全文获取类型
收费全文 | 968篇 |
免费 | 158篇 |
国内免费 | 373篇 |
专业分类
化学 | 783篇 |
晶体学 | 14篇 |
力学 | 65篇 |
综合类 | 18篇 |
数学 | 81篇 |
物理学 | 538篇 |
出版年
2024年 | 8篇 |
2023年 | 24篇 |
2022年 | 36篇 |
2021年 | 35篇 |
2020年 | 22篇 |
2019年 | 37篇 |
2018年 | 27篇 |
2017年 | 33篇 |
2016年 | 30篇 |
2015年 | 21篇 |
2014年 | 58篇 |
2013年 | 40篇 |
2012年 | 59篇 |
2011年 | 62篇 |
2010年 | 54篇 |
2009年 | 46篇 |
2008年 | 63篇 |
2007年 | 73篇 |
2006年 | 64篇 |
2005年 | 81篇 |
2004年 | 73篇 |
2003年 | 47篇 |
2002年 | 60篇 |
2001年 | 61篇 |
2000年 | 45篇 |
1999年 | 33篇 |
1998年 | 31篇 |
1997年 | 29篇 |
1996年 | 31篇 |
1995年 | 27篇 |
1994年 | 22篇 |
1993年 | 19篇 |
1992年 | 25篇 |
1991年 | 21篇 |
1990年 | 13篇 |
1989年 | 16篇 |
1988年 | 13篇 |
1987年 | 8篇 |
1986年 | 9篇 |
1985年 | 9篇 |
1984年 | 3篇 |
1983年 | 2篇 |
1982年 | 2篇 |
1981年 | 2篇 |
1980年 | 5篇 |
1979年 | 2篇 |
1963年 | 6篇 |
1957年 | 1篇 |
1948年 | 1篇 |
1946年 | 1篇 |
排序方式: 共有1499条查询结果,搜索用时 15 毫秒
11.
12.
采用溶胶-凝胶法合成了一种V2O5/C复合材料.扫描电镜(SEM)和红外光谱(FTIR)分析表明,这是一种外层V2O5胶体包覆内层乙炔分子的多孔复合材料.以V2O5/C作正极,锌片为负极,Zn(ClO4)2溶液为电解质组成水相锌二次电池,采用循环伏安(CV)和电化学阻抗谱(EIS)等方法研究发现:V2O5:C质量比为1:1时电极具有最好的电化学性能,电池开路电压达1.64 V; Zn2+能分别在1.01 V和1.26 V处分步嵌入V2O5/C结构中A、B两种位置,其嵌入电流密度峰值最高可达70 mA•g-1,并且具有较好的循环充放电性能;在一定放电深度下,V2O5/C电极反应速率受Zn2+的扩散过程控制. 相似文献
13.
14.
The paper shows the ability of the fluorochrome tris(2,2'-bipyridine) ruthenium (II) (Rubipy) to detect heparan sulfate, heparin, and heparinase activity of M3 murine mammary adenocarcinoma cells as well as bacterial heparinases I, II, and III in native polyacrylamide gel electrophoresis (PAGE). The technique is based on the electrophoretic mobility of high molecular weight heparins and subsequent staining with Rubipy (50 micrograms/mL). The minimum content of heparin detected by fluorescence in a UV transilluminator was 25-50 ng. The number of Rubipy molecules bound to heparin, determined in relationship to the number of disaccharide units (DU), showed that two to six heparin disaccharide units are bound by each fluorochrome molecule. Scatchard plot analysis showed one Rubipy-binding site (Kd = (8.56 +/- 2.97) x 10(-5) M). Heparinase activity was determined by densitometric analysis of the fluorescence intensity of the heparin-containing band of the gel. While heparinase I (EC 4.2.2.7.) degraded heparin and, to a lower degree, partially N-desulfated N-acetylated heparin (N-des N-Ac), heparinase II (no EC number) could efficiently degrade heparan sulfate (HS) and partially N-des N-Ac heparin. Finally, heparinase III (EC 4.2.2.8.) degraded HS almost exclusively. Only heparin and N-des N-Ac heparin were substrates for M3 tumor cell heparinases. We describe a qualitative, sensitive and simple method to detect heparinase activity and determine its substrate specificity using Rubipy fluorescence with heparin and heparan sulfate in multiple biological samples tested in parallel. 相似文献
15.
16.
用量子化学从头算方法(HF/6-31G)和密度泛函理论(DFT)的B3LYP方法,以6-31G标准基组加一个极化函数,对(ClAlNH)n(n=1-10)簇合物的几何构型,电子结构和红外光谱进行了优化,并讨论了聚合反应(ClAlNH)m→(ClAlNH)n的热力学效应,结果表明,(ClAlNH)n系列簇合物的基态稳定结构为Cs(n=1),D2h(n=2),D3h(n=3),Td(n=4),Cs(n=5),D3d(n=6),Cs(n=7),S4(n=8),D3h(n=9),C2h(n=10,n=2,4,6,8,10等偶数对应的(ClAlNH)n簇化合物的结构比n等于奇数量更稳定。 相似文献
17.
Fry FH Holme AL Giles NM Giles GI Collins C Holt K Pariagh S Gelbrich T Hursthouse MB Gutowski NJ Jacob C 《Organic & biomolecular chemistry》2005,3(14):2579-2587
Certain cancer cells proliferate under conditions of oxidative stress (OS) and might therefore be selectively targeted by redox catalysts. Among these catalysts, compounds containing a chalcogen and a quinone redox centre are particularly well suited to respond to the presence of OS. These catalysts combine the specific electrochemical features of quinones and chalcogens. They exhibit high selectivity and efficiency against oxidatively stressed rat PC12, human Jurkat and human Daudi cells in cell culture, where their mode of action most likely involves the catalytic activation of existent and the generation of new reactive oxygen species. The high efficiency and selectivity shown by these catalysts makes them interesting for the development of anti-cancer drugs. 相似文献
18.
Matsumoto GI Friedmann EI Watanuki K Ocampo-Friedmann R 《Journal of chromatography. A》1992,598(2):267-276
Saponified extracts of rock samples colonized by cryptoendolithic microbial communities from the McMurdo Dry Valleys of Southern Victoria Land, Antarctica, were separated into hydrocarbon and fatty acid fractions by silica gel column chromatography. Hydrocarbons and methyl esters of fatty acids were analyzed by capillary gas chromatography-mass spectrometry. Unusually, a suite of long-chain anteiso-alkanes (a-C20 to a-C30) and anteiso-alkanoic acids (a-C20 to a-C30) were detected in many samples, together with straight-chain, branched and/or cyclic and acyclic isoprenoid compounds. These novel compounds are probably derived from unidentified heterotrophic bacteria or symbiotic processes in a unique microbial community in the Antarctic cold desert and suggest the occurrence of a special biosynthetic pathway. Long-chain anteiso-alkanes are probably formed through microbial decarboxylation of corresponding anteiso-alkanoic acids. They may serve as new biomarkers in environmental and geochemical studies. 相似文献
19.
加速剂对化学镀镍层组成与结构的影响 总被引:3,自引:0,他引:3
加速剂对化学镀镍层组成与结构的影响方景礼,武勇,韩克平,张敏(南京大学应用化学研究所配位化学国家重点实验室南京210093)关键词化学镀镍,Ni0P合金,加速剂,硫脲化学镀镍磷合金具有耐蚀性、可焊性、厚度均匀和硬度高等优点,已得到广泛应用。为提高生产... 相似文献
20.
Campomanes P Menéndez MI Cárdenas-Jirón GI Sordo TL 《The journal of physical chemistry. A》2005,109(34):7822-7831
A theoretical analysis of the silver-induced ring expansion of N-chloro-N-methyl-1-hydroxycyclopropylamine to form N-methyl-2-azetidinone, and of the Cl(-) elimination from this substrate without Ag(+) assistance, was performed using the B3LYP method and the 6-31+G(d) basis set for C, N, O, H, and Cl atoms and the relativistic effective core pseudopotential LANL2DZ complemented with one set of f polarization functions (zeta(f) = 0.473) for the Ag atom. The partial Ag(+)-assisted extrusion of Cl(-) at the rate-determining transition state provokes an important change in the nodal properties of the frontier molecular orbitals of the H(3)CClNCOHAg(+) fragment, thus making very stabilizing HOMO-LUMO interactions between this fragment and the C(2)H(4) moiety possible. This interaction leads to the ring opening and release of most of the strain energy, giving rise to a low energy barrier for the process. Also, by assisting the Cl(-) extrusion, Ag(+) avoids the elimination of the hydroxyl hydrogen atom, which would provoke the fragmentation of the system instead of the formation of the beta-lactam. 相似文献