首页 | 本学科首页   官方微博 | 高级检索  
文章检索
  按 检索   检索词:      
出版年份:   被引次数:   他引次数: 提示:输入*表示无穷大
  收费全文   33207篇
  免费   4400篇
  国内免费   3067篇
化学   22672篇
晶体学   327篇
力学   2017篇
综合类   246篇
数学   3778篇
物理学   11634篇
  2024年   85篇
  2023年   549篇
  2022年   987篇
  2021年   1078篇
  2020年   1125篇
  2019年   1107篇
  2018年   923篇
  2017年   838篇
  2016年   1356篇
  2015年   1416篇
  2014年   1618篇
  2013年   2234篇
  2012年   2659篇
  2011年   2952篇
  2010年   1874篇
  2009年   1840篇
  2008年   1968篇
  2007年   1839篇
  2006年   1754篇
  2005年   1479篇
  2004年   1347篇
  2003年   1064篇
  2002年   970篇
  2001年   827篇
  2000年   719篇
  1999年   631篇
  1998年   539篇
  1997年   462篇
  1996年   510篇
  1995年   450篇
  1994年   447篇
  1993年   355篇
  1992年   361篇
  1991年   299篇
  1990年   284篇
  1989年   234篇
  1988年   181篇
  1987年   150篇
  1986年   144篇
  1985年   169篇
  1984年   111篇
  1983年   112篇
  1982年   85篇
  1981年   65篇
  1980年   61篇
  1979年   42篇
  1977年   42篇
  1975年   40篇
  1974年   49篇
  1973年   47篇
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
61.
62.
63.
Synthesis, single-crystal structure determination, and magnetic properties are reported for manganese carbodiimide, MnNCN. The presumably unstable but inert phase adopts the trigonal system (R3m) with a = 3.3583(4) A, c = 14.347(2) A, V = 140.13(3) A3, and Z = 3. Divalent manganese is octahedrally coordinated by nitrogen atoms at 2.26 A, and the NCN(2-) unit adopts the linear [N=C=N](2-) carbodiimide shape with two C=N double bonds of 1.23 A. MnNCN contains high-spin Mn(II) with five unpaired electrons and behaves like an antiferromagnet with an ordering temperature below 30 K.  相似文献   
64.
Reactions of Ta(NMe2)5 with D2SiR'Ph (R' = Me, Ph) were found to give a dideuteride eta 2-imine complex (Me2N)3Ta(mu-D)2(mu-N-eta 2-N,C-CH2NMe)Ta(NMe2)3(1-d2) through C-H activation of an amide ligand via beta-H abstraction, and the structure of 1 was confirmed by single crystal neutron and X-ray diffraction.  相似文献   
65.
A solid-phase microextraction (SPME) device was used as a time-weighted average sampler for n-valeraldehyde. The SPME device was first modified to improve the wearer's acceptance as a passive sampler. Then a poly(dimethylsiloxane)-divinylbenzene fiber was used and O-2,3,4,5,6-(pentafluorobenzyl)hydroxylamine hydrochloride (PFBHA) was loaded onto the fiber. Vapors of known concentrations around the threshold limit values time-weighted average of n-valeraldehyde and specific relative humidities (RHs) were generated by syringe pumps in a dynamic generation system. n-Valeraldehyde vapors in gas bags were also generated. An exposure chamber was designed to allow measurement of face velocities, temperatures, exposing vapor concentrations, and RHs. Gas chromatography with flame ionization detection was used for sample analysis. The appropriate adsorption time for SPME coating PFBHA was determined to be 2 min and the desorption time for oxime formed after sampling was optimized to be 2 min. The experimental sampling constant was found to be (3.86+/-0.13) x 10(-2) cm3/min and face velocity was not expect to have effect on the sampler.  相似文献   
66.
<正> 苯乙烯(简称St)-4(甲基丙烯酸)2,2,6,6-四甲基哌啶醇酯(简称MTMP)共聚物(简称PDS)是七十年代发展起来的一种新型高效光稳剂。本文用IR研究了一系列自由基聚合的PDS共聚物,找出了MTMP对序列结构敏感的吸收峰,发现MTMP的1152.5厘米~(-1)峰位置与三单元序列分布F_(SMS)值有一定线性关系,还对通过测量MTMP羰基伸缩振动ν_(C=O)峰位置来计算二单元序列分布P_(mm)的关系进行了讨论。  相似文献   
67.
A micellar electrokinetic chromatography method was established for the quantitative analysis of seven podophyllum lignans in Podophyllum emodi Wall. var. chinesis sprague. The optimum buffer system was 10 mM NaH2PO4-5 mM borate-100 mM sodium dodecylsulfate-30% isopropanol (pH 7.20). Voltage was 18 kV and detection at 214 nm. The second derivative chromatogram was used to determine a low-content component and those not fully separated from adjacent ones. The RSD values of migration times and peak areas were <2.2 and <5.5%, respectively. The effects of several CE parameters on the resolutions were studied systematically.  相似文献   
68.
氯过氧化物酶的手性催化活性在有机合成中的应用   总被引:2,自引:0,他引:2  
氯过氧化物酶(CPO)作为过氧化物酶家族中的一员对多种有机底物表现出了广泛的催化活性。自上世纪60年代被发现以来,CPO在有机合成中的应用一直是一个研究热点。它作为一种生物催化剂能催化广泛的底物合成手性化合物,且有高的产率和高的对映选择率。本文综述了氯过氧化物酶在手性有机合成中的应用,重点关注了卤化、醇氧化、羟基化、环氧化、磺化氧化等反应,并讨论了目前在该领域所面临的问题及今后的发展趋势。  相似文献   
69.
 This paper is the study of the fluorescence enhancement of Eu3+-1-ethyl-6-fluoro-4-oxo-7-(1-piperazinyl)-1,8-naphthyridin-3-carbonic acid (enoxacin, EFLX) system by surfactants. It was found that sodium dodecylbenzenesulfonate (SDBS) exhibits great enhancement on the fluorescence of the Eu-EFLX system. The molar ratio is 1:2:1 for Eu:EFLX: SDBS. Under the optimum conditions, the fluorescence intensity is a linear function of europium in the range of 1.0 × 10−8 ∼ 5.0 × 10−6 mol/L, the detection limit is 1.0 × 10−9 mol/L. The application of the Eu-EFLX-SDBS system for the determination of trace europium in rare earth samples gave satisfactory results. Received October 19, 2000. Revision August 10, 2001.  相似文献   
70.
The Suzuki cross-coupling methodology provides a facile synthetic approach for the modular preparation of meso-tetraaryl cofacial bisporphyrins anchored by xanthene and dibenzofuran. This synthetic method furnishes cofacial bisporphyrin templates with enhanced steric and electronic protection from mu-oxo formation and oxidative degradation. The ability of these platforms to support multielectron oxidation chemistry mediated by proton-coupled electron transfer (PCET) is demonstrated by their reactivity for the catalytic disproportionation of hydrogen peroxide to oxygen and water.  相似文献   
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号