全文获取类型
收费全文 | 1775篇 |
免费 | 56篇 |
国内免费 | 15篇 |
专业分类
化学 | 940篇 |
晶体学 | 10篇 |
力学 | 45篇 |
数学 | 201篇 |
物理学 | 650篇 |
出版年
2021年 | 14篇 |
2020年 | 12篇 |
2019年 | 18篇 |
2017年 | 17篇 |
2016年 | 29篇 |
2015年 | 21篇 |
2014年 | 35篇 |
2013年 | 94篇 |
2012年 | 59篇 |
2011年 | 88篇 |
2010年 | 61篇 |
2009年 | 34篇 |
2008年 | 84篇 |
2007年 | 100篇 |
2006年 | 67篇 |
2005年 | 60篇 |
2004年 | 61篇 |
2003年 | 30篇 |
2002年 | 58篇 |
2001年 | 46篇 |
2000年 | 40篇 |
1999年 | 17篇 |
1998年 | 22篇 |
1997年 | 19篇 |
1996年 | 19篇 |
1995年 | 31篇 |
1994年 | 36篇 |
1993年 | 39篇 |
1992年 | 33篇 |
1991年 | 27篇 |
1990年 | 21篇 |
1989年 | 16篇 |
1988年 | 28篇 |
1987年 | 14篇 |
1986年 | 19篇 |
1985年 | 32篇 |
1984年 | 17篇 |
1983年 | 17篇 |
1982年 | 24篇 |
1981年 | 20篇 |
1980年 | 27篇 |
1979年 | 24篇 |
1978年 | 31篇 |
1977年 | 21篇 |
1976年 | 32篇 |
1975年 | 34篇 |
1974年 | 20篇 |
1973年 | 33篇 |
1972年 | 14篇 |
1971年 | 15篇 |
排序方式: 共有1846条查询结果,搜索用时 218 毫秒
71.
Busch BB Paz MM Shea KJ Staiger CL Stoddard JM Walker JR Zhou XZ Zhu H 《Journal of the American Chemical Society》2002,124(14):3636-3646
Trialkyl and aryl organoboranes catalyze the polymerization of dimethylsulfoxonium methylide (1). The product of the polymerization is a tris-polymethylene organoborane. Oxidation affords linear telechelic alpha-hydroxy polymethylene. The polymer molecular weight was found to be directly proportional to the stoichiometric ratio of ylide/borane, and polydispersities as low as 1.01-1.03 have been realized. Although oligomeric polymethylene has been the most frequent synthetic target of this method, polymeric star organoboranes with molecular weights of 1.5 million have been produced. The average turnover frequency at 120 degrees C in 1,2,4,5-tetrachlorobenzene/toluene is estimated at >6 x 10(6) g of polymethylene (mol boron)(-1) h(-1). The mechanism of the polyhomologation reaction involves initial formation of a zwitterionic organoborane.ylide complex which breaks down in a rate-limiting 1,2-alkyl group migration with concomitant expulsion of a molecule of DMSO. The reaction was found to be first order in the borane catalyst and zero order in ylide. DMSO does not interfere with the reaction. The temperature dependence of the reaction rate yielded the following activation energy parameters (toluene, DeltaH(++) = 23.2 kcal/mol, DeltaS(++) = 12.6 cal deg/mol, DeltaG(++) = 19.5 kcal/mol; THF, DeltaH(++) = 26.5 kcal/mol, DeltaS(++) = 21.5 cal deg/mol, DeltaG(++) = 20.1 kcal/mol). 相似文献
72.
Edward F. Hayes Zareh Darakjian Robert B. Walker 《Theoretical chemistry accounts》1991,79(3-4):199-213
Summary The Bending Corrected Rotating Linear Model (BCRLM), developed by Hayes and Walker, is a simple approximation to the true multidimensional scattering problem for reactions of the type: A + BC AB + C. While the BCRLM method is simpler than methods designed to obtain accurate three-dimensional quantum scattering results, this turns out to be a major advantage in terms of our benchmarking studies. The computer code used to obtain BCRLM scattering results is written for the most part in standard FORTRAN and has been ported to several scalar, vector, and parallel architecture computers including the IBM 3090-600J, the Cray XMP and YMP, the Ardent Titan, IBM RISC System/6000, Convex C-1 and the MIPS 2000. Benchmark results will be reported for each of these machines with an emphasis on comparing the scalar, vector, and parallel performance for the standard code with minimum modifications. Detailed analysis of the mapping of the BCRLM approach onto both shared and distributed memory parallel architecture machines indicates the importance of introducing several key changes in the basic strategy and algorithms used to calculate scattering results. This analysis of the BCRLM approach provides some insights into optimal strategies for mapping three-dimensional quantum scattering methods, such as the Parker-Pack method, onto shared or distributed memory parallel computers. 相似文献
73.
74.
Chen JP Meziani ZE Beck D Boyd G Chinitz LM Day DB Dennis LC Dodge G Filippone BW Giovanetti KL Jourdan J Kemper KW Koh T Lorenzon W McCarthy JS McKeown RD Milner RG Minehart RC Morgenstern J Mougey J Potterveld DH Rondon-Aramayo OA Sealock RM Smith LC Thornton ST Walker RC Woodward C 《Physical review letters》1991,66(10):1283-1286
75.
76.
Strongin B Bofill J Friedman JI Fuess S Goodman MC Kendall HW Kistiakowsky V Lyons T Osborne LS Pitt R Schneekloth U Taylor FE Bogert D Koizumi G Stutte L Abolins M Brock R Cobau W Hatcher R Owen D Perkins G Tartaglia M Weerts H Belusevic R Walker JK White A Womersley J 《Physical review D: Particles and fields》1991,43(9):2778-2786
77.
78.
Mary Mulholland N. Walker J. A. van Leeuwen Luitgard Buydens F. Maris H. Hindriks Peter J. Schoenmakers 《Mikrochimica acta》1991,104(1-6):493-503
ESCA, Expert Systems Applied to Chemical Analysis, started its research in March 1987, with the aim of building prototype expert systems for HPLC method development. Results of this research have been published as the work has progressed. The project is now completed and this paper summarises some of the overall project conclusions. Seven different expert systems have been built which tackle problems throughout the process of method development, four stand-alone systems and three integrated systems. The object of ESCA was to evaluate the applicability of expert system technology to analytical chemistry and not all the systems were built for commercial uses. Many of the systems tackle problems specific to one or more of the partners and thus may not be useful outside this environment. However, the results of the work are still pertinent to analysts wishing to build their own systems. These results are described, however, the emphasis of the paper is on those systems developed for method validation.Method validation for HPLC is a complex task which requires many characteristics of the method to be tested, e.g. accuracy, precision, etc. The expert systems built within ESCA concern the validation of precision. Two systems were developed for repeatability testing and ruggedness testing. The method validation process can be divided into several discrete stages, these include: (1) The selection of the method feature to test, for instance which factors can influence the ruggedness of a method. (2) The definition of a test procedure, for instance an efficient statistical design. (3) The execution of experiments and the interpretation of results. (4) A diagnosis of any observed problem. This paper describes these two systems in some detail and summarises some of the results obtained from their evaluation. It concludes that expert systems can be useful in solving analytical problems and the integration of several expert systems can provide extremely powerful tools for the analyst. 相似文献
79.
Ramoplanin is a cyclicdepsipeptide antibiotic that inhibits peptidoglycan biosynthesis. It was proposed in 1990 to block the MurG step of peptidoglycan synthesis by binding to the substrate of MurG, Lipid I. The proposed mechanism of MurG inhibition has become widely accepted even though it was never directly tested. In this paper, we disprove the accepted mechanism for how ramoplanin functions, and we present an alternative mechanism. This work has implications for the design of ramoplanin derivatives and may influence how other proposed substrate binding antibiotics are studied. 相似文献
80.
We present a method for sample concentration within microfluidic devices using evaporation-induced flow. Evaporation-induced flow is easy to incorporate into microfluidic designs and can be used to concentrate a wide variety of molecules. The practicality of this method was demonstrated with 0.2 microm fluorescent spheres and FITC-labeled BSA. Thirty two percent of the 0.6 microL fluorescent sphere suspension was concentrated into a well within a microfluidic device. In the same amount of time, 93% of the 0.6 microL FITC-labeled BSA solution was concentrated. 相似文献