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   15031篇
  免费   2610篇
  国内免费   1895篇
化学   11166篇
晶体学   227篇
力学   835篇
综合类   130篇
数学   1607篇
物理学   5571篇
  2024年   44篇
  2023年   309篇
  2022年   457篇
  2021年   519篇
  2020年   579篇
  2019年   637篇
  2018年   502篇
  2017年   491篇
  2016年   693篇
  2015年   700篇
  2014年   892篇
  2013年   1206篇
  2012年   1405篇
  2011年   1553篇
  2010年   1033篇
  2009年   1008篇
  2008年   1014篇
  2007年   991篇
  2006年   796篇
  2005年   686篇
  2004年   582篇
  2003年   444篇
  2002年   415篇
  2001年   350篇
  2000年   328篇
  1999年   251篇
  1998年   212篇
  1997年   168篇
  1996年   186篇
  1995年   147篇
  1994年   154篇
  1993年   118篇
  1992年   115篇
  1991年   93篇
  1990年   87篇
  1989年   77篇
  1988年   44篇
  1987年   41篇
  1986年   42篇
  1985年   40篇
  1984年   29篇
  1983年   16篇
  1982年   6篇
  1981年   11篇
  1980年   5篇
  1979年   11篇
  1977年   6篇
  1976年   8篇
  1975年   6篇
  1957年   5篇
排序方式: 共有10000条查询结果,搜索用时 343 毫秒
171.
An efficient method has been developed for one-pot three-component coupling reactions of various aldehydes, 1-cyclohexen-2-one, and primary or secondary amines in the presence of a catalytic amount of Yb(OTf)3 under mild conditions to afford the corresponding 2-arylmethyl N-substituted anilines in good yields. In addition, the catalyst was easily recovered and could be reused for at least four cycles without any loss of activity.  相似文献   
172.
以高炉水淬渣合成的Ca-α-Sialon粉体为原料采用无压烧结技术制备了(Ca/Y)-α-Sialon陶瓷。通过用排水法、三点弯曲实验法、金相显微镜法、XRD法等手段研究了(Ca/Y)-α-Sialon陶瓷的烧结致密化过程、材料的力学性能、显微组织、相组成和材料的断裂特征。结果表明,适量的Y2O3促进材料的烧结致密化和提高材料的力学性能,但Y2O3过量(大于10%)时对材料的烧结和力学性能不利。掺杂Y^3+的(Ca/Y)-α-Sialon呈柱状晶,随着Y2O3含量的增加和烧结温度的提高,(Ca/Y)-α-Sialon呈柱状晶出现粗化和等轴化。含10%Y2O3的材料在1700℃烧结时可获得较高的力学性能。  相似文献   
173.
采用溶胶-凝胶法合成了一种V2O5/C复合材料.扫描电镜(SEM)和红外光谱(FTIR)分析表明,这是一种外层V2O5胶体包覆内层乙炔分子的多孔复合材料.以V2O5/C作正极,锌片为负极,Zn(ClO4)2溶液为电解质组成水相锌二次电池,采用循环伏安(CV)和电化学阻抗谱(EIS)等方法研究发现:V2O5:C质量比为1:1时电极具有最好的电化学性能,电池开路电压达1.64 V; Zn2+能分别在1.01 V和1.26 V处分步嵌入V2O5/C结构中A、B两种位置,其嵌入电流密度峰值最高可达70 mA•g-1,并且具有较好的循环充放电性能;在一定放电深度下,V2O5/C电极反应速率受Zn2+的扩散过程控制.  相似文献   
174.
Plasma-induced surface graft copolymerization of acrylic acid on polypropylene non-woven fabric (PP-g-AA) and polypropylene membrane were reported. The extents of grafting were controlled by the plasma and polymerization condition. Hexadecyltrimethyl ammonium bromide was then coupled with the carboxyl group of PP-g-AA to obtain a polyion complex (PIC). At last, CF4 plasma was used to give PICs hydrophobic property. The moisture regain and water-repellency of the processed PICs was investigated. The surfaces were characterized using ATR FT-IR and XPS. The result indicates that the products have very high ability to adsorb moisture, even better than cotton fiber. At the same time, the products show excellent hydrophobic property, which can‘t be wetted by those reagents whose surface tensions were higher than 327mN/m.  相似文献   
175.
A setup for recording surface tension curves at a mercury drop during potential scanning is designed based on photo-sensitive detection system. Surface tension spectrum at Hg drop can be recorded by voltammetric study. A Yb(III)-NO2- catalytic reduction system was used for characterization. The simple, sensitive technique can be expected to provide fresh information on molecular interactions at electrode surfaces.  相似文献   
176.
177.
As platforms for the design of metal-based therapeutic and diagnostic agents, macrocycles are rigid enough to provide strong metal binding sites and orient functional groups stereoselectively, yet flexible enough to accommodate structural changes required for induced-fit recognition of biological targets. We consider the recognition of the Zn(II) complex of the bis-tetraazamacrocycle xylyl-bicyclam, a potent anti-HIV agent, by the coreceptor CXCR4, a G-protein-coupled receptor used by HIV for membrane fusion and cell entry. NMR studies show that the macrocycles of Zn(II)(2)-xylyl-bicyclam perchlorate exist in aqueous solution as two major configurations, trans-I (nitrogen chirality R,S,R,S), and trans-III (S,S,R,R). Acetate addition induced a major structural change. X-ray crystallography shows that the acetate complex contains the unusual cis-V cyclam configuration (R,R,R,R and folded) with bidentate coordination of acetate to Zn(II) plus second-coordination-sphere double H-bond formation between diagonal NH protons on the opposite cyclam face and acetate carboxylate oxygens. Detailed 1D and 2D NMR studies show that the major configuration of Zn(II)(2)-xylyl-bicyclam acetate in aqueous solution is cis-V/trans-I. Molecular modeling shows that an analogous cis-V site can be formed when Zn(II)(2)-xylyl-bicyclam binds to CXCR4, involving the carboxylate groups of Asp262 (Zn(II) coordination) and Glu288 (double H-bonding). The second cyclam can adopt the trans-I (or trans-III) configuration with Zn(II) binding to Asp171. These interactions are consistent with the known structure-activity relationships for bicyclam anti-HIV activity and receptor mutation. Consideration of the anti-HIV activity of xylyl-bicyclam complexes of other metal ions suggests that affinity for carboxylates, configurational flexibility, and kinetic factors may all play roles in receptor recognition. For example, Pd(II) cyclam complexes interact only weakly with axial ligands and are inflexible and inactive, whereas Co(III) cyclams bind carboxylates strongly, are configurationally flexible, and yet have low activity. Our findings should aid the design of new generations of active macrocycles including highly specific chemokine receptor antagonists.  相似文献   
178.
IntroductionIndium-tin-oxide(ITO) has been widely used asthe anode material in organic light-emitting devices(OLEDs) because of its high transmittance in the visi-ble region and low electrical resistivity. In the pastyears, many investigations focused on …  相似文献   
179.
以石墨粉为原料, 采用Hummers法液相氧化合成了氧化石墨(GO), 然后用化学一步还原制得石墨烯负载钯催化剂. X射线衍射(XRD)、透射电镜(TEM)表征表明, Pd在石墨烯载体上有较好的分散度, 粒径为3-5 nm. 电化学活性面积(EASA)、循环伏安(CV)、计时电流(CA)和计时电位(CP)等电化学测试表明, 与传统Pd/Vulcan XC-72相比, Pd/石墨烯催化剂对碱性介质中乙醇电催化氧化的催化活性有了很大的提高.  相似文献   
180.
Liang A  Chao Y  Liu X  Du Y  Wang K  Qian S  Lin B 《Electrophoresis》2005,26(18):3460-3467
A capillary electrophoresis (CE) method was developed for the separation of heparin oligosaccharides compatible to study the interactions between the oligosaccharides and granulocyte-colony stimulating factor (G-CSF). Unfractionated heparin was eliminitively degraded to heparin oligosaccharides by an endolytic heparinase. The degraded smaller oligosaccharides (M(r) < 1000) were baseline-separated by CE under a 50 mM phosphate buffer (pH 9.0) in 10 min. Standard heparin disaccharides and larger oligosaccharides (1000 < M(r) < 8000) were all separated under optimized separation conditions. Compared with standard heparin disaccharides, smaller oligosaccharides contained one nonsulfated, two monosulfated, and two disulfated disaccharides, but trisulfated disaccharides were not found. The smaller oligosaccharides were also identified and molecular mass was deduced by electrospray ionization-mass spectrometry (ESI-MS). Furthermore, interactions between G-CSF and the oligosaccharides were studied by using capillary zone electrophoresis (CZE) under the above separation conditions. It was found that larger oligosaccharides could interact with G-CSF while smaller oligosaccharides were not observed to bind to G-CSF under the experimental conditions. In conclusion, the purified heparinase could selectively degrade heparin into oligosaccharides and the interaction between G-CSF and heparin was correlated with the chain length of heparin.  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