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   2729篇
  免费   690篇
  国内免费   872篇
化学   1933篇
晶体学   96篇
力学   215篇
综合类   85篇
数学   280篇
物理学   1682篇
  2025年   8篇
  2024年   52篇
  2023年   84篇
  2022年   97篇
  2021年   92篇
  2020年   104篇
  2019年   90篇
  2018年   79篇
  2017年   102篇
  2016年   94篇
  2015年   147篇
  2014年   197篇
  2013年   241篇
  2012年   262篇
  2011年   244篇
  2010年   257篇
  2009年   233篇
  2008年   262篇
  2007年   260篇
  2006年   224篇
  2005年   207篇
  2004年   156篇
  2003年   117篇
  2002年   132篇
  2001年   145篇
  2000年   74篇
  1999年   53篇
  1998年   40篇
  1997年   35篇
  1996年   32篇
  1995年   22篇
  1994年   25篇
  1993年   22篇
  1992年   30篇
  1991年   10篇
  1990年   7篇
  1989年   7篇
  1988年   3篇
  1987年   10篇
  1986年   2篇
  1985年   3篇
  1984年   3篇
  1983年   5篇
  1982年   4篇
  1979年   4篇
  1978年   2篇
  1971年   2篇
  1965年   2篇
  1964年   2篇
  1963年   2篇
排序方式: 共有4291条查询结果,搜索用时 15 毫秒
81.
Ferrocenylcyanide is a valuable precursor for preparation of nitrogen-containing ferrocenyl ligands. Originally, ferrocenylcyanide was prepared from ferrocenecarboxy- aldehyde by multi-steps transformations, at evaluated temperature. Very recently, a modi…  相似文献   
82.
A series of thiol-functionalied azobenzene derivatives (RAzoCnSH: R=H for n=3-6, abbreviated as AzoCnSH; R=CH(3)CONH for n=4, abbreviated as aaAzoC4SH) on gold electrodes were prepared and their self-assembly and electrochemical properties were studied by cyclic voltammetry. They all formed uniform and reproducible self-assembled monolayers (SAMs) on gold and showed well-behaved voltammetric responses in aqueous solution. Both the length of the alkyl chain spacer and the H-bonding of the end acetamino group had effects on the stability and the electrochemical kinetics of the SAMs, and the effect of the H-bonding was dominant. The surface coverage of the SAMs (AzoCnSH) is gradually increased with an increase of the alkyl chain spacer length, whereas the presence of the terminal acetamino group leads to a greater increase of the surface coverage. At a low scan rate, voltammetric responses corresponding to an irreversible two-electron, two-proton reduction/oxidation of the trans-azobenzene redox center were obtained in the range of +300 mV and -800 mV, which exhibited very large peak-to-peak splitting. At a high scan rate of 500 mV/s, two steps of reversible one-electron, one-proton reduction/oxidation corresponding to the cis-isomer in azobenzene-thiol SAMs (n is odd) was clearly observed between +300 and -200 mV. The apparent electron-transfer rate is decreased with increasing distance between the azobenzene redox center and the gold electrode. The existence of the end acetamino group which restricted the conformational change during the redox process also led to a decrease of the standard rate constant, and this restriction effect is more predominant than the distance effect.  相似文献   
83.
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   
84.
结合课题组近期的相关研究,对固体CD光谱在手性配合物研究中的应用,特别是手性样品固体CD光谱的测试方法进行了概述,通过对四对手性席夫碱M(II)(M=Ni、Cu)配合物的固体和溶液CD光谱进行比较研究,发现配合物的手性构型在固液相中保持一致,但其固液CD光谱之间存在不同程度的差异,可能是由于相应配合物在固体和溶液相中的四面体扭曲或构象的微妙不同所致.  相似文献   
85.
1 INTRODUCTION The ribosome-inactivating proteins (RIPs) are RNA N-glycosidases[1, 2] which inactivate ribosomes by cleaving a single N–C glycosidic bond between adenine and ribose at A4324 in the 28s rRNA of rat. Because of the removal of one adenine from rRNA, elongation factorⅡ(EF-2) can not bind to the 60S subunit, so RIPs can arrest protein synthesis. RIPs can be classified into three types based on the struc- tures of genes and mature proteins[3]. Type 1 RIPs with molec…  相似文献   
86.
A new compound, (S)-2, 4-dihydroxy-1-butyl (4-hydroxy) benzoate (1), and a known compound, fructigenines A (2), were isolated from fungus Penicillium auratiogriseum derived from sponge Mycale plumose, by bioassay-guided fractionation. Their structures were established by spectroscopic and chemical methods. Both compounds show.ed cytotoxic activity against tsFT210 cells.  相似文献   
87.
Two premeditated anionic rosette-layer architectures have been constructed using guanidinium and ubiquitous C3-symmetric oxoanions that carry unequal charges, employing bulky organic cations as interlayer templates. The undulate guanidinium-carbonate network occurs in 4[(C2H5)4N+].8[C(NH2)3+].3(CO3)2-.3(C2O4)2-.2H2O, in which the disordered (C2H5)4N+ guests are accommodated in pouches and channels within a complex three-dimensional hydrogen-bonded host framework. In [(C2H5)4N+]2.[C(NH2)3+].[1,3,5-C3H3(COO-)3].6H2O, ordered (C2H5)4N+ cations are sandwiched between planar guanidinium-trimesate host layers whose honeycomb cavities are tightly fitted with flattened-chair (H2O)6 clusters of symmetry 2.  相似文献   
88.
基于基团贡献法的思想,本文采用改进的SRK状态方程和修正的MHV1混合规则,将UNIFAC基团贡献法扩展用于HFC HC二元混合物气液相平衡性质的描述,给出了基团划分表和基团间的相互作用参数,使用该方法可以较好地再现HFC HC二元混合物的气液相平衡性质,并且具有良好的预测效果.  相似文献   
89.
水平管段塞流持液率波动规律研究   总被引:3,自引:0,他引:3  
以空气和水为工质,采用双平行电导探针,在水平多相流环道(d=50.00mm)中研究了段塞流持液率与压力波动的关系以及折算气速、折算液速变化对持液率的影响,并将持液率的试验值与预测模型进行了比较.结果表明:持液率波动能更真实地反映段塞流动特性,可以用来确定液塞频率;增加折算气速时,液塞持液率减小;增加折算液速时,持液率增大.  相似文献   
90.
合成并表征了铜配合物[CuL(Gly)]NO3·H2O(L=6-二(苯并咪唑-2′)吡啶(H2bzimpy);Gly为甘氨酸(Glycine).利用电子吸收光谱、荧光光谱和粘度等方法研究了配合物与DNA的作用,结果表明配合物以部分插入模式与DNA相互作用.  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