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   16504篇
  免费   2832篇
  国内免费   1884篇
化学   11669篇
晶体学   170篇
力学   1188篇
综合类   65篇
数学   1694篇
物理学   6434篇
  2024年   58篇
  2023年   358篇
  2022年   615篇
  2021年   624篇
  2020年   667篇
  2019年   617篇
  2018年   581篇
  2017年   522篇
  2016年   882篇
  2015年   776篇
  2014年   979篇
  2013年   1187篇
  2012年   1515篇
  2011年   1486篇
  2010年   1006篇
  2009年   940篇
  2008年   1088篇
  2007年   966篇
  2006年   870篇
  2005年   774篇
  2004年   537篇
  2003年   438篇
  2002年   426篇
  2001年   349篇
  2000年   305篇
  1999年   344篇
  1998年   274篇
  1997年   243篇
  1996年   285篇
  1995年   271篇
  1994年   192篇
  1993年   159篇
  1992年   155篇
  1991年   151篇
  1990年   128篇
  1989年   101篇
  1988年   85篇
  1987年   69篇
  1986年   51篇
  1985年   42篇
  1984年   30篇
  1983年   25篇
  1982年   14篇
  1981年   16篇
  1980年   9篇
  1978年   2篇
  1972年   1篇
  1971年   1篇
  1957年   6篇
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
161.
用动力学方法对Li2O·nB2O3-20%LiCl-H2O体系(n=1,2,3)20℃过饱和溶液结晶过程进行研究,结果表明每一种溶液只析出一种固相,Li2O∶B2O3=1∶1、1∶2和1∶3的氯化锂溶液分别结晶出Li2O·B2O3·4H2O, Li2O·2B2O3·3H2O和Li2O·5B2O3·10H2O,拟合并给出结晶动力学方程,同时对这三种固相的结晶反应机理进行了探讨。  相似文献   
162.
Upon the study of small-molecules binding to proteins, the traditional methods for calculating dissociation constants (Kd and Ki) have shortcomings in dealing with the single binding site models. In this paper, two equations have been derived to solve this problem. These two equations are independent of the total concentration or initial degree of saturation of receptor and the activity of the competitive molecule. Through nonlinear fitting against these two equations, Kd value of a probe can be obtained by binding assay, and Ki value of a ligand can be obtained by competitive assay. Moreover, only the total concentrations of receptor([R]t), ligand([L]t) and probe([P]t) are required for the data fitting. In this work, Ki values of some typical ligands of PPARγ were successfully determined by use of our equations, among which the Ki value of PPARγ-LY171883 was reported for the first time.  相似文献   
163.
An efficient method is reported for the synthesis of phenacyl esters by reaction of carboxylic acids with a-bromoacetophenone promoted by potassium fluoride in ionic liquid [Bmim]PF6, the yield of the reaction is almost quantitative and the products are essentially pure.  相似文献   
164.
[reaction: see text] A concise and enantioselective synthesis of (S)-2-cyclohexyl-2-phenylglycolic acid as a key intermediate for (S)-oxybutynin is reported. The crucial asymmetric tetrasubstituted carbon center was constructed with excellent stereoselectivity through the proline-catalyzed direct asymmetric aldol reaction between cyclohexanone and ethyl phenylglyoxylate under mild conditions.  相似文献   
165.
Cyano-bridged corrugated ladder-like chains are connected by mu(1,1)-N(3) (end-on, EO) bridges to form a layered coordination polymer, [Mn(N(3))(CH(3)OH)[Cr(phen)(CN)(4)].CH(3)OH (2), which is the first mixed cyano-azide bridged compound, and shows metamagnetism below 21.8 K, a temperature much higher than that (3.4 K) of the crossed double chain [Cr(phen)(CN)(4)](2) [Mn(H(2)O)(2)].4H(2)O (1) based on the same building block [Cr(phen)(CN)(4)](-).  相似文献   
166.
采用Ca(2+)选择电极,pH电极和电导电极对钠硼解石水溶液碳化过程进行跟踪测定。实验结果表明:反应分二步进行,反应最终结果是钠硼解石完全分解,硼全部进入溶液并大部分以H3BO3的形式存在,同时考察了温度,气流量对钠硼解石水溶液碳化结果的影响。根据碳化机理,提出了较佳的碳化条件。  相似文献   
167.
Metalloprotein tethered CdSe nanoparticles have been generated to provide selective and reagentless maltose biosensing. As opposed to cell or protein detection by semiconducting nanoparticle bioconjugates, a modular method for small-molecule detection using semiconducting nanoparticle bioconjugates has been difficult. Here we report a method for reagentless protein-based semiconducting nanoparticle biosensors. This method uses Ru(II) complex-CdSe nanoparticle interactions and the maltose-induced conformation changes of maltose binding protein to alter the CdSe nanoparticle fluorescence emission intensity. In this proof-of-principle system, the maltose-induced protein conformation changes alter the Ru(II) complex-CdSe nanoparticle interaction, which increases the CdSe emission intensity. Altered CdSe emission intensity effects are best described as electron transfer from the Ru(II) complex to the CdSe excited state forming the nonfluorescent CdSe anion. Four surface-cysteine, Ru(II) complex-attached maltose-binding proteins have been studied for maltose dependent alteration of CdSe emission intensities. With 3.0-3.5 nm diameter CdSe nanoparticles, all ruthenated maltose-binding proteins display similar maltose-dependent increases (1.4-fold) in CdSe emission intensity and maltose binding affinities (KA = 3 x 106 M-1). For these four systems, the only difference was the sample-to-sample variation in maltose-dependent responses. Thus, very few surface cysteine mutations need to be examined to find a successful biosensor, as opposed to analogous systems using organic fluorophores. This strategy generates a unimolecular, or reagentless, semiconducting nanoparticle biosensor for maltose, which could be applied to other proteins with ligand-dependent conformation changes.  相似文献   
168.
Small fixed aggregates of a poly(ethylene oxide)-block-polybutadiene diblock copolymer(PEO-b-PB)in THFsolution were obtained by adding a selective solvent for PB blocks,followed by cross-linking the PB shells.Themorphologies of the nanostructured particles with a cross-linked shell were investigated by atomic force microscopy andtransmission electron microscopy.The average behaviors of the PEO crystallization and melting confined within thenanostructured particles were studied by using differential scanning calorimetry experiments.For the deeply cross-linkedsample(SCL-1),the crystallization of the PEO blocks was fully confined.The individual nanoparticles only crystallized atvery low crystallization temperatures(T_cs),wherein the homogenous primary nucleation determined the overallcrystallization rate.For the lightly cross-linked sample(SCL-2),the confinement effect was T_c dependent.At T_c(?)42℃,thecrystallization and melting behaviors of SCL-2 were similar to those of the pure PEO-b-PB diblock copolymer.At T_c>42℃,SCL-2 could form PEO lamellae thicker than those of the pure PEO-b-PB crystallized at the same T_c.  相似文献   
169.
Green light emitting Zn2SiO4:Mn phosphors have been prepared via a low-temperature solid-state reaction using mesoporous silica SBA-15 template. This mesoporous silica template method features low-temperature formation of phosphors and easy doping. The structure and morphology of the phosphors were characterized by XRD, SEM, TEM, and N2 adsorption/desorption techniques, which confirmed the single crystallinity, ordered mesostructure, closed pore channels, and elongated ropelike morphology. The luminescent properties were examined by photoluminescence spectroscopy at room temperature, and the results of fluorescence decay time measurements show non-single-exponential decay behavior and a decrease of the decay time with an increase of the Mn concentration.  相似文献   
170.
高养馨  沈中和 《有机化学》1983,3(4):273-276
四氟乙烯和全氟4-甲基-3,6-二氧杂-△~7辛基磺酰氟在溶剂氟里昂-113(F-113)中进行自由基引发聚合反应时,共聚物(T-O)是否有链转移,可以通过测定所得共聚物中的含氯量来得以证实。我们首次应用质子X萤光分析法(PIXE)进行分析。结果表明,共聚物中含氯量小于1ppm,F-113溶剂并未发生链转移。同时,我们测定了已证明有F-113参与链转移反应的F_(40)试样,含氯量高达700ppm。  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