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   30118篇
  免费   4672篇
  国内免费   4806篇
化学   23543篇
晶体学   558篇
力学   1354篇
综合类   323篇
数学   3190篇
物理学   10628篇
  2024年   108篇
  2023年   564篇
  2022年   1135篇
  2021年   1168篇
  2020年   1228篇
  2019年   1310篇
  2018年   1065篇
  2017年   1112篇
  2016年   1446篇
  2015年   1510篇
  2014年   1863篇
  2013年   2290篇
  2012年   2619篇
  2011年   2743篇
  2010年   2066篇
  2009年   1925篇
  2008年   2156篇
  2007年   1797篇
  2006年   1763篇
  2005年   1526篇
  2004年   1239篇
  2003年   1036篇
  2002年   1163篇
  2001年   934篇
  2000年   671篇
  1999年   579篇
  1998年   428篇
  1997年   297篇
  1996年   324篇
  1995年   228篇
  1994年   204篇
  1993年   200篇
  1992年   152篇
  1991年   190篇
  1990年   104篇
  1989年   97篇
  1988年   58篇
  1987年   61篇
  1986年   59篇
  1985年   54篇
  1984年   23篇
  1983年   24篇
  1982年   11篇
  1981年   13篇
  1980年   9篇
  1979年   8篇
  1978年   9篇
  1977年   5篇
  1976年   6篇
  1936年   4篇
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
81.
a, a'-Bis(substituted benzylidene)cycloalkanones were efficiently prepared from cycloalkanones and benzaldehydes in [bmim][BF4] by using iron(III) chloride hexahydrate as a catalyst. It is shown that [bmim][BF4] and iron(III) chloride hexahydrate can be quantitatively recovered and be reused effectively for many times. Compared with the known methods, this novel process has the advantage of being an envkonmentally benign process together with good yields and mild reaction conditions.  相似文献   
82.
This work describes a study of the underpotential deposition (UPD) of Sn2+ on a polycrystalline gold disc electrode using cyclic voltammetry (CV) and chronocoulometry (CC). Sn2+ ions showed well-defined peaks from UPD and UPD stripping (UPD-S) in 1 mol/L HCl solutions, while bulk deposition (BD) and BD stripping (BD-S) of the ions were also observed. The measured UPD shifts, EUPD, between the UPD-S and the BD-S peaks were more than 200 mV. The UPD charge and the surface coverage of tin were measured by CC. A new method for determining Sn2+ was therefore developed, based on the excellent electrochemical properties of the Au/Sn UPD system. A plot of the UPD-DPASV (differential pulse anodic stripping voltammetry) signal versus the Sn(II) concentration was obtained for [Sn(II)] of 1.98×10–7 to 3.64×10–5 M. The method developed here has been applied to determine the tin in a tin plate sample.  相似文献   
83.
Water‐soluble low molecular weight chitosan of nanometer level and its copper complexes were prepared, and characterized by IR spectra, elemental analysis and gel permeation chromatography (GPC). The modes and mechanism of these copper complexes interaction with DNA were studied by a fluorescent probe method and electrophoresis analysis. It is suggested that there are electrostatic and intercalation modes of copper complexes interacting with DNA. At first, the cationic complex electrostaticly binds to the negatively charged phosphate backbone of DNA, and then a portion of the complex intercalates between the base pairs on the DNA duplex strand. Copyright © 2005 John Wiley & Sons, Ltd.  相似文献   
84.
Solvent-free organic reactions have been attracting great interest of chemists due to the elimination of the usage of harmful organic solvents,low costs,and simplicity in the procedure1.Solvent-free mechanochemical reactions of fullerenes were explored and are significant for the reactions of fullerenes because the low solubility of fullerenes in common organic solvents requires large quantity of organic solvents and some novel fullerene reactions could only occur in the solid-state reaction2.…  相似文献   
85.
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   
86.
The interactions of serum albumins such as human serum albumin (HSA) and bovine serum albumin (BSA) with emodin, rhein, aloe-emodin and aloin were assessed employing fluorescence quenching and absorption spectroscopic techniques. The results obtained revealed that there are relatively strong binding affinity for the four anthraquinones with HSA and BSA and the binding constants for the interactions of anthraquinones with HSA or BSA at 20 degrees C were obtained. Anthraquinone-albumin interactions were studied at different temperatures and in the presence of some metal ions. And the competition binding of anthraquinones with serum albumins was also discussed. The Stern-Volmer curves suggested that the quenching occurring in the reactions was the static quenching process. The binding distances and transfer efficiencies for each binding reactions were calculated according to the F?ster theory of non-radiation energy transfer. Using thermodynamic equations, the main action forces of these reactions were also obtained. The reasons of the different binding affinities for different anthraquinone-albumin reactions were probed from the point of view of molecular structures.  相似文献   
87.
硫代钼酸盐和硫代钨酸盐的合成性质和取代反应的研究   总被引:2,自引:0,他引:2  
本文提出了在水或水/醇溶液中[NH_4]_2[MO_nS_(4-n)](M=Mo、W,n=0-2)进行取代反应的方法。用该方法合成出[X]_2[MO_nS_(4-n)](X=(n-Bu)_4N、Ph_4P、py—C_(16)H_(33)共18个化合物,其中11个为新化合物,并采用元素分析、红外光谱、电子光谱和X-粉末衍射等方法对这些化合物进行了表征。  相似文献   
88.
合成1,3-二(3-羟丙基)四甲基二硅氧烷的新方法   总被引:2,自引:0,他引:2  
用二乙氧基二甲基硅烷与3-氯丙醇反应,合成了新化合物3-氯丙氧基乙氧基二甲基硅烷,然后用格氏反应代替Walter的钠缩合反应,最后经水解制备了1,3-二(3-羟丙基)四甲基二硅氧烷,总收率为42.0%。  相似文献   
89.
Ceria-supported copper-palladium catalysts have been tested in the hydrogenation of 1,3-butadiene. The SMSI behavior of the bimetallic catalysts depended on the temperature of reduction. They were analyzed by H2 chemisorption and XPS.  相似文献   
90.
A direct and efficient method for the conversion of alkyl aryl ketones to imidazo[1,2‐α]pyridines has been developed based on initial formation of α‐organosulfonyloxy ketones and their subsequent cyclocondensation by 2‐aminopyridines in one‐pot conditions.  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