全文获取类型
收费全文 | 850篇 |
免费 | 15篇 |
国内免费 | 1篇 |
专业分类
化学 | 491篇 |
晶体学 | 9篇 |
力学 | 28篇 |
数学 | 100篇 |
物理学 | 238篇 |
出版年
2023年 | 8篇 |
2022年 | 6篇 |
2020年 | 7篇 |
2019年 | 10篇 |
2017年 | 6篇 |
2016年 | 18篇 |
2015年 | 13篇 |
2014年 | 10篇 |
2013年 | 38篇 |
2012年 | 44篇 |
2011年 | 47篇 |
2010年 | 25篇 |
2009年 | 15篇 |
2008年 | 34篇 |
2007年 | 31篇 |
2006年 | 33篇 |
2005年 | 41篇 |
2004年 | 23篇 |
2003年 | 24篇 |
2002年 | 22篇 |
2001年 | 13篇 |
2000年 | 37篇 |
1999年 | 8篇 |
1998年 | 12篇 |
1997年 | 13篇 |
1996年 | 16篇 |
1995年 | 10篇 |
1994年 | 8篇 |
1993年 | 16篇 |
1992年 | 12篇 |
1991年 | 9篇 |
1990年 | 6篇 |
1989年 | 7篇 |
1988年 | 14篇 |
1987年 | 8篇 |
1986年 | 6篇 |
1985年 | 15篇 |
1984年 | 21篇 |
1983年 | 11篇 |
1982年 | 21篇 |
1981年 | 14篇 |
1980年 | 17篇 |
1979年 | 7篇 |
1977年 | 10篇 |
1976年 | 10篇 |
1975年 | 12篇 |
1974年 | 9篇 |
1973年 | 10篇 |
1972年 | 8篇 |
1966年 | 6篇 |
排序方式: 共有866条查询结果,搜索用时 15 毫秒
91.
Kundu S Bhangale AS Wallace WE Flynn KM Guttman CM Gross RA Beers KL 《Journal of the American Chemical Society》2011,133(15):6006-6011
Enzymes immobilized on solid supports are increasingly used for greener, more sustainable chemical transformation processes. Here, we used microreactors to study enzyme-catalyzed ring-opening polymerization of ε-caprolactone to polycaprolactone. A novel microreactor design enabled us to perform these heterogeneous reactions in continuous mode, in organic media, and at elevated temperatures. Using microreactors, we achieved faster polymerization and higher molecular mass compared to using batch reactors. While this study focused on polymerization reactions, it is evident that similar microreactor based platforms can readily be extended to other enzyme-based systems, for example, high-throughput screening of new enzymes and to precision measurements of new processes where continuous flow mode is preferred. This is the first reported demonstration of a solid supported enzyme-catalyzed polymerization reaction in continuous mode. 相似文献
92.
Strotman NA Baxter CA Brands KM Cleator E Krska SW Reamer RA Wallace DJ Wright TJ 《Journal of the American Chemical Society》2011,133(21):8362-8371
The first example of an intramolecular asymmetric reductive amination of a dialkyl ketone with an aliphatic amine has been developed for the synthesis of Suvorexant (MK-4305), a potent dual Orexin antagonist under development for the treatment of sleep disorders. This challenging transformation is mediated by a novel Ru-based transfer hydrogenation catalyst that provides the desired diazepane ring in 97% yield and 94.5% ee. Mechanistic studies have revealed that CO(2), produced as a necessary byproduct of this transfer hydrogenation reaction, has pronounced effects on the efficiency of the Ru catalyst, the form of the amine product, and the kinetics of the transformation. A simple kinetic model explains how product inhibition by CO(2) leads to overall first-order kinetics, but yields an apparent zero-order dependence on initial substrate concentration. The deleterious effects of CO(2) on reaction rates and product isolation can be overcome by purging CO(2) from the system. Moreover, the rate of ketone hydrogenation can be greatly accelerated by purging of CO(2) or trapping with nucleophilic secondary amines. 相似文献
93.
Manandhar E Broome JH Myrick J Lagrone W Cragg PJ Wallace KJ 《Chemical communications (Cambridge, England)》2011,47(31):8796-8798
A simple pyrene-based triazole receptor has been synthesised and shown to self-assemble in the presence of ZnCl(2) in an exclusively 2:1 ratio, whereas a mixture of 2:1 and 1:1 ratios are observed for other Zn(2+) salts. The pyrene units are syn in orientation; this is supported by a strong excimer signal observed at 410 nm in the presence of ZnCl(2) in acetonitrile. DFT calculations and 2D NMR support the proposed structure. 相似文献
94.
Free radicals are observed in γ-irradiated single crystals of 5-nitrouracil with the unpaired electron showing hyperfine interaction with one nitrogen atom. The principal values of hyperfine coupling are Ax = 22·5 g, Ay = 25·2 g, and Az = 40·0 g, and the principal values of the spectroscopic splitting factor are gu = 2·0117, gv = 2·0064 and gw = 2·0027. The relationship of the directions of the corresponding principal axes to the molecular orientations show that the unpaired electron must be located in an sp 2 orbital on either N(1) or N(5). Considerations of the mechanism of radical formation and comparison to radiation damage in other molecules make the N(1) location seem more probable. The π interaction of the nitro group on C(5) evidently prevents the formulation of free radicals with the unpaired electron on C(5). That carbon atom is the most common location of unpaired electron density in other pyrimidine free radicals. 相似文献
95.
The preparation and use of polymeric dispersed mercury electrodes were investigated. Both micro- and macroelectrodes were considered and it was found that the polymer-coated electrodes have greater chemical and mechanical stability than conventional mercury thin-film electrodes. It was also found that the polymeric microelectrodes display several advantages in performance over the macroelectrode counterpart. 相似文献
96.
97.
98.
The scaling equation of state for a system with short range interactions and a one-component order parameter is calculated to order ?3 in the ?-expansion. The results are not compatible with the linear parametric model. 相似文献
99.
100.