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   3091篇
  免费   559篇
  国内免费   336篇
化学   2263篇
晶体学   38篇
力学   192篇
综合类   20篇
数学   320篇
物理学   1153篇
  2024年   8篇
  2023年   88篇
  2022年   79篇
  2021年   127篇
  2020年   165篇
  2019年   144篇
  2018年   138篇
  2017年   92篇
  2016年   183篇
  2015年   148篇
  2014年   189篇
  2013年   206篇
  2012年   302篇
  2011年   340篇
  2010年   201篇
  2009年   224篇
  2008年   216篇
  2007年   168篇
  2006年   152篇
  2005年   118篇
  2004年   95篇
  2003年   77篇
  2002年   77篇
  2001年   58篇
  2000年   53篇
  1999年   56篇
  1998年   44篇
  1997年   33篇
  1996年   51篇
  1995年   24篇
  1994年   32篇
  1993年   17篇
  1992年   16篇
  1991年   17篇
  1990年   14篇
  1989年   10篇
  1988年   8篇
  1987年   3篇
  1986年   4篇
  1985年   1篇
  1984年   1篇
  1983年   2篇
  1982年   1篇
  1974年   1篇
  1957年   3篇
排序方式: 共有3986条查询结果,搜索用时 187 毫秒
31.
三(2-苯并咪唑亚甲基)胺硝酸镍(Ⅱ)配合物的合成及结构   总被引:5,自引:0,他引:5  
三(2-苯并咪唑亚甲基)胺简称NTB与Ni(Ⅱ)的硝酸盐形成配合物C28H35N9O9S2Ni。本文报道其合成,红外光谱及晶体结构。该化合物为三斜晶系,空间P1↑-,a=9.650(3),b=12.716(2),c=14.436A,α=11.46(2),β=91.66(3),γ=97.55(2)°,V=1718(2)A^3,Z=2,F(000)=793,Dc=1.48g/cm^3,Mr=764.1  相似文献   
32.
研究了固载化聚乙二醇三相催化下香豆素的合成,探讨了影响反应的主要因素。结果表明,该反应的最佳反应条件为:水杨醛与碳酸钾的摩尔比为 1: 0.75,反应温度为175℃,反应时间为3.5 h,该条件下香豆素的收率为 65.7%。  相似文献   
33.
The desulfurization of thiophene on Raney Ni and rapidly quenched skeletal Ni (RQ Ni) has been studied in ultrahigh vacuum (UHV) by X-ray photoelectron spectroscopy (XPS). The Raney Ni or RQ Ni can be approximated as a hydrogen-preadsorbed polycrystalline Ni-alumina composite. It is found that thiophene molecularly adsorbs on Raney Ni or RQ Ni at 103 K. At 173 K, thiophene on alumina is desorbed, while thiophene in direct contact with the metallic Ni in Raney Ni undergoes C-S bond scission, leading to carbonaceous species most probably in the metallocycle-like configuration and atomic sulfur. On RQ Ni, the temperature for thiophene dissociation is about 100 K higher than that on Raney Ni. The lower reactivity of RQ Ni toward thiophene is tentatively attributed to lattice expansion of Ni crystallites in RQ Ni due to rapid quenching. The existence of alumina and hydrogen may block the further cracking of the metallocycle-like species on Raney Ni and RQ Ni at higher temperatures, which has been the dominant reaction pathway on Ni single crystals. By 473 K, the C 1s peak has disappeared, leaving nickel sulfide on the surface.  相似文献   
34.
利用荧光技术研究了在人体生理酸度条件下,苏丹Ⅰ与牛血清白蛋白相互作用,发现苏丹Ⅰ对牛血清白蛋白有较强的荧光猝灭作用,用Stern-Volmer和Line Weaver-Burk方程处理荧光猝灭数据,得到了反应的结合常数、结合热力学性质和结合位点等参数。根据热力学常数确定了该药物与血清白蛋白之间的作用力类型,在此基础上依据F rster非辐射能量转移机理探讨了苏丹Ⅰ与BSA相互结合时其供体-受体间的距离。  相似文献   
35.
Dinuclear Silylene Bridged Cyclopentadienylrhodiumbis(ethene) Complexes, Photochemical Reaction with Benzene Derivatives, and Selective Inclusion of Methylcyclopentane into the Crystal Lattice of [Me2Si{3-But-C5H3Rh(C2H4)2}2] By reaction of [{(C2H4)2RhCl}2] with Na2[Me2Si(C5H4)2] or with Li2[Me2Si(3-But-C5H3)2] in THF the dinuclear silylene bridged complexes [Me2Si{C5H4Rh(C2H4)2}2] 1 and [Me2Si{3-But-C5H3Rh(C2H4)2}2] 2 , respectively, were synthesized. Due to the asymmetric substitution of the five-membered rings and their hindered rotation around the Si? C axes, 2 is formed as three isomers. The X-ray structure analysis of 2 obtained from hexane reveals the selective inclusion of methylcyclopentane, the content of which in the solvent is about 17%, into the crystal lattice. UV irradiation of 1 in hexane in the presence of benzene causes elimination of the ethene ligands yielding the μ-η33 benzene complex [Me2Si(C5H4Rh2)2C6H6] which cannot be separated from unreacted 1 . However, separation is possible in case of the hexamethylbenzene compound 4 analogous with 3 .  相似文献   
36.
The properties of the triplet excited state of [60] fullerene-containing cyclic sulphoxide have been investigated by time-resolved absorption spectroscopy. Transient absorption bands of [60] fullerene-containing cyclic sulphoxide showed two decay-components, which wrer attributed to triplet excited states of different spin multiplicity. The properties of photoexcited states of [60] fullerene-containing cyclic sulphoxide are also reported.  相似文献   
37.
构筑了MgO部分稳定的ZrO2基固体电解质电化学电池测量EAF的实验装置,测定了Sm2CuO4的标准Gibbs生成自由能。结果表明化合物RE2CuO23(RE=La,Nd,Sm,Eu)随着镧系元素离子半径减小,热力学稳定性下降,并用晶体场理论解释了这一规律。  相似文献   
38.
Two new compounds from Zingiber officinale   总被引:1,自引:0,他引:1  
A new cyclic diarylheptanoid,1,5-epoxy-3-hydroxy-1-(3-methoxy-4,5-dihydroxyphenyl)-7-(4-hydroxyphenyl)-heptane (1),as well as a new monoterpene,10-O-β-D-glucopyranosyl-hydroxy cineole (2) were isolated from the rhizomes of Zingiber officinale. The structures of compounds 1 and 2 were established based on their spectral data.In addition,the antioxidant activities of these compounds were also measured.  相似文献   
39.
A fluorogenic probe for bacteria imaging was reported. The binding with anionic bacterial surfaces disassembled the self-assembly probe to turn-on the fluorescence and shift pyrene monomer/excimer ratiometric signals.  相似文献   
40.
The covalent binding of acrylonitrile (CH(2)=CH-C triple bond N) and the formation of a C=C-C=N structure on Si(100) have been investigated using high-resolution electron energy loss spectroscopy (HREELS), X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS), and density functional theory (DFT) calculations. For chemisorbed acrylonitrile, the absence of nu(C triple bond N) at 2245 cm(-1) and the appearance of nu(C=N) at 1669 cm(-1) demonstrate that the cyano group directly participates in the interaction with Si(100), which is further supported by XPS and UPS observations. Our experimental results and DFT calculations unambiguously demonstrate a [2 + 2] cycloaddition mechanism for acrylonitrile chemisorption on Si(100) through the binding of C triple bond N to Si dimers. The resulting chemisorbed monolayer with a C=C-C=N skeleton can serve as a precursor for further chemical syntheses of multilayer organic thin films in a vacuum and surface functionalization for in situ device fabrication.  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