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   1001篇
  免费   154篇
  国内免费   183篇
化学   1112篇
晶体学   29篇
力学   7篇
综合类   7篇
物理学   183篇
  2023年   9篇
  2022年   15篇
  2021年   31篇
  2020年   44篇
  2019年   34篇
  2018年   20篇
  2017年   32篇
  2016年   60篇
  2015年   53篇
  2014年   66篇
  2013年   108篇
  2012年   67篇
  2011年   61篇
  2010年   46篇
  2009年   62篇
  2008年   55篇
  2007年   53篇
  2006年   79篇
  2005年   74篇
  2004年   85篇
  2003年   49篇
  2002年   22篇
  2001年   18篇
  2000年   13篇
  1999年   20篇
  1998年   18篇
  1997年   30篇
  1996年   20篇
  1995年   21篇
  1994年   16篇
  1993年   13篇
  1992年   15篇
  1991年   8篇
  1990年   4篇
  1989年   8篇
  1988年   2篇
  1987年   3篇
  1986年   2篇
  1985年   1篇
  1984年   1篇
排序方式: 共有1338条查询结果,搜索用时 31 毫秒
51.
The gallium(I) derivative [Ga({N(dipp)CMe}2CH)] ( 1 ; dipp=2,6‐diisopropylphenyl) undergoes facile oxidative addition reactions with various element–hydrogen bonds including N? H, P? H, O? H, Sn? H, and H? H bonds. This was demonstrated by its reaction with triphenyltin hydride, ethanol, water, diethylamine, diphenylphosphane, and dihydrogen. All products were characterized by means of single‐crystal X‐ray structure determination, NMR spectroscopy, IR spectroscopy, and mass spectrometry.  相似文献   
52.
二(o-甲基苄基)二氯化锡与N-(o-甲基苄基)羟胺在碱性条件下反应,合成了有机锡配合物{[(o-MeC6H4CH2)2Sn(O)]2(o-MeC6H4CH2NHO)}2。经X-射线衍射方法测定了化合物的晶体结构。该化合物晶体属三斜晶系,空间群P-1,晶体学参数 a =1.0604(5) nm,b =1.3078(7) nm,c = 1.3742(47 nm,α=105.174(12)?,β = 90.229(7)?,γ=101.028(6)?,Z = 1,V =1.8025(15) nm3,Dc=1.522Mg•m-3,?(MoKa)= 1.423 mm-1,F(000)= 834,R1=0.0455,wR2=0.1017。化合物是三个以Sn2O2构成的平面四元环组成的梯状结构,锡原子均为五配位的畸变三角双锥构型。测定了配合物的体外抗癌活性,结果表明配合物对WiDr和MCF-7等癌细胞有一定的抑制能力。  相似文献   
53.
二(对甲基苄基)二氯化锡和氢氧化钠溶液反应,合成了梯形结构二(对甲基苄基)锡氧(氯)簇合物,经X-射线衍射测定了其晶体结构。属三斜晶系,空间群为P1,晶体学参数a=0.979 52(16) nm,b=1.313 8(2) nm,c=1.419 5(2) nm,α=62.965(10)°,β=88.551(12)°,γ=73.709(11)°,V=1.550 5(5) nm3,Z=1,Dc=1.563 g·cm-3,μ(Mo Kα)=17.38 cm-1,F(000)=727,R=0.024 2,wR=0.057 9。簇合物为由Sn2O2构成的平面四元环形成的1个中心内环和2个由Sn2OCl(O)构成的平面四元外环组成的梯形结构。锡原子均为五配位三角双锥构型。对其结构进行量子化学从头计算,探讨了配合物的稳定性、分子轨道能量以及一些前沿分子轨道的组成特征。  相似文献   
54.
A voltammetric sensor for sensitive and specific determination of trans‐resveratrol (RES) were prepared based on immobilization of an RES‐imprinted film on the surface of functionalized Indium Tin Oxide (ITO) electrode, which was modified with γ‐methacyloxypropyl trimethoxysilane (γ‐MPS). Cyclic Voltammetry (CV) was presented to extract RES from the molecularly imprinted polymer film and RES were extracted rapidly and completely. The binding performance of the imprinted electrode with the template RES were investigated using differential pulse voltammetry (DPV). The results showed that the imprinted ITO film can give selective recognition to the template RES over that of structurally analogous molecules. A linear response to RES in the concentration range of 2.0×10?6 M to 2.0×10?5 M was observed with a correlation coefficient of 0.992, and the detection limit of the electrochemical sensor was 8.0×10?7 M. Whereas, binding to the reference nonimprinted electrode, made in the same way but without the addition of template RES, there was almost no response to RES.  相似文献   
55.
This article describes an electrochemical strategy to achieve low background‐current levels in horse‐radish peroxidase (HRP)‐based electrochemical immunosensors. The strategy consists of (i) the use of an HRP substrate/product redox couple whose formal potential is high and (ii) the use of an electrode that shows moderate electrocatalytic activity for the redox couple. The strategy is proved by a model biosensor using a catechol/o‐benzoquinone redox couple and an indium tin oxide (ITO) electrode. The combined effect of high formal potential and moderate electrocatalytic activity allows o‐benzoquinone electroreduction with minimal catechol electrooxidation and H2O2 electroreduction. The detection limit for mouse‐IgG is 100 pg/mL.  相似文献   
56.
Platinum–tin complexes were prepared by the reduction of Pt(IV) with Sn(II) in HCl media and studied by light absorption spectrometry, X-ray photoelectron spectroscopy (XPS), and electron microscopy. The formation of three complexes, H3[Pt(SnCl3)5], H2[Pt(SnCl3)2Cl2], and H2[Pt3(SnCl3)8], depending on HCl and SnCl2 concentrations, has been shown. The glassy carbon (GC) electrode modified in the complexes solutions was found to be an electrocatalyst for borohydride oxidation in a 1.0-M NaOH solution. Comparison of BH4 electrooxidation on Pt and on GC modified with platinum–tin complexes has shown that catalytic hydrolysis of BH4 did not proceed in the latter case in contrast to its oxidation on the Pt electrode, and only direct BH4 oxidation has been observed in the positive potentials scan. The activity of Pt–Sn complexes for BH4 oxidation changes with time and eventually decreases due to Sn(II), bound in the complex with Pt(II), oxidation by atmospheric oxygen. The complexes may be renewed by addition of missing amounts of SnCl2 and HCl.  相似文献   
57.
In this study, the effect of ultraviolet treatment on the band bending at the poly(3,4-ethylenedioxythiophene) doped with poly(4-styrenesulfonate)/indium tin oxide (PEDOT:PSS/ITO) interfaces were researched. The authors suggested that ultraviolet treatment could lead to a reduction in the band bending at the PEDOT:PSS/ITO interface, owing to the removal of carbon contamination at the ITO surfaces and a decrease in the number of the trap-states at the PEDOT:PSS/ITO interface.  相似文献   
58.
Perfluoroalkytin compounds R(4−n)Sn(Rf)n (R = Me, Et, Bu, Rf = C4F9, n = 1; R = Bu, Rf = C4F9, n = 2, 3; R = Bu, Rf = C6F13, n = 1) have been synthesized, characterized by 1H, 13C, 19F and 119Sn NMR, and evaluated as precursors for the atmospheric pressure chemical vapour deposition of fluorine‐doped SnO2 thin films. All precursors were sufficiently volatile in the range 84–136 °C and glass substrate temperatures of ca 550 °C to yield high‐quality films with ca 0.79–2.02% fluorine incorporation, save for Bu3SnC6F13, which incorporated <0.05% fluorine. Films were characterized by X‐ray diffraction, scanning electron microscopy, thickness, haze, emissivity, and sheet resistance. The fastest growth rates and highest quality films were obtained from Et3SnC4F9. An electron diffraction study of Me3SnC4F9 revealed four conformations, of which only the two of lowest abundance showed close F Sn contacts that could plausibly be associated with halogen transfer to tin, and in each case it was fluorine attached to either the γ‐ or δ‐carbon atoms of the Rf chain. Copyright © 2005 John Wiley & Sons, Ltd.  相似文献   
59.
The fluorine-doped tin oxide (FTO) thin film deposited on a soda-lime glass substrate was annealed by a defocus ultraviolet (UV) laser irradiation at ambient temperature. The mechanical and optoelectric properties of FTO films annealed by using the various laser processing parameters were reported. After the FTO films were subjected to laser post-annealing, the microhardness were slightly less but the reduced modulus values were larger than that of unannealed FTO films, respectively. The average optical transmittance in the visible waveband slightly increased with increasing the laser annealing energy and scan speed. Moreover, all the sheet resistance of laser annealed films was less than that of the unannealed ones. We found that the sheet resistance decrease was obviously influenced by annealing. The suitable annealing conditions could maintain the film thickness and relief the internal stress generated in the film preparation process to improve the electrical conductivity via decreasing laser energy or increasing scan speed.  相似文献   
60.
The preparation and characterization of octadecylsilane, C18, monolayers on indium–tin oxide (ITO) have been studied carefully. A reproducible procedure was developed for the formation of C18/ITO employing octadecyltrimethoxysilane (OTMS) as a monomer. The films were studied by means of electrochemistry, wettability, infrared and atomic force microscopy. All these measurements provide evidence for the formation of a disorganized, ‘brush-type’ monolayer with a maximum surface fractional coverage of 0.90±0.04. The surface coverage can be controlled through the silanization time. The applications and implications of such disorganized monolayers in electroanalytical chemistry are discussed.  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