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   105128篇
  免费   6934篇
  国内免费   12550篇
化学   74362篇
晶体学   1272篇
力学   4550篇
综合类   1074篇
数学   17925篇
物理学   25429篇
  2024年   150篇
  2023年   860篇
  2022年   2261篇
  2021年   2227篇
  2020年   2640篇
  2019年   2521篇
  2018年   2223篇
  2017年   3277篇
  2016年   3541篇
  2015年   2984篇
  2014年   4042篇
  2013年   7687篇
  2012年   6984篇
  2011年   5796篇
  2010年   4887篇
  2009年   6582篇
  2008年   6817篇
  2007年   7088篇
  2006年   6377篇
  2005年   5346篇
  2004年   4989篇
  2003年   4241篇
  2002年   5365篇
  2001年   3167篇
  2000年   3002篇
  1999年   2785篇
  1998年   2439篇
  1997年   1907篇
  1996年   1658篇
  1995年   1558篇
  1994年   1376篇
  1993年   1139篇
  1992年   1058篇
  1991年   741篇
  1990年   636篇
  1989年   598篇
  1988年   456篇
  1987年   372篇
  1986年   334篇
  1985年   309篇
  1984年   278篇
  1983年   165篇
  1982年   250篇
  1981年   205篇
  1980年   247篇
  1979年   241篇
  1978年   203篇
  1977年   158篇
  1976年   146篇
  1973年   75篇
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
911.
(η^2—C60)[Pt(PPh3)2]8的合成与表征   总被引:6,自引:2,他引:6  
C60是高度共轭的宠状结构碳素体.分子结构中六元环间的共价碳碳双键是富电子区,其反应性能与烯键类似,以碳碳双键与中心金属形成η2配位化合物.富勒烯η2配合物的合成及性能研究是当前研究热点之一[1~7].本文在(η2-C60)[Pt(PPh3)2]n(n=1~6)系列研究[7]的基础上制备了(η2-C60)[Pt(PPh3)2]8,并用元素分析、红外光谱和光电子能谱进行鉴定和表征.1实验部分四(三苯基膦)合铂Pt(PPh3)4按文献[8]方法制备;C60纯度为99%;其余试剂均为分析纯.元素分析在ERLA-1106型元素分析仪上进行;光电子能谱在VGESCA…  相似文献   
912.
The polarographic behaviour of salicylaldehyde-2-pyridylhydrazone (SAPH) has been studied in aqueous buffer solution containing 40% ethanol using DC and DP polarographic methods. In the pH range 1.8–7.5 the observed single irreversible reduction wave is assigned to the splitting of the N-N bond and reduction of C=N centre. In alkaline medium, a second wave appears at a more negative potential due to the reduction of the salicylaldehyde which is formed by hydrolytic decomposition of the SAPH molecule. The effect of pH on the limiting current andE 1/2 as well as the reduction mechanism are discussed and compared with similar compounds. The kinetic parameters of the electrode reaction have been calculated.The analytical properties of the copper(II)-SAPH system is described. The complex gave rise to a single irreversible well-defined wave (E 1/2=–0.58 V at pH=5.2). The reaction process is diffusion controlled. A method is suggested for the determination of Cu(II) in presence of different metal ions as the difference in theirE 1/2 values is sufficient for the purpose.This work is taken partly from the M. Sc. Thesis of Jamal S. Shalabi  相似文献   
913.
针对以往电子俘获光存储材料存在的问题,利用高温固相反应发制备了一种Eu^2 掺杂的氟氧化物玻璃陶瓷,研究表明在该材料中具有光激励发光(PSL)特性,并可用于电子俘获光存储。XRD分析表明该材料含有大量的BaF2微晶。根据其与BaF2相似的发光特性,推断玻璃陶瓷的PSL有可能来源于微晶中Eu^2 的5d-4f发射。但是决定光激励发光过程中的电子(空穴)陷阱的存在方式、电子迁移途径都有待进一步探讨的问题。与传统的BaFCl:Eu相比,这种材料的光激励发光衰减速度较慢。  相似文献   
914.
溶胶-凝胶法合成纳米铬酸锶镧的工艺研究   总被引:1,自引:3,他引:1  
以硝酸镧、硝酸铬、硝酸锶为原料,乙二醇为分散剂,柠檬酸为胶溶剂,用溶胶-凝胶法合成纳米级的铬酸锶镧粉体。利用TG,DSC,XRD分析研究了粉料的晶化过程。利用HREM分析了煅烧温度、含锶量对粉料粒径的影响。研究表明,获得纳米晶的最佳烧结温度在800℃。随着锶掺杂量的增加,粉料的粒径逐渐变小。  相似文献   
915.
The root of Carlina acanthifolia All. (Asteraceae) contained 1.0% of essential oil (expressed in g per 100 g of dried plant material). Using GC and GC/MS, nine components were identified (100% of total oil). The structure of benzyl 2-furylacetylene (carlina oxide), which is the principal component of the oil (91.5%), was spectrometrically identified. __________ Published in Khimiya Prirodnykh Soedinenii, No. 4, pp. 331–332, July–August, 2005.  相似文献   
916.
Shin-ichi Naya 《Tetrahedron》2004,60(23):4953-4958
The synthesis and properties of a novel type of 7,7-bis(heteroazulen-3-yl)-8,8-dicyano-1,4-quinodimethanes (9a-c) are studied. The synthetic method is based on a TFA-catalyzed electrophilic aromatic substitution on the heteroazulenes with 4-(dicyanomethyl)benzaldehyde to afford the corresponding methane derivatives, followed by oxidative hydrogen abstraction with DDQ. The polarization of 9a-c is evaluated by the inspection of their 13C NMR and IR spectra. Based on the investigation of the UV-Vis spectra of 9a-c and protonated cations 10a-c, conformational changes of the heteroazulene-moiety and (dicyanomethyl)phenyl group are suggested. In the CV measurements of 9a-c, two reversible reduction waves are observed, indicating the stabilizing ability of heteroazulenes toward the corresponding radical and anion species. Furthermore, 9a-c exhibit two irreversible oxidation waves, which suggest a conformational change in the radical cation during the redox process. The conformational change is rationalized on the basis of the MO calculations.  相似文献   
917.
S-Alkylation of 2-acetamido-9-(2-acetoxyethoxymethyl)-6-oxo-8-thioxopurine was used to synthesize its novel S- and N(7)-substituted derivatives. We have established the effect of the structure of the alkylating agent on the reaction conditions and its regioselectivity. We have shown that the synthesized guanine derivatives can be modified further.  相似文献   
918.
《Electroanalysis》2003,15(14):1192-1197
The investigation of the electrochemical reduction processes of C6H5SSC6H5 and C6H5SH in CH3CN using cyclic voltammetry indicates a different behavior on GC and Au electrodes. On GC surface adsorption phenomena are absent, the electrochemical reduction process is irreversible and diffusion controlled. For both the starting molecules the same species, C6H5S?, is formed upon reduction. The E° values of the reduction processes were determined by convolution method and the standard free energy of the S? S bond of C6H5SSC6H5 estimated. On Au surface instead, a self‐assembled monolayer of C6H5SAuads originated after the S? S or S? H bond breaking can be observed by simply dipping the electrode in solution of C6H5SSC6H5 and C6H5SH, respectively. The properties of the SAM were investigated by electrochemical reduction of the adsorbed thiolates. On Au electrode the reduction processes involve C6H5SAuads and give rise to desorbed C6H5S?. A neutral radical is obtained by electrochemical oxidation of thiolate anion. It reacts rapidly with the electrode surface to give the S‐Au bond again.  相似文献   
919.
Summary.  Novel N-(3-oxobutyl)-hydroxy- and acetoxypyrido[2,3-d]pyridazinones were synthesized and tested in vivo for their sedative and anticonvulsant activity. The Michael-type reaction of quinolinic acid hydrazide and methyl vinyl ketone afforded a mixture of two isomers, 5-hydroxy-N 7-(3-oxobutyl)-pyrido[2,3-d]pyridazin-8(7H)-one and 8-hydroxy-N 6-(3-oxobutyl)-pyrido[2,3,-d]pyridazin-5-(6H)-one, in a ratio of 2:1 which were separated by crystallization. Subsequent acetylation of both isomers yielded the corresponding 5- and 8-acetoxy compounds. The structures of the compounds were proven and completely assigned on the basis of 1H, 13C, 15N NMR, and 1D NOE difference spectra as well as 2D C,H-correlation experiments. Preliminary pharmacological tests showed low acute toxicity with a LD 50 > 1000 mg/kg in the mouse and sedative activity for the title compounds. 5-Acetoxy-N 7- (3-oxobutyl)-pyrido[2,3-d]pyridazin-8(7H)-one displayed a borderline anticonvulsant activity in the metrazole test model. Corresponding author. E-mail: edith.goessnitzer@uni-graz.at Received March 20, 2002; accepted April 3, 2002  相似文献   
920.
Monodisperse poly(methyl methacrylate) (PMMA) particles containing various concentrations of stearyl methacrylate (SMA) were prepared, and a liquid crystal (LC) was swollen into the particles using a solute co-diffusion method (SCM). Phase separation behaviors between the polymer and LC were monitored by utilizing an optical and a polarized microscope (OM/POM). The monodisperse LC microcapsules were then applied to a polymer-dispersed liquid crystal (PDLC), and the electro-optical properties were investigated. As a result, the threshold and driving voltages were improved when the SMA content increased. The long alkyl chains of SMA in the capsules should exist at the interface of the LC and polymer resulting in an enhancement of phase separation between the polymer and LC, which largely influences the electro-optical properties of PDLC.  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