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   17640篇
  免费   2414篇
  国内免费   1631篇
化学   8014篇
晶体学   162篇
力学   865篇
综合类   105篇
数学   1250篇
物理学   4987篇
综合类   6302篇
  2024年   81篇
  2023年   360篇
  2022年   600篇
  2021年   689篇
  2020年   612篇
  2019年   567篇
  2018年   502篇
  2017年   465篇
  2016年   721篇
  2015年   775篇
  2014年   954篇
  2013年   1075篇
  2012年   1350篇
  2011年   1292篇
  2010年   1040篇
  2009年   1023篇
  2008年   1018篇
  2007年   934篇
  2006年   906篇
  2005年   795篇
  2004年   537篇
  2003年   468篇
  2002年   489篇
  2001年   380篇
  2000年   346篇
  1999年   470篇
  1998年   400篇
  1997年   415篇
  1996年   397篇
  1995年   344篇
  1994年   274篇
  1993年   237篇
  1992年   190篇
  1991年   192篇
  1990年   176篇
  1989年   168篇
  1988年   129篇
  1987年   83篇
  1986年   64篇
  1985年   35篇
  1984年   20篇
  1983年   15篇
  1982年   16篇
  1981年   7篇
  1980年   9篇
  1975年   7篇
  1973年   4篇
  1972年   7篇
  1965年   6篇
  1964年   5篇
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
71.
The La(III) complex with a new amide‐type tripodal ligand,2,2′.2″‐nitrilotris{[(2′‐benzylaminofomyl)‐phenoxylethyl)amine (L), was synthesized and characterized by X‐ray crystallographic analysis. Crystal data: C48H55.50LaN7O18.75, Mr=1169.40, monoclinic. space group, P21/n, a= 1.0644(3) nm. b=2.3889(5) nm, c= 2.1917(5) nm, β=90.65°, V=5.573(2) nm3, Z=1, Dc=1.394 g°cm?3, R1=0.0487, wR [1>2s?(I)]=0.1266. The results reveal that each La(III) ion binds to 9 oxygen atoms, three of which belong to carbonyl groups from three tripodal ligands and six to three bidentate nitrate groups and a two‐dimensional sheet of 4.82 networks is assembled by metal‐ligand coordination interaction. L, a heptadentate compound, merely acts as a tridentate bridging spacer due to its steric hindrance and links the La(III) ions as three‐connected nodes.  相似文献   
72.
In order to elucidate the mechanism of reaction M+ + SCO, both triplet and singlet potential energy surfaces (PESs) for the reaction of Sc+ + SCO have been theoretically investigated using the DFT (B3LYP/6-311+G*) level of theory. The geometries for reactants, intermediates, transition states and products were completely optimized. All the transition states were verified by the vibrational analysis and the intrinsic reaction coordinate calculations. The involving potential energy curve-crossing dramatically affects reaction mechanism, reaction rate has been discussed, and the crossing points (CPs) have been localized by the approach suggested by Yoshizawa et al. The present results show that the reaction mechanism are insertion–elimination mechanism both along the C–S and C–O bond activation branches, but the C–S bond activation is much more favorable in energy than the C–O bond activation. All theoretical results not only support the existing conclusions inferred from early experiment, but also complement the pathway and mechanism for this reaction.  相似文献   
73.
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   
74.
The behavior of153Sm-EDTMP in vitro and vivo is analyzed by the size exclusion HPLC. The experimental results show that EDTMP amounts have an obvious effect on the stability in vitro and uptake of153Sm-EDTMP in the liver. HPLC analysis of urine sample indicates that153Sm-EDTMP es excreted in the original form. The behavior in vivo of153Sm-EDTMP containing 4 μg is similar to that of153Sm-EDTMP containing 50 μg EDTMP at 1 h post-injection.  相似文献   
75.
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   
76.
将加热活化的AlCl_3与三氯化稀土在苯溶液中反应,合成了2个新的轻稀土中性芳烃配合物RE(C_6H_6)(AlCl_4)_3C_6H_6(RE=La或Nd)。并用元素分析和红外光谱对其进行了表征。测定了含Nd配合物的晶体结构。对2个配合物结构的比较表明,中心金属离子对配合物的结构无明显影响,其键参数的差别主要来自“镧系收缩”。  相似文献   
77.
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   
78.
79.
为了研究白血病骨髓移植病人全血微量元素铜的变化及其意义 ,用原子吸收光谱法检测了正常对照组与白血病骨髓移植患者预处理前及移植后骨髓空虚期全血微量元素铜的含量。结果表明 ,正常对照组全血铜浓度与白血病骨髓移植患者预处理前全血铜浓度差异无显著性 (P >0 0 5 ) ,而与骨髓空虚期全血铜浓度有显著性差异 (P <0 0 5 ) ,说明白血病缓解后血铜接近正常对照组水平 ,而白血病骨髓移植患者预处理后骨髓空虚期全血铜含量高于正常对照组 ,说明预处理影响微量元素铜的代谢 ,本文就其影响机理进行了研究  相似文献   
80.
The migration of radionuclides 85+89Sr2+, 134Cs+, 125I- and 75SeO3 2- in calcareous soil from Yuzhong county of Gansu Province (China) at pH 7.8±0.2 and 152+154Eu(III) in red earth from Yingtan county of Jiangxi Province (China) at pH 4.6±0.2, in presence of CaCl2 was studied using column experiments. Results indicate that the negative anions, iodide and selenide are mobile nuclides while the migration of positive cations is related to the sorption capacity for the element. Iodide can be assumed to be non-reactive in calcareous soil. The breakthrough curves (BTCs) were fitted to the analytical solution or numerical solution of one-dimensional convection-dispersion transport models. Good agreements were obtained between the measured and predicted concentration profiles.  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