |
1998年 | 1018篇 |
1997年 | 832篇 |
1996年 | 832篇 |
1995年 | 740篇 |
1994年 | 697篇 |
1993年 | 528篇 |
1992年 | 543篇 |
1991年 | 321篇 |
1990年 | 265篇 |
1989年 | 207篇 |
1988年 | 197篇 |
1987年 | 140篇 |
1986年 | 125篇 |
1985年 | 136篇 |
1984年 | 108篇 |
1983年 | 86篇 |
1982年 | 81篇 |
1981年 | 74篇 |
1980年 | 71篇 |
1979年 | 72篇 |
1978年 | 55篇 |
1977年 | 56篇 |
1974年 | 44篇 |
1973年 | 50篇 |
排序方式: 共有10000条查询结果,搜索用时 14 毫秒
71.
叙述了用θ-2θ型X射线衍射仪精确测定电解质溶液结构的新实验技术。设计制作了具有恒温功能的超厚液体样品池,并建立了样品池窗口强度的校正方法。优化了液体X射线衍射数据和结构参数精细化的计算机程序,获得了非常令人满意的实验结果。由θ-2θ型X射线衍射仪精确测定的径向分布函数与θ-θ型衍射仪自由散射比较,表明DRF分辨率有所提高。 相似文献
72.
73.
Synthesis, properties, and structure of dimethylgold(III) complexes [(CH3)2AuI]2 and (CH3)2AuS2CN(C2H5)2 总被引:1,自引:0,他引:1
Volatile diethyldithiocarbamate of dimethylgold(III) was prepared by the interaction of dimethylgold(III) iodide with sodium diethyldithiocarbamate. The complex is examined by the elemental analysis, DTA, IR and electronic spectroscopy. The starting dimeric complex [(CH3)2AuI]2 and a novel monomeric volatile gold(III) complex (CH3)2AuS2CN(C2H5)2 with the AuC2S2 coordination core were investigated by single crystal X-ray diffraction for the first time. 相似文献
74.
The ab initio calculation of the title compound was carried out at HF as well as DFT level of theory. The full geometry optimization of the ligand was carried out using 6-31G(d) basis set. The results obtained were correlated with the single crystal X-ray data, also reported in this paper, shows close resemblance between these two. The influence of electron correlation effects also was studied by carrying out geometry optimization at the MP2 level. The attempts were also made to ascertain the most stable tautomer of the said compound. 相似文献
75.
Yu. B. Vysotsky V. S. Bryantsev O. A. Gorban 《Chemistry of Heterocyclic Compounds》2002,38(12):1451-1468
The effects of benzannellation, phenyl substitution at the nitrogen atom, protonation at the carbene carbon, ionization, and the state of the carbene center (2 or 2) on the electronic structure, diamagnetic susceptibility, induced -electron ring currents, the 1H, 13C, and 14N chemical shifts, and the energies of the lowest electronic transitions of imidazol-2-ylidenes and their oxo and thio analogs were examined in the bound version of -electron perturbation theory. The calculated and experimental data are compared. 相似文献
76.
Evert J. Ditzel Xavier L. R. Fontaine Norman N. Greenwood John D. Kennedy Mark Thornton-Pett 《无机化学与普通化学杂志》1992,616(10):79-85
The action of SMe2 on the ten-vertex nido-ruthenaborane [6-(η6-C6Me6)RuB9Hl3] ( 1 ) provides a high-yield route to the unsubstituted isocloso-ruthenaborane [1-(η6-C6Me6)RuB9H9] (2). The benzene analogue [1-(η6-C6Me6)RuB9H9] is prepared similarly. By contrast, reaction of (1) with PhNH2 gives a variety of B-phenylamino isocloso derivatives, including orange crystals of [1-(η6-C6Me6)-2-(PhNH)-isocloso-1-RuB 9 H8] ( 3 ), red-orange [1-(η6-C6Me6)-2,3-(PhNH)2-isocloso-1-RuB9H7] ( 4 ) and dark-red [1-(η6-C6Me6)-5,6,7-(PhNH)3-isocloso-1-RuB9H6] ( 5 ). Detailed 1H and 11B nmr properties of these various compounds are described. The structure of ( 3 ) has been established by a single-crystal X-ray diffraction study of the solvate [1-(η6-C6Me6)-2-(PhNH)-isocloso-1-RuB9H8] · 1/2 CH2Cl2; the crystals were monoclinic, space group C2/c, with a = 1895.1(3), b = 1556.6(3), c = 1716.4(3) pm, β = 104.37(1)° and z = 8. 相似文献
77.
The reaction of alkali metal hexacyanoferrate(II/III) with (CH2)6N4 (hexamethylenetetramine, abbreviated HMT) in an acidic medium yielded crystalline compounds of stoichiometries HK2[Fe111(CN)6]·2HMT·4H2O, H2K2[Fe11(CN)6]·2HMT·4H2O, and HNa2[Fe111(CN)6]· 2HMT·5H2O. Their crystal structures are based on a packing of three molecular components: neutral and/orprotonated HMT, hexacyanoferrate, and an alkali metal ion-water cluster. The resulting three-dimensional supramolecular framework is constructed from the coordination of the alkali metal ion by aqua ligands as well as [Fe(CN)6]{n–} and HMT units, and further stabilization is achieved by hydrogen bonding between water molecules and the noncoordinated nitrogen atoms of HMT and hexacyanoferrate. 相似文献
78.
The Reaction of SeCl4 with Transition Metal Tetrachlorides. Synthesis and Crystal Structures of (SeCl3)2MCl6 with M = Zr, Hf, Mo, Re The transition metal tetrachlorides ZrCl4, HfCl4 and MoCl4 react with SeCl4 in closed ampoules at temperatures of 140°C to (SeCl3)2MCl6 (M = Zr, Hf, Mo) which are all isotypic and crystallize in the (SeCl3)2ReCl6 structure type (orthorhombic, Fdd2, Z = 8, lattice constants for M = Zr: a = 1165.7(1)pm, b = 1287.2(2)pm, c = 2180.2(2)pm; for M = Hf: a = 1162.9(2)pm, b = 1285.0(2)pm, c = 2178.2(3)pm; for M = Mo: a = 1153.8(1)pm, b = 1267.7(1)pm, c = 2147.4(2)pm). The Cl? ions form a hexagonal closest packing with one fourth of the octahedral holes filled by Se4+ and M4+ in an ordered way. The MCl6 octahedra are regular, the SeCl6 octahedra are distorted with 3 short and 3 long Se? Cl bonds (mean 215 pm and 287 pm). The structures can thus be regarded as built of SeCl3+ and MCl62? ions. Magnetic susceptibility measurements show for M = Zr the expected diamagnetic behavior, for M = Mo and Re paramagnetic behavior according to the Curie-Weiss law with magnetic moments of 2.5 B. M. for M = Mo and 3.7 B. M. for M = Re corresponding to 2 and 3 unpaired electrons respectivly. 相似文献
79.
Many polysaccharide chains can adopt ordered helical and ribbon-like secondary structures. It seems however that these chains are often so stiff and extended that the cooperative interactions necessary for stability in the solvent environment can only be achieved when inter-chain as well as intra-chain interactions are favorable. Hence we commonly find two-or more-stranded associations of helices, of ribbons, or of helices with ribbons. These can be regarded as tertiary and higher levels of structure. The ordered secondary structure characteristically requires a regular repeating sequence of sugar residues, and the termination of this sequence by insertion of a residue of different type may also terminate the secondary structure and hence the association in which it is involved. This is the mechanism by which native polysaccharides may link up to form three dimensional networks, or gels, in which state they perform their natural roles in maintaining the hydration and integrity of biological tissues. For several polysaccharides there is evidence that the mechanism of biological control over the fine topology and properties of the gel network is mediated by enzymes which modify sugar residues at the polymer level to change the pattern of “interrupting” sugar residues. 相似文献
80.
SANS data have been obtained for C12H25 (OC2H4)2SO4 Na. Results have been obtained for i) a series of solutions of variable concentration of the surfactant, ii) an approximately 0.07 M surfactant concentration to which variable amounts of NaCl were added, iii) a series of solutions 0.058M in surfactant but in different D2O-H2O mixtures. The SANS data can be described in terms of a model of monodispersed hard spheres interacting via a screened Coulombic potential. The micelles seem to be able to tolerate substantial amounts of salt without changing the internal structure. 相似文献