全文获取类型
收费全文 | 6996篇 |
免费 | 933篇 |
国内免费 | 883篇 |
专业分类
化学 | 5330篇 |
晶体学 | 76篇 |
力学 | 314篇 |
综合类 | 65篇 |
数学 | 906篇 |
物理学 | 2121篇 |
出版年
2024年 | 15篇 |
2023年 | 129篇 |
2022年 | 218篇 |
2021年 | 250篇 |
2020年 | 226篇 |
2019年 | 244篇 |
2018年 | 194篇 |
2017年 | 189篇 |
2016年 | 295篇 |
2015年 | 301篇 |
2014年 | 351篇 |
2013年 | 458篇 |
2012年 | 505篇 |
2011年 | 553篇 |
2010年 | 377篇 |
2009年 | 368篇 |
2008年 | 435篇 |
2007年 | 400篇 |
2006年 | 359篇 |
2005年 | 325篇 |
2004年 | 299篇 |
2003年 | 312篇 |
2002年 | 322篇 |
2001年 | 259篇 |
2000年 | 178篇 |
1999年 | 188篇 |
1998年 | 143篇 |
1997年 | 128篇 |
1996年 | 131篇 |
1995年 | 117篇 |
1994年 | 80篇 |
1993年 | 57篇 |
1992年 | 76篇 |
1991年 | 58篇 |
1990年 | 42篇 |
1989年 | 35篇 |
1988年 | 49篇 |
1987年 | 25篇 |
1986年 | 26篇 |
1985年 | 17篇 |
1984年 | 21篇 |
1983年 | 7篇 |
1982年 | 8篇 |
1981年 | 4篇 |
1980年 | 10篇 |
1979年 | 4篇 |
1976年 | 7篇 |
1975年 | 3篇 |
1972年 | 2篇 |
1957年 | 2篇 |
排序方式: 共有8812条查询结果,搜索用时 0 毫秒
41.
Chen-Xi Zhang Zhi-Liang Liu Dai-Zheng Liao Zong-Hui Jiang Shi-Ping Yan 《Journal of Molecular Structure》2003,650(1-3):21-26
A novel complex [Cu(NIT2Py)(PDA)(H2O)]·(CH3OH)(H2O) has been synthesized and structurally characterized by X-ray diffraction methods. It crystallizes in the monoclinic space group P2(1)/c. The structure consists of [Cu(NIT2Py)(PDA)(H2O)] moiety, one solvent methanol molecule and one water molecule. The copper(II) ion is in a distorted octahedral environment: one nitrogen atom and one oxygen atom from the NIT2Py, one nitrogen atom from the PDA (2,6-pyridine dicarboxylic acid) and one oxygen atom from the aqueous in the basal plane; two oxygen atoms from the PDA in the axial position. The units of [Cu(NIT2Py)(PDA)(H2O)] were connected as one dimension chain by the intermolecular hydrogen bonds. The complex exhibits intramolecular antiferromagnetic interactions between the Cu(II) ion and the NIT2Py. 相似文献
42.
报道了用Co3O4 作覆盖氧化剂分析有机锗化合物中碳氢元素的方法。通过对 9个样品的十几次分析 ,碳、氢的相对误差分别小于± 1.30 % ,4 .4 0 %。方法简便 ,结果稳定可靠 ,可用于含锗有机化合物的碳氢分析。 相似文献
43.
复合生物材料的研究进展 总被引:11,自引:0,他引:11
从力学性能的改善和降解速率的可调度等角度,总结了复合生物材料与单一组分的材料相比,在生物医学领域应用中所表现出的综合使用性能的优越性。综述了复合生物材料,特别是用于骨修复的各类有机/无机复合材料近年来的研究进展状况。提出将与人骨中磷灰石微晶类似的羟基磷灰石纳米粒子与可降解聚酯材料进行复合,能够得到具有优越骨诱导性能并且能够降解的新型骨修复材料。这方面的研究代表了有机/无机复合生物材料领域新的发展方向。 相似文献
44.
Diels-Alder reactions of six o-benzoquinones with dimethyl acetylenedicarboxylate has been examined. The yields of adducts vary with the natures of the o-benzoquinones, 3,4-Di-n-propyl-(1c), 3,6-di-n-propyl (1d). 3. 4-diallyl-(1e) and 3, 6-diallyl-o-benzoquinone (1f) are found to give bicyclic a-diketones exclusively without the formation of 1,4-dioxine derivatives, the yields ranging from 20 to 70%. In the case of 4, 5-dimethoxy-o-benzoquinone, dimethyl 4, 5-dimethoxyphthalate is produced in 42% yield, presumably derived from the decomposition of the corresponding initially formed α-diketone. 3, 6-Di-n-propyl-4, 5-dimethoxy-o-benzoquinone deteriorates without addition to dimethyl acetylenedicarboxylate upon heating. The additions of o-benzoquinones 1c , 1d and 1f to phenylacetylene are also studied. The yields of adducts, α-diketones, range from 23% to 82%. 相似文献
45.
An easily prepared and highly efficient monodentate phosphoramidite ligand derived from BINOL, (S)-2,2'-O,O-(1,1'-binaphthyl)-dioxo-N,N-diethylphospholidine, was examined in the hydrogenation of both enamides and alpha-dehydroamino acid derivatives. The catalyst provided remarkably high enantioselectivities (up to 99.6% ee for enamides and >99.9% ee for alpha-dehydroamino acid derivatives). 相似文献
46.
Lee JC Chang SW Liao CC Chi FC Chen CS Wen YS Wang CC Kulkarni SS Puranik R Liu YH Hung SC 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(2):399-415
A novel and convenient route for the synthesis of biologically potent and rare L-hexose derivatives from D-glucose is described. Conversion of diacetone-alpha-D-glucose (14) into 1,2:3,5-di-O-isopropylidene-beta-L-idofuranose (19) was efficiently carried out in two steps. Orthogonal isopropylidene rearrangement of compound 19 led to 1,2:5,6-di-O-isopropylidene-beta-L-idofuranose (27), which underwent regioselective epimerization at the C3 position to give the L-talo- and 3-functionalized L-idofuranosyl derivatives. Hydrolysis of compound 19 under acidic conditions furnished 1,6-anhydro-beta-L-idopyranose (35) in excellent yield, which was successfully transformed into the corresponding L-allo, L-altro, L-gulo, and L-ido derivatives via regioselective benzylation, benzoylation, triflation and nucleophilic substitution as the key steps. Applications of these 1,6-anhydro-beta-L-hexopyranoses as valuable building blocks to the syntheses of 4-methylcoumarin-7-yl-alpha-L-iduronic acid and the disaccharide moieties of bleomycin A(2) as well as heparan sulfate are highlighted. 相似文献
47.
2H-吡喃-2-酮及其衍生物是有机合成的蓬要中间体。对于它们的合成已有许多报道,例如利用烯醇醚或烯醇砖醚与丁酰氯反应;羰基化合物与甲氧亚甲螭丙二酸二甲酯反应;α-苯基丙醛酸酯与丙酮的成环缩合2,6-二氯-3-三氯甲基吡啶与亚甲基丁二酸酯的反应,邻氰基苯乙炔、二苯乙二酮和丙酮的反应。但上述方法往往原料较难得到,产率较低或操作麻烦。 相似文献
48.
A series of novel two-dimensional (2D) and three-dimensional (3D) praseodymium coordination polymers, namely, {[Pr3(PDA)4(HPDA)(H2O)8] x 8H2O}n (2), {[Pr2(PDA)3(H2O)3] x H2O}n (3), {[Pr(PDA)(H2O)4] x ClO4}n (4), and { [Pr2(PDA)2(H2O)5SO4] x 2H2O}n (5) (PDA = pyridine-2,6-dicarboxylic anion), was designed and synthesized under hydrothermal conditions. Complexes 1-3 (chainlike polymer, {[Pr(PDA)(HPDA)(H2O)2] x 4H2O}n (1) was also obtained independently by us, although it has been reported recently by Ghosh et al.) were fabricated successfully by simply tuning the Pr/PDA ratio and exhibited various and intriguing topological structures from a 1D chain to a 3D network. While the synthetic strategy of 5 was triggered and further performed only after 1 was structurally characterized. The complexes were characterized by X-ray single-crystal determination, spectroscopic, and variable-temperature magnetic susceptibility analyses. In complex 2 an unusual nanosized square motif as a building block constructed by eight Pr ions was further assembled into a highly ordered 2D grid compound. In complex 3 the decanuclear Pr metal-based structure as a repeat unit interpenetrated to form a novel 3D polymer. Complex 4 was a 3D network polymer fabricated through a hexanuclear Pr ring as a building block, and ClO4- anions as guests were trapped in the cavity. In complex 5 six Pr atoms, two SO4(2-) anions, and carboxylic oxygen bridges constructed an intriguing rectangle structure as a repeat unit in the grid to form a 2D coordination polymer in which the unique bi-bidentate coordination mode of SO4(2-) anion was observed. 相似文献
49.
Thermal treatment of Zn(NH3)(4)2+ precursor in ethanol solvent led to the formation of the tubular ZnO which exhibited strong ultraviolet photoluminescence around 385 nm at room temperature; TEM images showed the hollow tubules with approximately 450 nm in diameter and approximately 4 microns in length were built up by ZnO polycrystals. 相似文献
50.
Summary Three novel heterotrinuclear complexes have been prepared, [Cu2(oxdn)2Zn](ClO4)2 (1) and [Cu2(oxdn)2-M(H2O)2](ClO4)2 with M=Mn (2) and Co (3) [oxdn-oxamidobis (propionato)], and characterized by spectral data. The temperature dependence of the magnetic susceptibilities of (2) and (3) has been studied in the 4–300K range, and the exchange integrals J=–20.90cm–1 for (2) and J=–62.36cm–1 for (3) calculated. These results are commensurate with antiferromagnetic interactions between the adjacent metal ions. 相似文献