全文获取类型
收费全文 | 1069篇 |
免费 | 15篇 |
国内免费 | 105篇 |
专业分类
化学 | 959篇 |
晶体学 | 2篇 |
力学 | 9篇 |
综合类 | 1篇 |
数学 | 140篇 |
物理学 | 78篇 |
出版年
2024年 | 20篇 |
2023年 | 200篇 |
2022年 | 13篇 |
2021年 | 10篇 |
2020年 | 18篇 |
2019年 | 26篇 |
2018年 | 30篇 |
2017年 | 26篇 |
2016年 | 13篇 |
2015年 | 17篇 |
2014年 | 48篇 |
2013年 | 73篇 |
2012年 | 35篇 |
2011年 | 57篇 |
2010年 | 42篇 |
2009年 | 66篇 |
2008年 | 60篇 |
2007年 | 72篇 |
2006年 | 55篇 |
2005年 | 49篇 |
2004年 | 55篇 |
2003年 | 17篇 |
2002年 | 25篇 |
2001年 | 11篇 |
2000年 | 9篇 |
1999年 | 13篇 |
1998年 | 19篇 |
1997年 | 11篇 |
1996年 | 21篇 |
1995年 | 7篇 |
1994年 | 11篇 |
1993年 | 11篇 |
1992年 | 7篇 |
1991年 | 5篇 |
1990年 | 8篇 |
1989年 | 2篇 |
1988年 | 4篇 |
1987年 | 4篇 |
1986年 | 1篇 |
1985年 | 5篇 |
1984年 | 1篇 |
1983年 | 3篇 |
1982年 | 3篇 |
1981年 | 2篇 |
1978年 | 1篇 |
1970年 | 1篇 |
1968年 | 2篇 |
排序方式: 共有1189条查询结果,搜索用时 0 毫秒
21.
Helmut Simon Johann Bader Helmut Günther Stefan Neumann Jordanes Thanos 《Angewandte Chemie (International ed. in English)》1985,24(7):539-553
It has been known for many decades that chiral compounds can be obtained by stereospecific biocatalytic reduction. Further significant methodological developments in this field have, however, only been made during the past ten years; they include the application of previously unused microorganisms and electron donors, the discovery of additional substrates for the known reductases, the development of methods for regenerating reduced pyridine nucleotides, and the discovery of new reductases which were sought for specific preparative purposes. Many chiral compounds can now be synthesized by microbial hydrogenation using H2 and hydrogenase-containing microorganisms as well as by electromicrobial or electroenzymatic reduction. In the two latter methods, anaerobic or aerobic organisms are supplied with electrons from electrochemically reduced, artificial mediators, e.g., methyl viologen. Reductases that do not require pyridine nucleotides and can accept electrons directly from reduced viologens are especially useful. Two examples of this type of enzyme are described which are of preparative interest. Many cells contain methyl viologen-dependent NAD(P) reductases, a large number of which have still not been characterized. A productivity number is proposed which allows different methods of bioconversion with microorganisms to be compared. The productivity numbers of compounds synthesized by the methods described in this review are often 10- to 100-fold higher than those of substances obtained by conventional techniques. 相似文献
22.
K. Wagner 《Angewandte Chemie (International ed. in English)》1970,9(1):50-54
Addition compounds of formic acid with tertiary organic bases in ratios higher than that required for salt formation (3:1 and 2:1 adducts) contain formic acid in a highly activated form. In particular, the 3:1 adducts of formic acid with trimethylamine and triethylamine are liquid reducing agents that are convenient to handle and are suitable for use in many selective reductions. These addition compounds have a surprisingly strong reducing action on sulfur dioxide, which is rapidly converted, even at low concentrations, into crystalline rhombic sulfur. Sulfones and polysulfones can be prepared in good yields by three-component reactions from activated formic acid, sulfur dioxide, and polarized vinyl compounds. 相似文献
23.
Albert Lévai Gábor Tóth Áron Szőllősy Tibor Timár 《Monatshefte für Chemie / Chemical Monthly》1990,121(5):403-411
Summary Arylsulfonyloxy-2,2-dimethyl-2H-chromenes (26–35) have been synthesized by reduction of arylsulfonyloxy-2,2-dimethyl-4-chromanones (6–15) followed by dehydration.
Synthese von Benzopyranderviaten. 15. Mitt.: Darstellung von Arylsulfonyloxy-2,2-dimethyl-2H-chromenen
Zusammenfassung Reduktion von Arylsulfonyloxy-2,2-dimethyl-4-chromanonen (6–15) und anschließende Dehydratisierung liefert Arylsulfonyloxy-2,2-dimethyl-2H-chromene (26–35).相似文献
24.
Abhimanyu S. Paraskar 《Tetrahedron》2006,62(20):4907-4916
Sodium borohydride in combination with a catalytic amount of CoCl2 has been found to be an excellent catalytic system in reductive cyclizations of suitably substituted azido and cyano groups of α,β-unsaturated esters to afford γ and δ-lactams in high yields. The process has been demonstrated for the enantioselective synthesis of (R)-baclofen, (R)-rolipram, and (R)-4-fluorophenylpiperidinone, a key intermediate for (−)-paroxetine. 相似文献
25.
Jean Michel Brunel 《Tetrahedron》2007,63(18):3899-3906
A new and efficient mild Pd/P(t-Bu)3 catalyst for selective reduction of various alkenes under transfer hydrogen conditions has been developed leading to the corresponding saturated derivatives in chemical yields varying from 65 to 98%. Mechanistic rationale of this reaction has been also demonstrated. 相似文献
26.
在SmI_2-HMPA-THF-t-BuOH体系中,硫代碳酸酯的酰硫键发生还原断裂反应,得到相应的二硫醚产物。 相似文献
27.
Summary Steroid ketoximes were reduced with sodium tetrahydroborate in the presence of nickel chloride or molybdenum trioxide. These processes yielded 17- and 20-aminosteroids (1c–5c) in higher yields than common reduction methods.
Steroide, 53. Mitt.: Neue Wege zu Aminosteroiden
Zusammenfassung Oxime von Ketosteroiden wurden mit NaBH4 in Gegenwart von NiCl2 und MoO3 reduziert. Dieses Verfahren lieferte 17- und 20-Aminosteroide(1c–5c) in größeren Ausbeuten als übliche Methoden.相似文献
28.
The Landau-Lifshitz fluctuating fluxes in fluctuating hydrodynamics are derived from the deterministic Boltzmann equation with the aid of a reduction method developed by Fujisaka and Mori. Thus it is shown that the hydrodynamic fluctuations innonequilibrium systems are generated by the reduction of variables from the-space distribution function to its five momentum moments, i.e., the hydrodynamic variables. This differs from the Bixon-Zwanzig and Fox-Uhlenbeck theories, in which the Landau-Lifshitz fluctuating fluxes are derived from the molecular fluctuating force in thestochastic Boltzmann-Langevin equation, which is, however, negligible in nonequilibrium systems. Thus the present method improves the Chapman-Enskog reduction method so as to include the hydrodynamic fluctuations generated by the reduction of variables.Supported in part by the Scientific Research Fund of the Ministry of Education. 相似文献
29.
The reaction of [(CO)PPh3)2Re(μ-H)2(μ-NCHPh)Ru(PPh3)2(PhCN)] (2) with HBF4-Me2O generates [(CO)PPh3)2Re(μ- H)2(μ,η1,η2HNCHPh)Ru(PPh3)2(PhCN)][BF4] (3). Monitoring the reaction by NMR spectroscopy shows the intermediate formation of [(CO)(PPh3)2 HRe(μ-H)2(μ-NCHPh)Ru(PPh3)2(PhCN)][BF4] (4). Attempted reduction of the imine ligand by a nucleophile (H− or CN−) failed, regenerating 2. Under dihydrogen at 50 atm, 3 is slowly transformed into [(CO)(PPh3)2HRe(μ-H)3Ru(PPh3)2(PhCN)][BF4] (5) with liberation of benzyl amine. 相似文献
30.
Kabir-ud-DinEmail author S.?M.?Shakeel?Iqubal Zaheer?Khan 《Colloid and polymer science》2005,284(3):276-283
Kinetics of the redox reaction between colloidal MnO2 and glycolic acid have been studied spectrophotometrically by monitoring the decay in the absorbance of colloidal MnO2 in absence and presence of surfactants. Anionic sodium dodecyl sulfate has no effect, non-ionic Triton X-100 catalyzed the reaction and experiments were not possible in presence of cationic cetyltrimethylammonium bromide due to the precipitation of MnO2.The reaction followed the same type of kinetic behavior, i.e., fractional-, first- and fractional-order dependencies, respectively, in [glycolic acid], [MnO2] and [H+ ] in both the media. Effects of gum arabic and manganese(II) have also been studied and discussed. Mechanisms in accordance with the experimental data are proposed for the reaction. 相似文献