全文获取类型
收费全文 | 3085篇 |
免费 | 84篇 |
国内免费 | 24篇 |
专业分类
化学 | 2208篇 |
晶体学 | 12篇 |
力学 | 41篇 |
数学 | 366篇 |
物理学 | 389篇 |
无线电 | 177篇 |
出版年
2023年 | 14篇 |
2022年 | 35篇 |
2021年 | 34篇 |
2020年 | 46篇 |
2019年 | 36篇 |
2018年 | 32篇 |
2017年 | 32篇 |
2016年 | 68篇 |
2015年 | 51篇 |
2014年 | 66篇 |
2013年 | 146篇 |
2012年 | 170篇 |
2011年 | 198篇 |
2010年 | 135篇 |
2009年 | 125篇 |
2008年 | 205篇 |
2007年 | 187篇 |
2006年 | 148篇 |
2005年 | 179篇 |
2004年 | 173篇 |
2003年 | 137篇 |
2002年 | 140篇 |
2001年 | 45篇 |
2000年 | 44篇 |
1999年 | 35篇 |
1998年 | 47篇 |
1997年 | 37篇 |
1996年 | 39篇 |
1995年 | 22篇 |
1994年 | 30篇 |
1993年 | 34篇 |
1992年 | 35篇 |
1991年 | 31篇 |
1990年 | 19篇 |
1989年 | 30篇 |
1988年 | 14篇 |
1987年 | 19篇 |
1986年 | 21篇 |
1985年 | 30篇 |
1984年 | 18篇 |
1983年 | 15篇 |
1982年 | 24篇 |
1981年 | 17篇 |
1980年 | 24篇 |
1979年 | 15篇 |
1978年 | 17篇 |
1977年 | 22篇 |
1976年 | 29篇 |
1975年 | 18篇 |
1973年 | 16篇 |
排序方式: 共有3193条查询结果,搜索用时 15 毫秒
61.
A synthesis of N-acetylcolchinol, a key intermediate in the synthesis of ZD6126, was developed. The enantiodifferentiating step required the catalytic asymmetric hydrogenation of an enamide. After screening a range of metal and ligand combinations it was found that (S,S)-iPr-FerroTANE Ru(methallyl)2 and [(S,S)-tBuFerroTANE Rh(COD)]BF4 gave both high enantioselectivity (>90% ee) and high catalyst utility (molar S/C = 1000). 相似文献
62.
A series of commercial monomeric and polymeric C(18), C(27), and C(30) stationary phases were compared with immobilized poly(ethylene-co-acrylic acid) stationary phases synthesized in-house. The columns were characterized on the basis of methylene selectivity, silanol activity, metal activity, pore size, shape selectivity, and the ability to separate tocopherol isomers and carotenoid isomers. Monomeric and polymeric C(30) phases were shown to yield excellent separations of the tocopherol isomers while the polymeric C(30) and polyethylene phases were more appropriate to the separation of carotenoids. 相似文献
63.
Odile Meyer Jean-Franois Hoeffler Catherine Grosdemange-Billiard Michel Rohmer 《Tetrahedron》2004,60(52):12153-12162
An optimised gram scale synthesis allows the production of 1-deoxy-d-xylulose and 1-deoxy-d-xylulose 5-phosphate with possible deuterium labelling at C-5. Such substrates are required for investigations on the mevalonate-independent 2-C-methyl-d-erythritol 4-phosphate pathway for isoprenoid biosynthesis in bacteria and chloroplasts of phototrophic eukaryotes and for the biosynthesis of vitamins B1 (thiamine diphosphate) and B6 (pyridoxol phosphate) in bacteria. 相似文献
64.
The effect of nine peak measurement/analysis parameters on chiral capillary electrophoresis (CE), followed by UV detection, was studied. The parameters pertained UV-detection (detection wavelength, reference wavelength, and wavelength bandwidths), signal processing (data acquisition rate, type and amount of filtering) and peak detection (detection threshold and peak width). The influence of these factors on the chiral separation of dimethindene enantiomers was studied at two different concentrations (i.e., at high and low signal-to-noise (S/N) ratio) by the means of experimental designs. The electropherogram characteristics considered were the resolution between the two enantiomers, the peak areas, and the S/N ratio. A D-optimal design was first used as screening design to identify the most critical parameters. Afterwards, a modelling of the different responses as a function of these critical parameters was performed based on the results of a face-centered central composite design. The results showed that the signal-processing parameters should be carefully selected when developing a CE separation since very important variations in the separation, the S/N ratio and the peak area of the substances can occur by setting these parameters at different levels. The detection wavelength should also be carefully chosen for optimal peak area measurement. The role of these parameters becomes more important with decreasing concentration of the analytes (i.e., low S/N ratio). This study showed that the peak measurement/analysis parameters should be optimized as the chemical and physical parameters of a method. They also should always be well specified in order to allow a good transfer of a method from one instrument to another. 相似文献
65.
Castro C Karney WL Valencia MA Vu CM Pemberton RP 《Journal of the American Chemical Society》2005,127(27):9704-9705
Density functional and coupled cluster calculations show that facile thermal configuration change in [12]annulene occurs via a twist-coupled bond-shifting mechanism. The transition state for this process is highly aromatic with M?bius topology. At the CCSD(T)/cc-pVDZ//BH&HLYP/6-311+G** level, the isomerization of tri-trans-[12]annulene 1a (CTCTCT) to its di-trans isomer 2 (CCCTCT) via such a mechanism has a barrier of 18.0 kcal/mol, in good agreement with earlier experiments. Two other aromatic M?bius bond-shifting transition states were located that result in configuration change for other [12]annulene conformers. This mechanism contrasts sharply with diradical configuration change for acyclic polyenes and with planar bond-shifting mechanisms generally assumed for annulenes. This constitutes evidence that neutral M?bius aromatic annulenes play a role in the dynamic processes of neutral [4n]annulenes. 相似文献
66.
The objective of this paper is to propose an architecture for aCAble TeleVision (CATV) network, capable of supporting two-way transmission. This evolution is necessary for the survival of the CATV industry in an era of deregulation and of the development of the B-ISDN by the telecommunications companies. A communication transactional service is then considered and performance analysis is done under realistic assumptions. 相似文献
67.
Dietmar Krämer Erwin Rosenberg Achim Krug Robert Kellner Wolfgang Hutter Werner Hampel 《Mikrochimica acta》1994,116(4):183-189
Chloride is determined indirectly by Spectrophotometric flow injection analysis. Two systems are compared, both based on the principle of ion exchange of easily detectable anions versus chloride from suitable mercury salts. The first method is based on the exchange of chloride with chloranilate which is detected at 332 nm or at 306 nm in neutral or in acidic medium respectively. In the second case, chloride reacts with Hg(SCN)2. The liberated thiocyanate forms a strongly coloured complex with Fe(III) in acidic solution with an absorption maximum at 460 nm. Both methods have a detection limit of about 5 mol Cl–/l (175 ng/ml). In the case of the thiocyanate method, the relative standard deviation is about 2% (7 measurements) in the range of 5 to 150 mol/l and decreases significantly to a value of approximately 0.2% at higher concentrations; for the chloranilate method it is 10% for lower and about 1% for higher concentrations respectively. 相似文献
68.
69.
Catherine J. Murphy 《Journal of Cluster Science》1996,7(3):341-350
One of the most exciting frontiers in materials chemistry in recent years is the optoelectronics of quantum-confined semiconductor nanoclusters. These nanoclusters are 10–200 A in diameter, and in this size regime exhibit extra-ordinarily interesting quantum mechanical effects. Cadmium sulfide is a popular semiconductor for these studies, and reviewed here is the synthesis and charac-terization of such CdS nanoclusters, with emphasis on how chemical control of the surface by thiolates influences product formation and properties. Also described are the syntheses and structures of true molecular clusters of CdS capped with thiolate ligands. 相似文献
70.