全文获取类型
收费全文 | 929篇 |
免费 | 29篇 |
国内免费 | 7篇 |
专业分类
化学 | 678篇 |
晶体学 | 8篇 |
力学 | 20篇 |
数学 | 138篇 |
物理学 | 121篇 |
出版年
2023年 | 6篇 |
2022年 | 11篇 |
2021年 | 13篇 |
2020年 | 18篇 |
2019年 | 13篇 |
2018年 | 12篇 |
2017年 | 14篇 |
2016年 | 14篇 |
2015年 | 19篇 |
2014年 | 24篇 |
2013年 | 57篇 |
2012年 | 70篇 |
2011年 | 62篇 |
2010年 | 38篇 |
2009年 | 12篇 |
2008年 | 47篇 |
2007年 | 58篇 |
2006年 | 50篇 |
2005年 | 42篇 |
2004年 | 46篇 |
2003年 | 47篇 |
2002年 | 31篇 |
2001年 | 11篇 |
2000年 | 13篇 |
1998年 | 5篇 |
1997年 | 10篇 |
1996年 | 12篇 |
1995年 | 13篇 |
1994年 | 12篇 |
1993年 | 4篇 |
1992年 | 11篇 |
1991年 | 11篇 |
1990年 | 8篇 |
1989年 | 6篇 |
1988年 | 4篇 |
1987年 | 7篇 |
1985年 | 4篇 |
1984年 | 9篇 |
1982年 | 7篇 |
1981年 | 7篇 |
1980年 | 6篇 |
1979年 | 5篇 |
1978年 | 13篇 |
1977年 | 8篇 |
1976年 | 12篇 |
1975年 | 11篇 |
1974年 | 7篇 |
1973年 | 9篇 |
1972年 | 7篇 |
1970年 | 7篇 |
排序方式: 共有965条查询结果,搜索用时 24 毫秒
111.
112.
Phillip J. Black 《Tetrahedron》2005,61(5):1363-1374
This paper describes the activation of 2-cyclohexen-1-ol (1) and 2-cyclopenten-1-ol (11) through the use of aluminium-catalysed transfer hydrogenation. The electronically activated substrates are demonstrated to undergo facile conjugate addition and, when the alcohol functional group is subsequently restored in a one-pot procedure, this leads to an indirect addition of nucleophiles to allylic alcohols. This novel methodology has been termed catalytic electronic activation.The aluminium tert-butoxide catalysed conversion of 2-cyclohexen-1-ol (1) into 2-(3-hydroxycyclohexyl)-2-methylmalononitrile (18) and 2-cyclopenten-1-ol (11) into 2-(3-hydroxycyclopentyl)-2-methylmalononitrile (16) in 90 and 60% yield, respectively has been demonstrated through an efficient domino Oppenauer/Michael addition/Meerwein-Ponndorf-Verley process. 相似文献
113.
Kidder MK Britt PF Zhang Z Dai S Hagaman EW Chaffee AL Buchanan AC 《Journal of the American Chemical Society》2005,127(17):6353-6360
Mesoporous silicas such as SBA-15 and MCM-41 are being actively investigated for potential applications in catalysis, separations, and synthesis of nanostructured materials. A new method for functionalizing these mesoporous silicas with aromatic phenols is described. The resulting novel hybrid materials possess silyl aryl ether linkages to the silica surface that are thermally stable to ca. 550 degrees C, but can be easily cleaved at room temperature with aqueous base for quantitative recovery of the organic moieties. The materials have been characterized by nitrogen physisorption, FTIR, NMR, and quantitative analysis of surface coverages. The maximum densities of 1,3-diphenylpropane (DPP) molecules that could be grafted to the surface were less than those measured on a nonporous, fumed silica (Cabosil) and were also found to decrease as a function of decreasing pore size (5.6-1.7 nm). This is a consequence of steric congestion in the pores that is magnified at the smaller pore sizes, consistent with parallel studies conducted using a conventional silylating reagent, 1,1,3,3-tetramethyldisilazane. Pyrolysis of the silica-immobilized DPP revealed that pore confinement leads to enhanced rates and altered product selectivity for this free-radical reaction compared with the nonporous silica, and the rates and selectivities also depended on pore size. The influence of confinement is discussed in terms of enhanced encounter frequencies for bimolecular reaction steps and pore surface curvature that alters the accessibility and resultant selectivity for hydrogen transfer steps. 相似文献
114.
115.
The convergence of the full perturbation theory expansion for the Fermi contact term in the spin-spin coupling constant of hydrogen fluoride has been studied. By examining the contribution of higher virtual states as the basis set is expanded to 18 atomic orbitals, it is shown that at this level of approximation the expansion does not converge. The need to also establish convergence before accepting values calculated from configuration interaction wavefunctions is discussed.The Puerto Rico Nuclear Center is operated by the University of Puerto Rico for the United States Atomic Energy Commission under Contract No. AT(40-1)-1833. 相似文献
116.
117.
118.
Phillip Zhe Sun 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2010,202(2):155-161
Chemical exchange saturation transfer (CEST) MRI is increasingly used to probe mobile proteins and microenvironment properties, and shows great promise for tumor and stroke diagnosis. However, CEST MRI contrast mechanism is complex, depending not only on the CEST agent concentration, exchange and relaxation properties, but also varying with experimental conditions such as magnetic field strength and RF power. Hence, it remains somewhat difficult to quantify apparent CEST MRI contrast for properties such as pH, temperature and protein content. In particular, CEST MRI is susceptible to RF spillover effects in that RF irradiation may directly saturate the bulk water MR signal, leading to an optimal RF power at which the CEST contrast is maximal. Whereas RF spillover is generally considered an adverse effect, it is noted here that the optimal RF power strongly varies with exchange rate, although with negligible dependence on labile proton concentration. An empirical solution suggested that optimal RF power may serve as a sensitive parameter for simultaneously determining the labile proton content and exchange rate, hence, allowing improved characterization of the CEST system. The empirical solution was confirmed by numerical simulation, and experimental validation is needed to further evaluate the proposed technique. 相似文献
119.
Black PJ Cami-Kobeci G Edwards MG Slatford PA Whittlesey MK Williams JM 《Organic & biomolecular chemistry》2006,4(1):116-125
Alcohols have been employed as substrates for C-C bond-forming reactions which involve initial activation by the temporary removal of hydrogen to form an aldehyde. The intermediate aldehyde is converted into an alkene via a Horner-Wadsworth-Emmons reaction, nitroaldol and aldol reactions. The 'borrowed hydrogen' is then returned to the alkene to form a C-C bond. 相似文献
120.