全文获取类型
收费全文 | 73894篇 |
免费 | 13224篇 |
国内免费 | 5488篇 |
专业分类
化学 | 67081篇 |
晶体学 | 880篇 |
力学 | 2447篇 |
综合类 | 260篇 |
数学 | 6254篇 |
物理学 | 15684篇 |
出版年
2024年 | 108篇 |
2023年 | 709篇 |
2022年 | 1418篇 |
2021年 | 1548篇 |
2020年 | 2578篇 |
2019年 | 3834篇 |
2018年 | 2141篇 |
2017年 | 1764篇 |
2016年 | 4923篇 |
2015年 | 5082篇 |
2014年 | 5327篇 |
2013年 | 6619篇 |
2012年 | 6315篇 |
2011年 | 5698篇 |
2010年 | 5136篇 |
2009年 | 5013篇 |
2008年 | 4921篇 |
2007年 | 4015篇 |
2006年 | 3591篇 |
2005年 | 3389篇 |
2004年 | 2772篇 |
2003年 | 2350篇 |
2002年 | 3085篇 |
2001年 | 2104篇 |
2000年 | 1968篇 |
1999年 | 1085篇 |
1998年 | 640篇 |
1997年 | 600篇 |
1996年 | 595篇 |
1995年 | 462篇 |
1994年 | 392篇 |
1993年 | 326篇 |
1992年 | 318篇 |
1991年 | 283篇 |
1990年 | 232篇 |
1989年 | 213篇 |
1988年 | 126篇 |
1987年 | 151篇 |
1986年 | 117篇 |
1985年 | 130篇 |
1984年 | 82篇 |
1983年 | 68篇 |
1982年 | 58篇 |
1981年 | 34篇 |
1980年 | 30篇 |
1979年 | 24篇 |
1978年 | 26篇 |
1977年 | 26篇 |
1976年 | 26篇 |
1975年 | 24篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
991.
RajanBabu TV Nomura N Jin J Nandi M Park H Sun X 《The Journal of organic chemistry》2003,68(22):8431-8446
Through a systematic examination of ligand and counterion effects, new protocols for a nearly quantitative and highly selective codimerization of ethylene and various functionalized vinylarenes have been discovered. In a typical reaction, 4-bromostyrene and ethylene undergo codimerization in the presence of 0.0035 equiv each of [(allyl)NiBr]2, triphenylphosphine, and AgOTf in CH2Cl2 at -56 degrees C to give 3-(4-bromophenyl)-1-butene in >98% yield and selectivity. Corresponding reactions with [(allyl)PdX]2 are much less efficient and less selective and may require further optimization before a viable system can be identified. Another useful protocol that gives comparable yield and selectivity involves the use of a single-component catalyst prepared from allyl 2-diphenylphosphinobenzoate, Ni(COD)2, and (C6F5)3B. Recognition of a synergistic relationship between a chiral hemilabile ligand (for example, (R)-2-methoxy-2'-diphenylphosphino-1,1'-binaphthyl, MOP) and a highly dissociated counteranion (BARF or SbF6) in an enantioselective version of the Ni-catalyzed reaction raises the prospects of developing a practical route for the synthesis of 3-arylbutenes. Several pharmaceutically relevant compounds, including widely used 2-arylpropionic acids, can be synthesized from these key intermediates. This reaction appears to be quite general. Synthesis of several new 2-diphenylphosphino-1,1-binaphthyl derivatives, prepared to probe the effect of hemilabile coordination on the efficiency and selectivity of the reaction, are also described. 相似文献
992.
Jung JH Pomeroy JC Zhang H Wisian-Neilson P 《Journal of the American Chemical Society》2003,125(50):15537-15542
Heating pure samples of the cyclic phosphazenes, cis- or trans-[Me(Ph)PN](3), yielded mixtures of the cis and trans isomers of the cyclic phosphazene trimers, [Me(Ph)PN](3), and all four geometric isomers of the tetramers, [Me(Ph)PN](4). Varying the temperature and heating times changes the ratio of these components. Following the thermolysis by NMR spectroscopy indicated that only a mixture of the two isomeric trimers occurred initially. Longer heating times produced mixtures of the isomers of the tetramer. Column chromatography and solubility differences were used to separate each of the isomers of the tetramer. Spectroscopic and X-ray crystallographic studies suggest that the four different geometrical isomers of the tetramer can be described as cone, partial cone, 1,2-alternate, and 1,3-alternate by analogy to calix[4]arene. 相似文献
993.
IntroductionItiswellknownthatmetallocenesactivatedwithmethylaluminoxane (MAO)arehighlyactivehomogeneousZiegler Nattacatalyststhatproducepolyolefinwithcon trolledstereoregularityandnarrowmolecularweightdistri bution ,1 4 however,themolecularweightofthepolym… 相似文献
994.
In the reaction of methane and carbon dioxide to C2 hydrocabons under non-equilibrium plasma, methane conversion was decreased,but selectivity of C2 hydroxarbons was increased when using La2O3/γ-Al2O3 as catalyst. So the yield of C2 hydrocarbons was higher than using plasma alone. The synergism of La2O3/γ-Al2O3 and plasma gave methane conversion of 24.9% and C2 yield of 18.1%. The distribution of C2 hydrocarbons changed when Pd-La2O3/γ-Al2O3 was used as catalyst,the major C2 product was ethylene. 相似文献
995.
996.
G. Keller I. Barzen R. Erz W. Dötter S. Ulrich K. Jung H. Ehrhardt 《Fresenius' Journal of Analytical Chemistry》1991,341(5-6):349-352
Summary It is shown that small variations of the deposition parameters during magnetron sputtering of tungsten carbide thin films may result in drastic changes of film properties. An increasing working gas pressure for example lowers stress and hardness values. Simultaneously, the texture of the WC1–x cristallites turns from 200 preferential orientation to 111, whereas the composition of the films does not change. In reactive sputtering with a tungsten target there is a narrow range from 2 to 3% C2H2 gas admixture to the working gas where the films are stochiometric (WC) and hard, and grain size and morphology are similar to that of non-reactively sputtered films. The generation of different crystallite structures and orientations in the range of 0–3% C2H2 admixtures are used to produce a multiphase thin film with extremely low crack propagation. 相似文献
997.
本文介绍一种自制环境等温型高温量热计, 其原理基于差热分析。在1300 K下所测纯铁等相变热与文献值吻合甚好, 证明仪器可靠。应用此仪器系统测量了Fe-Cr-V三元系九种不同成份的α-合金生成焓, 以及它们的α-α相变焓。为该体系的热力学研究提供了一些必要的热化学数据。 相似文献
998.
G. M. Sun S. H. Byun H. D. Choi 《Journal of Radioanalytical and Nuclear Chemistry》2003,256(3):541-552
Prompt k
0-factors relative to chlorine and relative g-emission intensities were determined for the strong non-1/v absorbers 113Cd, 149Sm, 151Eu,155Gd and 157Gd. Measurements were performed using the SNU-KAERI prompt gamma activation analysis (PGAA) facility at the Korea Atomic Energy Research Institute (KAERI). For proper experimental determination of the prompt k
0-factors, the effective g-factor and cadmium ratio were taken into account, in consideration of the effects from the non-1/v capture cross section and neutron spectrum in the thermal and epithermal energy region. By using the actual spectrum of the neutron beam in this study, the effective g-factor was obtained by calculation, and the influence of epithermal neutrons on the capture rate was corrected by measuring the cadmium ratio for each non-1/v target isotope. The measured prompt k
0-factors were used to check the consistency between the existing dataset of the absolute g-emission intensity and the 2200 m/s capture cross section for these isotopes. 相似文献
999.
Theoretical elucidation of kinetic and thermodynamic control of radical addition regioselectivity 总被引:1,自引:0,他引:1
Leach AG Wang R Wohlhieter GE Khan SI Jung ME Houk KN 《Journal of the American Chemical Society》2003,125(14):4271-4278
The cyclizations of two structurally similar 2-oxo-5-hexenyl-type radicals have been investigated by ab initio and density functional (UB3LYP/6-31+G**//UHF/6-31G* and UB3LYP/6-31G*//UB3LYP/6-31G*) calculations. The origin of apparently contradictory reports of 6-endo and 5-exo cyclizations is determined. Kinetic control favors 6-endo cyclization, while thermodynamic control gives 5-exo cyclization, and the observation of different products from different research groups arises from the difference in experimental conditions used by the two groups. The outcome of a new cyclization reaction was predicted by using these theoretical techniques. Kinetic control is predicted to yield exclusively the products of 6-endo cyclization, while thermodynamic control would lead to an approximately equal mixture of one 6-endo and one 5-exo cyclized product. Experimental studies revealed that the reaction yields only the products of 6-endo cyclization through kinetic control. 相似文献
1000.
The intramolecular Diels-Alder reaction of allenic ketones containing a furyl unit (IMDAF) to generate oxatricyclic systems in good yields is described. The alkene dienophiles 1ab give poor yields of the cycloadducts 2ab, presumably due to the facile retro Diels-Alder reaction. However, the analogous allenic dienophile 7 afforded the desired cycloadduct 8 in 91% yield on treatment with dimethylaluminum chloride. When the allene bears an alkyl substituent on the terminal carbon, complete diastereoselectivity is seen in the IMDAF, e.g. cyclization of 14 gave only the cycloadduct 15 in 80% yield presumably due to greater steric hindrance in the transition state II as compared to that in I. Finally we report complete chirality transfer of the stereochemistry of an allene to the carbon framework of the oxatricyclic system. Thus, the optically active allenic ketone 20 afforded only the desired cycloadduct 21 with the correct absolute stereochemistry needed for the synthesis of the arisugacin class of natural products. 相似文献