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   4477篇
  免费   806篇
  国内免费   539篇
化学   3296篇
晶体学   40篇
力学   270篇
综合类   48篇
数学   426篇
物理学   1742篇
  2024年   11篇
  2023年   124篇
  2022年   105篇
  2021年   172篇
  2020年   214篇
  2019年   171篇
  2018年   147篇
  2017年   132篇
  2016年   204篇
  2015年   180篇
  2014年   253篇
  2013年   288篇
  2012年   399篇
  2011年   387篇
  2010年   291篇
  2009年   289篇
  2008年   318篇
  2007年   313篇
  2006年   294篇
  2005年   208篇
  2004年   147篇
  2003年   117篇
  2002年   109篇
  2001年   89篇
  2000年   87篇
  1999年   99篇
  1998年   90篇
  1997年   90篇
  1996年   65篇
  1995年   90篇
  1994年   75篇
  1993年   44篇
  1992年   58篇
  1991年   45篇
  1990年   39篇
  1989年   25篇
  1988年   16篇
  1987年   12篇
  1986年   8篇
  1985年   8篇
  1984年   4篇
  1983年   1篇
  1982年   2篇
  1981年   1篇
  1980年   1篇
排序方式: 共有5822条查询结果,搜索用时 31 毫秒
81.
Self-assembled monolayers (SAMs) of functionalized azobenzene thiols (RAzoCnSH, n=3-6 for R=H, abbreviated as AzoCnSH; and n=4 for R=CH(3)CONH, abbreviated as aaAzoC4SH) on different substrates RAzoCnSz.sbnd;z.sfnc;S (S represents substrates of vacuum-deposited gold (Au), silver foil (Ag), HNO(3) etched silver foil (EAg), and silver mirror (mAg)) have been studied by SERS in the near-infrared region. SERS of the SAMs on EAg and/or mAg exhibit SERS effects that vary with etching time and/or deposition time. The most appropriate time is 5 s for etching in 1:1 HNO(3) and 40 s for deposition in 0.1 M Ag(NH(3))(2)NO(3). Further, a layer of Ag mirror was conveniently deposited on the top of the SAMs on different substrates, yielding a more efficient SERS-active system possessing a "sandwiched" structure of mAgz.sfnc;RAzoCnS-z.sfnc;S. An appropriate surface roughness is required for the strongest SERS effect. Scanning electron microscopy (SEM) indicates that there exist a large number of projects around 100 nm on the surface showing the strongest SERS effect. When the surface roughness is decreased or increased, the SERS effect decreases sharply. The relationship between the SERS effect and the structural nature was investigated and showed that the enhancement factor decays exponentially with increasing in distances of the azobenzene group from the underlying substrate or the overlying silver mirror. This result reveals that the SERS effect may be the result of the electromagnetic coupling effect between two metal layers.  相似文献   
82.
We present low stress cubic boron nitride (cBN) films with a transition layer deposited on the metal alloy substrates by tuned substrate radio-frequency magnetron sputtering. The films were characterized by Fourier transform infrared spectroscopy and transmission electron microscopy (TEM). The IR peak position of cubic boron nitride at 1006.3 cm−1, which is close to the stressless state, indicates that the film has very low internal stress. The TEM image shows that pure CBN phase exists on the surface of the film. Several phases of boron nitride were found at the medium implantation dose. It is believed that the transition from the low ordered phases to cBN phase occurred during implantation.  相似文献   
83.
Zhou J  Zou SF  Liang WA 《Talanta》1993,40(6):925-929
We have developed a method that makes use of dual isosbestic points in a dual ligand, single metal system that allows the determination of the equilibrium constants of complexes in which two ligands compete for the same metal ion, and one complex is colourless. The competition of methyl thymol blue and citrate was used to test the model.  相似文献   
84.
A stepwise deposition method was employed to create ordered polyaniline (PANI) nanowires with remarkably enhanced capacitance. Cyclic voltammetry, AC impedance, and galvanostatic charge/discharge cycling were employed to investigate the electrochemical performance of the PANI electrodes. The PANI-deposited electrode exhibits much higher capacitance than those prepared by one-step deposition method, which were mainly contributed from the unique nano structure of PANI and the increased biological, economical, and technical surface areas. The superior capacitive behaviors of the nano PANI electrodes show great potential in preparation of high efficient electrochemical capacitors or rechargeable batteries.  相似文献   
85.
Currently, there is great interest in the development of methods suitable for determining the stoichiometry of biomolecules attached to nanoparticles. We describe the use of the dynamic light-scattering technique (DLS) to determine the stoichiometry of the protein cytochrome P450(BSbeta) attached to CdS and CdSe quantum dots (QDs). The enzyme-conjugated QDs have different diffusion characteristics compared to the QD and enzyme precursors, expressed in their size, scattering intensity as well as zeta-potential values. The significant enhancement of the scattering intensity of QDs observed upon conjugation with the P450(BSbeta) due to the refractive-index increment and the systematic variation in zeta potential resulting from charge neutralization of the anionic QDs by the cationic histidine-tagged P450(BSbeta) have been used for stoichiometry determination.  相似文献   
86.
对含有常见取代基的92个二取代苯化合物进行了结构优化和静电势及其导出参数的计算,运用多元线性回归方法对化合物的疏水常数与分子的结构参数进行了关联.结果表明,分子表面负静电势的加和ΣV-S、分子空间内最负的静电势Vmin、表面最大静电势Vs,max以及分子体积V、极性表面积APS和分子的偶极密度μ/V这六个参数,可以很好地用于表达这些化合物疏水性与分子结构间的定量关系,而不用具体考虑分子中极性基团间的相互作用.用建立起来的QSPR(quantitative structure-property relationship)关系式对111个类似化合物的疏水性进行了预测,获得了满意的结果.  相似文献   
87.
利用晶体场理论,推导出Yb3+离子基态(2F7/2)与Nd3+离子基态(4I9/2)最大分裂能之间的关系式为△E(2F7/2)=1.4667△E(4I9/2),从实验数据拟合得到的关系式为△E(2F7/2)=1.0987△E(4I9/2).理论计算与实验拟合存在差异,分析了出现差异的原因,认为差异主要是由相同晶体场对于不同掺杂离子的影响即晶体场参数Nv值不完全相同而引起的.  相似文献   
88.
固相热分解反应最可几机制的判断   总被引:1,自引:0,他引:1  
固相热分解反应最可几机制的判断高永煜,邹文樵,冯仰婕(华东理工大学化学系上海200237)关键词热分解,动力学方程,反应机制固相热分解反应机制的判断,是热分析动力学中令人感兴趣的领域。常用的方法是从含机制函数的非等温积分动力学方程出发,分别用Sest...  相似文献   
89.
Liu Y  Jiang Y  Song W  Lu N  Zou M  Xu H  Yu Z 《Talanta》2000,50(6):1261-1266
A method for the determination of the major serotonin metabolite — 5-hydroxyindole-3-acetic acid (5-HIAA) in human gastric juice by cyclic voltammetry was described. The measurement conditions were investigated. The potential window was chosen from +0.1 to +0.9 V, the supporting electrolyte was 0.025 M PBS solution (pH 2.0). The method allowed determination in the concentration range from 2.0 ×10−7 to 2.0 ×10 −5 M and a detection limit of 80 nM. When samples of gastric juice were analyzed with the method, we obtained the mean content of 5-HIAA in the gastric juice. Meanwhile, interference from other ions and substances were examined. The experimental results indicate that the method for the determination of gastric juice samples is successful.  相似文献   
90.
张成仁  王柳  葛燕丽  巨修练 《有机化学》2007,27(11):1432-1437
设计并以噁唑、苯并噁唑及1,3,4-噁二唑硫醇与卤代烃反应合成了14个硫醚类杂环化合物, 其中13个化合物未见文献报道. 目标化合物的结构均通过1H NMR谱、MS和元素分析进行了表征. 采用MTT [3-(4,5-dimethylthiagol-2-yl)- 2,5-diphenyltetrogolium bromide]法对14个目标化合物进行了体外抗肿瘤活性测定, 结果表明: 在10-5 mol/L 浓度下, 10个化合物对肿瘤细胞具有抑制活性.  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