全文获取类型
收费全文 | 40676篇 |
免费 | 4369篇 |
国内免费 | 7419篇 |
专业分类
化学 | 34984篇 |
晶体学 | 1927篇 |
力学 | 2296篇 |
综合类 | 323篇 |
数学 | 2246篇 |
物理学 | 10688篇 |
出版年
2024年 | 76篇 |
2023年 | 351篇 |
2022年 | 624篇 |
2021年 | 846篇 |
2020年 | 1200篇 |
2019年 | 1080篇 |
2018年 | 962篇 |
2017年 | 1158篇 |
2016年 | 1619篇 |
2015年 | 1544篇 |
2014年 | 1885篇 |
2013年 | 3010篇 |
2012年 | 3419篇 |
2011年 | 2386篇 |
2010年 | 2052篇 |
2009年 | 2547篇 |
2008年 | 2732篇 |
2007年 | 2819篇 |
2006年 | 2633篇 |
2005年 | 2416篇 |
2004年 | 2378篇 |
2003年 | 2016篇 |
2002年 | 2160篇 |
2001年 | 1376篇 |
2000年 | 1425篇 |
1999年 | 1141篇 |
1998年 | 1003篇 |
1997年 | 825篇 |
1996年 | 812篇 |
1995年 | 728篇 |
1994年 | 686篇 |
1993年 | 520篇 |
1992年 | 542篇 |
1991年 | 319篇 |
1990年 | 264篇 |
1989年 | 155篇 |
1988年 | 153篇 |
1987年 | 93篇 |
1986年 | 80篇 |
1985年 | 91篇 |
1984年 | 66篇 |
1983年 | 41篇 |
1982年 | 40篇 |
1981年 | 33篇 |
1980年 | 28篇 |
1979年 | 30篇 |
1978年 | 13篇 |
1977年 | 15篇 |
1976年 | 10篇 |
1973年 | 15篇 |
排序方式: 共有10000条查询结果,搜索用时 18 毫秒
991.
Contributions to the Chemistry of Transition Metal Alkyl Compounds. 63. Preparation and Crystal Structure of Tetramethyltitanium Tetrahydrofuran Me4Ti · 2THF 1 dissoziates partially in n-pentane. The formed Me4Ti · THF 2 could be isolated. According to X-ray structure determination the molecules of 2 have a trigonalbipyramidal shape with the THF molecule in axial position. 相似文献
992.
Synthesis and Structure of Li3RhH6 — a Ternary Hydride with Isolated [RhH6]3? Octahedra The ternary rhodium hydride Li3RhH6 was synthesized by the reaction of lithium hydride with rhodium under a hydrogen pressure of 80 bar. X-ray investigations on powdered samples and an elastic neutron diffraction experiment on the deuterated compound led to the complete structure determination (space group: Pnma, Z = 4). The atomic arrangement is isotypic to the Na3RhH6 structure type. The crystal structure contains isolated [RhH6]3? octahedra, which are separated by the lithium ions. 相似文献
993.
新型化合物[Ni(en)3]2[Ni(en)2(H2O)2][As6V15O42]·4H2O晶体的水热合成与表征 总被引:1,自引:0,他引:1
金属氧酸盐因其在医药临床、工业催化、功能材料等方面的广泛应用而引起人们的关注[1~6], 其中, 有关钒化学的研究一直很活跃, 钒具有与钼、钨明显不同的结构特性, 钒可以采取VO4, VO5和VO6方式配位, 同时, 钒的价态可以是+3, +4和+5价. 由于钒可采取多种配位方式及多种价态, 与钼酸盐和钨酸盐相比, 钒酸盐更具有结构柔顺性, 同时易形成低价或混合价态物种.在以往的文献中, 有关P-V-O体系多金属氧酸盐的水热合成的研究已有大量的报道[7], 在常规溶液合成中, 人们已对As-V-O体系进行了相对深入的研究, 而有关水热合成的研究报道却很少, 已见报道的砷钒化合物有K6*6H2O[8,9], 4-[10], 6-[11](X=SO2-3, SO2-4, H2O). 为了探究水热条件下As-V-O体系的反应特性, 我们开展了这方面的研究工作, 并取得了突破性进展. 本文采用中温水热技术合成了含有机基团的砷矾超分子化合物2**4H2O, 探讨这类化合物的非线性光学性质、催化性质及其它功能特性将是一个非常有意义的研究领域. 相似文献
994.
Xi Yan Fuli Wu Yun Liu Jiamian Li Zebao Zheng Huiquing Yan Shufeng Si 《Frontiers of Chemistry in China》2006,1(3):315-319
A new water soluble compound trisodium 5,3′,5′-trisulfonate-2,3,4,4′-tetrahydroxy-deoxybenzoin (TTDB) was synthesized and
characterized by IR, UV, 1H NMR, and elemental analysis. The single crystal of TTDB was determined by X-ray single crystal diffraction. The scavenging
effect of compounds on hydroxy radicals was detected by fluorescent spectrophotometry. The electrochemical behavior of compounds
in nonaqueous solution DMF was carried out by means of cyclic voltammetry. The experimental result shows that the crystal
[C14H17Na3O18S3] belongs to monoclinic, space group C2/c with unit cell constants a = 1.4223(4) nm, b = 2.4327(8) nm, c = 1.3596(4) nm, α = 90°, β = 113.044(5)°, γ = 90°, Z = 8, V = 4.329(2) nm3, D
c = 1.925 mg/m3, F(000) = 2568, F
w = 638.43, R
1 = 0.0950, wR
2 = 0.2648. The half effective concentration EC50 of scavenging hydroxy radicals of compound THDB is 53.1 μmol/L, while that of scavenging hydroxy radicals of compound TTDB
is 47.3μmol/L. The electrochemistry redox processes of THDB and TTDB are different from each other.
__________
Translated from Chemical Journal of Chinese Universities, 2005, 26(9) (in Chinese) 相似文献
995.
Xi-yan Liu Dong Qiu Mei-li Guo Zhen-zhong Yang 《高分子科学》2005,(5):561-566
Sub-micron sized phenolic epoxy resin waterborne particles were prepared by phase inversion emulsification. Micro-phase separation occurred during the curing process at high temperature. The as-prepared samples possessed one glass transition temperature (Tg) and two exothermal processes during DSC heating scannings. After being thermally treated above the exothermal peak temperature, they possessed two glass transition temperatures with the disappearance of exothermal peaks, whilst a core/shell structure was formed. This was likely related with the outward diffusion of reactive oligomers to the outer layer of particles. 相似文献
996.
A. G. Matveeva E. I. Matrosov Z. A. Starikova G. V. Bodrin S. V. Matveev P. V. Petrovskii E. E. Nifant’ev 《Russian Chemical Bulletin》2005,54(11):2519-2534
The trifunctional ligand, 2,6-bis(diphenylphosphorylmethyl)-4-methylphenol (L
2), forms complexes with cerium(III) nitrate having a ligand to metal ratio of 1: 1, 2: 1, and 3: 1. The structures of these complexes in the solid state and
in solution were studied by X-ray diffraction, IR and NMR (1H and 31P) spectroscopy, and conformational analysis (molecular mechanics). The 2: 1 complexes of L
2 with lanthanum(III) and neodymium(III) nitrates were synthesized and characterized. In all complexes, the neutral ligand is coordinated through both phosphoryl
oxygen atoms. The hydroxy oxygen atom is coordinated only in some complexes, and the hydrogen atom of the hydroxy group is
involved in hydrogen bonding. The compositions and structures of the resulting complexes depend on the method of synthesis
and the nature of solvent. The ligand was found to undergo easy inner-sphere oxidation. The structure of one of the transformation
products was established by X-ray diffraction. Unlike the coordinated ligand, the free ligand is very stable to oxidation.
Dedicated to Corresponding Member of the Russian Academy of Sciences T. A. Mastryukova.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2440–2454, November, 2005. 相似文献
997.
The title compound N'-tert-butylaminocarbonyl-N-2-chlorophenoxyacetylthiou- rea has been synthesized for the first time. Complete assignments were achieved by IR, 1H NHR and single-crystal X-ray diffraction analyses. The inhibitory rate of the cellular growth of K562 cells (chronic myeloid 1eukemic cells) was measured using MTT [3-(4,5-dimethylthiazo-2-y1)-2,5-di- phenyltetra-zolium bromide] assay. The cell apoptosis was assessed by agarose gel electrophoresis to find that the title compound has antiproliferation and apoptosis inducing effects on K562 cells. In order to investigate the relationship between structure and activity of the target compound, we report its crystal structure and biological behavior in the present paper. Crystallographic data: C14H18- ClN3O3S, Mr = 343.82, orthorhombic, space group Pnma, a = 19.786(6), b = 6.789(2), c = 12.938(4) , V = 1738.0(9) 3, Z = 4, Dc = 1.314 g/cm3, F(000) = 720, μ(MoKα) = 0.354 mm-1, R = 0.0378 and wR = 0.0941. The molecule is a planar structure. 相似文献
998.
999.
Preparation and Crystal Structure of Rb2Ni3Se4 The compound Rb2Ni3Se4 was synthesized by heating a mixture of rubidium carbonate, nickel and selenium at 850°C in an atmosphere of hydrogen. The compound has a golden lustre and crystallizes with the K2Pd3S4-type structure; a = 10.555(3) Å, b = 27.588(6) Å, c = 6.031(6) Å, Z = 8, Fddd (No. 70). The structure can be described as a stacking of layers of the composition Rb2Ni3Se4 with a stacking sequence abcd. The electrostatic part of lattice energy (MAPLE) will be discussed for compounds of the compositions A2M3X4 (A K, Rb, Cs; M Ni, Pd, Pt and X S, Se). 相似文献
1000.
U(Ⅳ)配合物UNa2(pdc)3·6H2O的合成、结构及磁性研究 总被引:1,自引:4,他引:1
合成了一种含有+4价铀的配合物UNa2(pdc)3·6H2O(H2pdc=吡啶-2,6-二羧酸), 并详细研究了其晶体结构和磁学性质. 晶体属于单斜晶系, P21/n空间群, 晶胞参数a=1.0205(2) nm, b=2.2221(4) nm, c=1.2537(3) nm, β=94.98(3)°, V=2.8323(10) nm3, Z=4. 化合物的中心铀原子为九配位, π-π相互作用和氢键使得该化合物形成了三维立体结构. 相似文献