全文获取类型
收费全文 | 4166篇 |
免费 | 71篇 |
国内免费 | 17篇 |
专业分类
化学 | 2478篇 |
晶体学 | 27篇 |
力学 | 121篇 |
数学 | 762篇 |
物理学 | 866篇 |
出版年
2021年 | 39篇 |
2020年 | 36篇 |
2019年 | 41篇 |
2017年 | 26篇 |
2016年 | 63篇 |
2015年 | 67篇 |
2014年 | 67篇 |
2013年 | 156篇 |
2012年 | 141篇 |
2011年 | 172篇 |
2010年 | 104篇 |
2009年 | 89篇 |
2008年 | 170篇 |
2007年 | 133篇 |
2006年 | 127篇 |
2005年 | 114篇 |
2004年 | 89篇 |
2003年 | 86篇 |
2002年 | 108篇 |
2001年 | 72篇 |
2000年 | 80篇 |
1999年 | 77篇 |
1998年 | 57篇 |
1997年 | 68篇 |
1996年 | 54篇 |
1995年 | 67篇 |
1994年 | 57篇 |
1993年 | 55篇 |
1992年 | 63篇 |
1991年 | 39篇 |
1990年 | 45篇 |
1989年 | 38篇 |
1988年 | 54篇 |
1987年 | 50篇 |
1986年 | 52篇 |
1985年 | 74篇 |
1984年 | 51篇 |
1983年 | 45篇 |
1982年 | 56篇 |
1981年 | 52篇 |
1980年 | 70篇 |
1979年 | 52篇 |
1978年 | 43篇 |
1977年 | 60篇 |
1976年 | 47篇 |
1975年 | 42篇 |
1974年 | 42篇 |
1973年 | 29篇 |
1971年 | 29篇 |
1933年 | 24篇 |
排序方式: 共有4254条查询结果,搜索用时 15 毫秒
111.
The enthalpy of formation of methylhydroxycarbene, CH(3)COH, has been determined from measurements of the threshold energy for collision-induced dissociation of protonated 2,3-butanedione in a flowing afterglow-triple quadrupole mass spectrometer and found to be 16 +/- 4 kcal/mol, 57 +/- 4 kcal/mol higher than that of acetaldehyde. From the measured enthalpy of formation, the difference between the first and second C-H BDEs in ethanol is found to be 17 kcal/mol, which implies a singlet-triplet splitting of 28 kcal/mol in the carbene. The activation energies for loss of ketene and carbon monoxide from protonated butanedione are found to be 60 +/- 4 and 50 +/- 4 kcal/mol, respectively. On the basis of experimental and computational results, the loss of carbon monoxide is proposed to proceed through a tight transition state. Although calculations also suggest a tight transition state for loss of ketene, the experimental data indicate that it occurs via a loose transition state, possibly forming by proton transfer along the direct dissociation pathway. 相似文献
112.
Friedrich J Dolg M Gansäuer A Geich-Gimbel D Lauterbach T 《Journal of the American Chemical Society》2005,127(19):7071-7077
The mechanism of titanocene mediated 3-exo cyclizations was investigated by a combined theoretical and experimental study. A gradient corrected density functional theory (DFT) method has been scaled against titanocene dichloride, the parent butenyl radical, and in bond dissociation energy (BDE) calculations. The BP86 method using density fitting, and a basis set of triple-zeta quality emerged as a highly reliable tool for studying titanocene mediated radical reactions. The computational results revealed important kinetic and thermodynamic features of cyclopropane formation. Surprisingly, the beta-titanoxy radicals, the first intermediates of our investigations, were demonstrated to possess essentially the same thermodynamic stabilization as the corresponding alkyl radicals by comparison of the calculated BDEs. In contrast to suggestions for samarium mediated reactions, the cyclization was shown to be thermodynamically favorable in agreement with earlier kinetic studies. It was established that stereoselectivity of the cyclization is governed by the stability of the intermediates and thus the trans disubstituted products are formed preferentially. The observed ratios of products are in good to excellent agreement with the DFT results. By a combination of computational and experimental results, it was also shown that for the completion of the overall cyclopropane formation the efficiency of the trapping of the cyclopropylcarbinyl radicals is decisive. 相似文献
113.
114.
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
115.
Pierre-Luc Girard-Lauriault Juan-Carlos Ruiz Thomas Gross Michael R. Wertheimer Wolfgang E. S. Unger 《Plasma Chemistry and Plasma Processing》2011,31(4):535-550
Nitrogen (N)-rich organic thin films were deposited using both low-pressure plasma- and vacuum-ultraviolet-based techniques, from mixtures of ammonia (NH3) and ethylene (C2H4). These films were investigated using angle-resolved and excitation energy resolved X-ray photoelectron spectroscopy (ARXPS and ERXPS, respectively) in order to determine their sub-surface chemical profiles. These two techniques enable one to tune the ??XPS 95%?? information depth, z 95%, by varying either the angle or the excitation energy. Using a combination of both techniques, z 95% can be varied continuously from 0.7 to 11 nm. The surface-near chemistry is investigated using both high-resolution C 1s spectra and elemental concentrations derived from elemental peak intensities. Results show that while laboratory XPS, and even ARXPS, suggest homogenous surface chemistries, the novel combination of ARXPS and ERXPS points to the existence of a compositional profile in the extreme outer surface layer. Our conclusions are supported by simulations using SESSA software. 相似文献
116.
Friedrich Hecht und Richard Reissner 《Fresenius' Journal of Analytical Chemistry》1935,103(3-4):88-98
Ohne Zusammenfassung 相似文献
117.
Viroids: a class of subviral pathogens 总被引:13,自引:0,他引:13
118.
E. Krös L. Ladányi V. Friedrich Zs. Nagy Á. Kis 《Reaction Kinetics and Catalysis Letters》1974,1(4):455-460
The Ru(dipy)
3
2+
-bromate-malonic acid oscillating system was in vestigated. It has been established that at early stages of the reaction the period of oscillation is about 20 sec and the potential change is about 170 mV; chloride at concentrations hiherg than 10–3M is an inhibitor. The rates of both heat evolution and formation of bromomalonic acid are periodic. The activation energy of the oscillating (E) is 16.2 kcal mol–1. Ru(dipy)
3
2+
-- . , 20 , 170 ; , - 10–3 M, . . (E) 16,2 /. 相似文献
119.
120.