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   3563篇
  免费   343篇
  国内免费   368篇
化学   2513篇
晶体学   44篇
力学   222篇
综合类   37篇
数学   434篇
物理学   1024篇
  2024年   5篇
  2023年   55篇
  2022年   100篇
  2021年   112篇
  2020年   121篇
  2019年   132篇
  2018年   111篇
  2017年   90篇
  2016年   128篇
  2015年   133篇
  2014年   174篇
  2013年   230篇
  2012年   256篇
  2011年   290篇
  2010年   206篇
  2009年   169篇
  2008年   211篇
  2007年   219篇
  2006年   203篇
  2005年   183篇
  2004年   106篇
  2003年   98篇
  2002年   123篇
  2001年   91篇
  2000年   60篇
  1999年   54篇
  1998年   65篇
  1997年   57篇
  1996年   68篇
  1995年   61篇
  1994年   48篇
  1993年   35篇
  1992年   51篇
  1991年   30篇
  1990年   41篇
  1989年   26篇
  1988年   23篇
  1987年   19篇
  1986年   13篇
  1985年   16篇
  1984年   15篇
  1983年   9篇
  1982年   6篇
  1981年   7篇
  1980年   4篇
  1979年   5篇
  1978年   4篇
  1975年   3篇
  1961年   1篇
  1954年   1篇
排序方式: 共有4274条查询结果,搜索用时 453 毫秒
81.
A novel protocol allowing convenient and highly selective visual recognition of melamine in raw milk via selective metallo-hydrogel formation at a concentration as low as 10 ppm without any tedious pretreatment has been developed.  相似文献   
82.
Li H  Tu H  Cai Q  Xian Y  Jin L 《The Analyst》2001,126(5):669-672
A Pt microelectrode modified with nickel(II) polytetramethyldibenzo[b,i]tetraaza[14]annulene was prepared by electropolymerization of nickel(II) tetramethyldibenzo[b,i]tetraaza[14]annulene monomers and applied to determine sulfur dioxide in vitriol plant wastewater. For determination of SO2 with this electrochemically modified Pt microelectrode, the linear range was from 9.6 x 10(-6) to 2.4 x 10(-4) mol L-1, the sensitivity was 1.8 x 10(-4) A L mol-1, the detection limit was calculated to be 4.8 x 10(-6) mol L-1 (S/N = 3), the response time was less than 20 s and the relative standard deviation was found to be 2.1% on analyzing 4.8 x 10(-5) mol L-1 SO2 solution repeatedly (n = 7). These results demonstrated good accuracy compared with those obtained by the conventional iodimetric method.  相似文献   
83.
红四氮唑作为电化学嵌合剂的核酸杂交生物传感器   总被引:6,自引:0,他引:6  
提出了一种以红四氮唑 (TTC)作为嵌合剂 ,采用石墨修饰电极监测核酸杂交过程和测定特定 DNA片段的灵敏的电化学方法 . TTC具有背景电流低 ,电活性强和对双链 DNA(ds DNA)选择性好等一系列优点 ,可在石墨电极表面形成 ds DNA-TTC层 .在电化学测定中 ,TTC的还原电流与靶 DNA浓度具有良好的线性关系 ,对 DNA的检测限可低达 6× 1 0 - 1 1 mol/L .  相似文献   
84.
Zn-Fe-SiO2复合镀层的制备工艺及其耐蚀性研究   总被引:1,自引:0,他引:1  
在酸性硫酸盐体系中电沉积制备了Zn-Fe-SiO2复合镀层,并研究了工艺因素对镀层SiO2含量的影响.随着电流密度由4.8A/dm2增加到6A/dm2时,镀层中SiO2的含量由0.21%上升到0.47%,但是当电流密度继续增加到7.2A/dm2时,SiO2含量反而下降到了0.18%.当镀液中SiO2浓度由20g/L增加到60g/L时,镀层中SiO2含量由0.40%上升到0.51%.当镀液pH值由2增加到4时,镀层中SiO2含量由0.22%上升到1.17%.采用5%NaCl溶液浸泡试验考察了Zn镀层、Zn-Fe合金镀层与Zn-Fe-SiO2复合镀层的耐蚀性,并研究了镀层中SiO2含量对镀层耐蚀性的影响.结果表明,Zn-Fe-SiO2复合镀层无需钝化处理,其耐蚀性优于Zn镀层及Zn-Fe合金镀层,并且镀层的耐蚀性随着镀层中SiO2含量增大而提高.  相似文献   
85.
Zr(Y)O2衬底上大面积YBCO薄膜表面组织状态的研究   总被引:1,自引:0,他引:1  
使用配备有EDS和ECP附件的SEM、AEM、和STM研究在750和800℃的Zr(Y)O2衬底上磁控溅射沉积的大面积YBCO超导薄膜的表面组织。YBCO薄膜为c轴取向单晶,但衬底温度为800℃时,膜表面的突出组织多为CuO颗粒,小坑较多,表面粗糙;衬底温度为750℃时,突出组织多为棒状和多边形123结构,很少小坑,表面较平整。  相似文献   
86.
1. INTRODUCTION Study on the deposition of metal ions on ACFs indicated that such a process consists of several consecutive steps [1]: (1) transfer of the solvated ions (metal ions) from the bulk solution to the proximity of the ACFs surface; (2) absorpt…  相似文献   
87.
1-Butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF4]) is one of the promising room-temperature ionic liquids. To test the refined force field for [bmim][BF4] proposed in our previously work (J. Phys. Chem. B, 2004, 108, 12978-12989), thermodynamic properties of mixtures of [bmim][BF4](1)+ acetonitrile (2) are presented by using molecular dynamics over the whole concentration range. The calculated densities are in good agreement with the experimental data with deviations less than 2%, indicating the force field is applicable to the mixtures. In addition, the diffusion constants, viscosities, heats of vaporization, cohesive energy densities and excess properties of the mixtures are reported. The microscopic structures are discussed in detail, corresponding to the thermodynamic properties.  相似文献   
88.
Oral clonidine, used as an antihypertensive, can result in some side effects such as dry mouth, drowsiness, dizziness and sedation; thus, clonidine transdermal drug delivery (TDD) was considered. Use of the controlled release membrane was one of the methods in TDD systems to regulate the permeation properties. A new type of copolymer membrane that controlled clonidine linear release in TDD system was synthesized by UV radiation. This membrane consisted of three monomers: 2-hydroxy-3-phenoxypropylacrylate, 4-hydroxybutyl acrylate and diethyl maleate. The membrane had both fine permeation properties and perfect physical properties when three monomers were in the weight ratio of 4:4:2; this type of membrane was chosen as an optimized membrane. It was found that the membrane controlled clonidine zero-order release, the permeation rates decreased with the thicknesses of membranes increasing, and the permeation rates were linearly dependent on the square root of the concentration of clonidine. Furthermore, the optimized membranes were characterized by FTIR, DSC and SEM.  相似文献   
89.
The thermal reaction of HNCO has been studied in a static cell at temperatures between 873 and 1220 K and a constant pressure of 800 torr under highly diluted conditions. The reaction was measurable above 1000 K by FTIR spectrometry. The products detected include CO, CO2, HCN, NH3, and the unreacted HNCO. In this moderate temperature regime, the rates of product formation and HNCO decay cannot be accounted for by a previously established high-temperature mechanism, assuming HNCO → NH + CO (1) as the initiation process. Instead, a new bimolecular reaction, 2HNCO → CO2 + HNCNH (2), has been invoked to interpret the disappearance of HNCO as well as the formation of various products, most importantly CO2. The concentration profiles of all measured species can be quantitatively modeled, throughout the temperature range analyzed, by varying k2 using a modified mechanism. The kinetically modeled values of k2 can be effectively represented by This result agrees closely with that computed with the conventional transition-state theory using the TST parameters predicted by the BAC-MP4 method: The bimolecular reaction takes place via a stable 4-membered ring intermediate which is isoelectronic with diketene; viz.   相似文献   
90.
In this paper a deeper insight into the chorismate-to prephenate-rearrangement, catalyzed by Bacillus subtilis chorismate mutase, is provided by means of a combination of statistical quantum mechanics/molecular mechanics simulation methods and hybrid potential energy surface exploration techniques. The main aim of this work is to present an estimation of the preorganization and reorganization terms of the enzyme catalytic rate enhancement. To analyze the first of these, we have studied different conformational equilibria of chorismate in aqueous solution and in the enzyme active site. Our conclusion is that chorismate mutase preferentially binds the reactive conformer of the substrate--that presenting a structure similar to the transition state of the reaction to be catalyzed--with shorter distances between the carbon atoms to be bonded and more diaxial character. With respect to the reorganization effect, an energy decomposition analysis of the potential energies of the reactive reactant and of the reaction transition state in aqueous solution and in the enzyme shows that the enzyme structure is better adapted to the transition structure. This means not only a more negative electrostatic interaction energy with the transition state but also a low enzyme deformation contribution to the energy barrier. Our calculations reveal that the structure of the enzyme is responsible for stabilizing the transition state structure of the reaction, with concomitant selection of the reactive form of the reactants. This is, the same enzymatic pattern that stabilizes the transition structure also promotes those reactant structures closer to the transition structure (i.e., the reactive reactants). In fact, both reorganization and preorganization effects have to be considered as the two faces of the same coin, having a common origin in the effect of the enzyme structure on the energy surface of the substrate.  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