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   42891篇
  免费   3421篇
  国内免费   1755篇
化学   29632篇
晶体学   474篇
力学   1850篇
综合类   83篇
数学   4351篇
物理学   11677篇
  2023年   462篇
  2022年   732篇
  2021年   1060篇
  2020年   1144篇
  2019年   1093篇
  2018年   901篇
  2017年   782篇
  2016年   1469篇
  2015年   1448篇
  2014年   1641篇
  2013年   2698篇
  2012年   3324篇
  2011年   3490篇
  2010年   2203篇
  2009年   2064篇
  2008年   2795篇
  2007年   2528篇
  2006年   2331篇
  2005年   2177篇
  2004年   1812篇
  2003年   1471篇
  2002年   1418篇
  2001年   1036篇
  2000年   884篇
  1999年   663篇
  1998年   470篇
  1997年   462篇
  1996年   550篇
  1995年   443篇
  1994年   436篇
  1993年   412篇
  1992年   380篇
  1991年   308篇
  1990年   259篇
  1989年   217篇
  1988年   207篇
  1987年   177篇
  1986年   140篇
  1985年   220篇
  1984年   156篇
  1983年   119篇
  1982年   143篇
  1981年   111篇
  1980年   115篇
  1978年   106篇
  1977年   137篇
  1976年   122篇
  1975年   130篇
  1974年   92篇
  1973年   110篇
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
韩广甸  薛天汉 《有机化学》1986,6(4):249-356
本文综述了利用分子对称性简化天然有机产物合成设计的策略,讨论了具有下述四种对称性的分子的合成:一、对称中心和旋转对称轴;二、对称平面;三、潜在的对称性;四、局部的对称性。  相似文献   
992.
Nguyen TM  Lee D 《Organic letters》2001,3(20):3161-3163
[reaction: see text] A novel reaction between 1,3-dienes and selenium dioxide to give syn 1,2- and 1,4-diol cyclic selenites was studied in detail. This study indicates that an initial concerted [4 + 2] cycloaddition followed by a stereospecific carbon-selenium bond oxidation is involved in this unprecedented syn dihydroxy addition reaction mediated by selenium dioxide.  相似文献   
993.
We report the effects of added acid in the reaction of singlet oxygen with trans-4-propenylanisole (1). We provide evidence that solvent acidity modifies the behavior of the transient intermediates. Relative to reactions in aprotic solvent, enhanced dioxetane concentrations are observed in MeOH and in nonprotic solvents with acid. We suggest a new mechanism that invokes a proton transfer from MeOH and benzoic acid to perepoxide (2) and zwitterion (3) intermediates.  相似文献   
994.
[reaction: see text] The enzymatic degradation of starch can be monitored electronically using single-walled carbon nanotubes (SWNTs) as semiconducting probes in field-effect transistors (FETs). Incubation of these devices in aqueous buffer solutions of amyloglucosidase (AMG) results in the removal of the starch from both the silicon surfaces and the side walls of the SWNTs in the FETs, as evidenced by direct imaging and electronic measurements.  相似文献   
995.
This work reports the fabrication of proton exchange membranes (PEM) with stronger resistance to methanol penetration than Nafion®117. A three-component acrylic polymer blend (TCPB) consisting of a copolymer of 4-vinylphenol-methyl methacrylate, poly(butyl methacrylate) (PBMA) and a copolymer of methyl methacrylate-ethyl acrylate is used as the methanol barrier. In order to implant a proton source phase within the membrane as homogeneously as possible, the hydrophilic monomers, 2-acrylamido-2-methyl propanesulfonic acid (AMPS), 2-hydroxyethyl methacrylate (HEMA) and poly(ethylene glycol) dimethylacrylate (PEGDMA), are polymerized only after they have been embedded in the TCPB matrix. The embedded polymerization has resulted in an asymmetric membrane structure, in which the hydrophilic network is sandwiched by two layers of matrixes with high percentages of TCPB. As expected, this asymmetric membrane structure exhibits lower methanol uptake than Nafion®117; and a proton conductivity in the range of 10−3–10−4 S/cm, which is dependent on the concentration of the sulfonic acid content. It is suggested that the two external layers in this asymmetric membrane provide primarily methanol-blocking and supporting proton-conducting properties; while the middle layer supplies protons and conserves water. This unique sandwiched PEM structure from embedded polymerization is confirmed by microstructure characterizations and by physical property measurements.  相似文献   
996.
A new series of 1beta-methylcarbapenems 1a-d bearing 5-methyl-4-mercaptopyrrolidinone rings has been prepared and evaluated for in vitro antibacterial activity and pharmacokinetic parameters. Most compounds showed excellent antibacterial activity and high stability to dehydropeptidase-1. We have synthesized optically active 5-methyl-4-hydroxypyrrolidinones from enantiomerically pure aziridine esters.  相似文献   
997.
本文报道用环加成-芳构化串连反应制备多取代芳香族化合物的方法。将1-氯-2-卤-3-苯硒基-1,3-丁二烯(5)与丁炔二酸二甲酯进行Diels-Alder反应时,能直接生成多取代的芳香族化合物4-苯硒基-5-卤代邻苯二甲酸二甲酯(4)。若用2-卤素-3-苯硒基-1,3-丁二烯(1)与丁炔二酸二甲酯进行Diels-Alder反应,只得到正常的加成产物4-苯硒基-5-卤素-1,4-环己二烯-1,2-二甲酸二甲酯(3),需再用DDQ处理,才得到多取代芳香族化合物(4)。  相似文献   
998.
5,6-Dimethoxy isobenzofuran is generated in situ from the dimethylacetal of 6-hydroxymethyl veratraldehyde and intercepted by a variety of dienophiles to produce the expected oxygen-bridged adducts in good yield. Many of the latter are easily aromatised to naphthalenes.  相似文献   
999.
软刻蚀及其应用   总被引:2,自引:0,他引:2  
软刻蚀是一类基于自组装和复制模塑等原理的非光刻微米和纳米加工方法。它为形成和制作微米、纳米图案提供了简便、有效、价廉的途径。在软刻蚀中,用一个表面带图案的弹性模板来实现图案的转移,其加工的分辨率可达30nm-100μm。软刻蚀是微接触印刷、复制模塑、转移微模塑、毛细微模塑、溶剂辅助微模塑等的总称。本文将简介软刻蚀的原理、方法以及它们在微米和纳米加工、微电子学、材料科学、光学、微电子机械系统、表面化学等方面的应用。  相似文献   
1000.
A series of potassium-doped MgO catalysts loaded with KOH up to 15 mol% was prepared and evaluated for a single step synthesis of propionitrile from acetonitrile methylation with methanol. As the amount of potassium dope increased, both the acetonitrile conversion and the selectivity toward propionitrile increased. Based on the activity data coupled with CO2-TPD and NH3-IR ones, it was concluded that potassium doping to MgO resulted in the enhancement of both basicity and bifunctionality — methylation and hydrogenation.  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