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   6971篇
  免费   427篇
  国内免费   503篇
化学   3512篇
晶体学   60篇
力学   225篇
综合类   29篇
数学   343篇
物理学   1042篇
综合类   2690篇
  2024年   20篇
  2023年   71篇
  2022年   175篇
  2021年   161篇
  2020年   143篇
  2019年   145篇
  2018年   138篇
  2017年   146篇
  2016年   193篇
  2015年   226篇
  2014年   277篇
  2013年   426篇
  2012年   331篇
  2011年   346篇
  2010年   261篇
  2009年   343篇
  2008年   358篇
  2007年   433篇
  2006年   381篇
  2005年   356篇
  2004年   330篇
  2003年   264篇
  2002年   574篇
  2001年   240篇
  2000年   214篇
  1999年   161篇
  1998年   170篇
  1997年   134篇
  1996年   124篇
  1995年   115篇
  1994年   99篇
  1993年   105篇
  1992年   80篇
  1991年   71篇
  1990年   49篇
  1989年   59篇
  1988年   42篇
  1987年   23篇
  1986年   25篇
  1985年   23篇
  1984年   14篇
  1983年   6篇
  1982年   9篇
  1981年   10篇
  1980年   5篇
  1979年   9篇
  1978年   3篇
  1977年   3篇
  1976年   2篇
  1973年   3篇
排序方式: 共有7901条查询结果,搜索用时 15 毫秒
11.
The apparent molal volumes and compressibilities of NaCl, KCl, and CsCl in mixtures of 18-Crown-6 and water have been calculated from density and speed-of-sound measurements at 25°C. The partial molal volumes and compressibilities of the salts when all cations have formed complexes with 18-Crown-6 molecules have been evaluated. The sign and magnitude of the volume and compressibility changes of complex formation strongly suggest that the charge of the cation becomes very effectively screened by the crown ether.  相似文献   
12.
Summary. The study of delphinidin complexation with trivalent aluminum in acidic aqueous buffered (pH 3.0 and 3.8) and methanolic solutions was performed utilizing electronic absorption spectroscopy and quantum chemical calculations. In its structure delphinidin possesses several chelating sites in competition towards aluminum(III). Molar ratio plots denoted the formation of only one aluminum(III):delphinidin complex of stoichiometry of 1:1 in both investigated media. Semiempirical calculations, performed at the restricted HF AM1 level, enabled the determination of the structural features of free delphinidin and structural modifications caused by chelation of aluminum(III). Considering the pigment molecular structure and the results of the theoretical calculations it is possible to equally implicate C3′–C4′ and C4′–C5′ hydroxyl groups as those with the predominant chelating power.  相似文献   
13.
The first examples of diborane (4) compounds derived from amine cyanoboranes are described. A series of monobromo derivatives of amine cyanoboranes (A:BHBrCN), and dibromo derivatives (A:BBr2CN), 1-7, were prepared. Lithiation of the monobromo derivative of trimethylamine cyanoborane, using n-BuLi, did not produce the C-lithiated intermediate Li+ [CH2NMe2BHBrCN], but instead the B-lithiated intermediate Li+ [Me3NBHCN], was obtained. This intermediate, when allowed to react for 16 h, coupled with the un-lithiated trimethylamine monobromocyanoborane (Me3NBHBrCN) and resulted in diborane (4) derivative formation as the 2LiBr complex. The same result was obtained when one equiv of the trimethylamine monobromocyanoborane was added to the reaction mixture 1 h after lithiation. Following the same procedure, novel diborane (4) derivatives of amine cyanoboranes were successfully obtained, 8-11, as their 2LiBr complexes from the monobromo derivatives of the corresponding amine cyanoboranes. Molecular structures of the trimethylamine dibromocyanoborane, 6, and the triethylamine dibromocyanoborane, 7, were determined using X-ray crystallography.  相似文献   
14.
本文提出了富烯碳原子簇的石墨层间闭合形成机理,由该机理推出的许多结果与实验事实符合很好。我们认为碳原子簇自由基的快速淬灭及其淬灭速度是富烯碳原子簇形成及其丰度的决定因素。由此得出富烯碳原子簇在给定实验条件下产生的必然性,并预言不同大小的富烯碳原子簇可以通过优化实验条件选择性地合成。  相似文献   
15.
运用文化语言学的理论,从汉语词汇的意义、结构和交际三个方面进行论证,提出词汇与文化具有“融合关系”、“渗透关系”和“制约关系”。这些关系说明文化对词汇的理解、运用和规范有着很大的影响,重视文化因素对全面灵活地理解词汇的意义、深入细致地了解词汇的结构、准确扎实地掌握词汇的运用技巧大有裨益。每一语言系统中有相当一部分词汇的内涵是以民族文化为依托,文化是这些词义产生、发展、衍变的关键。在汉语词汇系统中,表义的结构形式反映了汉民族的思维方式、特点,是它们形成了汉语词汇的构成规则。传统的伦理等级观念、约定俗成的民族表达习惯附加给词汇各种文化色彩的语用意义,这些多维的复合性文化使开放的词汇系统变得有序可循。  相似文献   
16.
An electrostatic bond energy model is formulated to fit the enthalpies of formation and dipole moments of the alkanes and chloroalkanes. In this model, the charge distributions are calculated by an electrostatic approach similar to the "MSE" method, and the enthalpy of formation of a molecule is the sum of the bond energy terms plus the electrostatic energy of the interactions between the charges on all atoms. All parameters of this model are obtained by parameterization. The calculated dipole moments for 13 chloroalkanes and enthalpies of formation for 19 alkanes and non-geminal chloroalkanes agree with the determined values very well. To calculate the enthalpies of formation of geminal chloroalkanes, a correction mainly attributed to the van der Waals interactions in the geminal substituted group, about 24 kJ/mol per pair of geminal chlorine atoms, is introduced.  相似文献   
17.
从光干涉方式,瞳窗关系和光源带宽等基本关系出发,利用空间不变系统理论解析了相移显微干涉检测系统中衍射效应的影响。为了减小横向分辨率对纵向分辨率的影响,利用相关信息提取或数字滤波的方法,获得了纳米分辨率的三维形貌。  相似文献   
18.
An unequivocal synthesis of 5-chloro-7-methyl- (8) and 7-methyl-1,2,4-triazolo[1,5-a]pyrimidine (10) from 2-amino-4-chloro-6-methylpyrimidine (5) through the corresponding amidine6 and formamide oxime7 was developed. It was unambigously shown by comparison of the chemical shifts and the magnitude of coupling constants that the compounds obtained by condensation of 3-amino-1,2,4-triazole (12) and ethyl acetoacetate (13) and some further transformations are isomeric 5-methyl substituted 1,2,4-triazolo[1,5-a]pyrimidines1,9, and11.
Eine eindeutige Synthese einiger substituierter 1,2,4-Triazolo[1,5-a]pyrimidine
Zusammenfassung Es wurde ein eindeutiger Syntheseweg für 5-Chlor-7-methyl- (8) und 7-Methyl-1,2,4-triazolo[1,5-a]pyrimidin (10) ausgehend von 2-Amino-4-chlor-6-methylpyrimidin (5) über das entsprechende Amidin6 und das Formamidoxim7 entwickelt. Durch Vergleich von chemischen Verschiebungen und Kopplungskonstanten konnte eindeutig gezeigt werden, daß die Verbindungen, die bei der Kondensation von 3-Amino-1,2,4-triazol (12) and Ethylacetoacetat (13), sowie einige weitere Transformationsprodukte, isomere 5-Methylsubstituierte 1,2,4-Triazolo[1,5-a]pyrimidine sind (1,9,11).
  相似文献   
19.
Syntheses are reported for representatives of a new class of derivatives of -cyanoacrylic acid, namely, its salts with brucine, tert-butyldimethylamine, and diisopropylmethylamine.A. N. Nesmeyanov Institute of Organometallic Compounds, Russian Academy of Sciences, 117813 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 1, pp. 212–214, January, 1992.  相似文献   
20.
Dynamic interfacial tension values obtained by drop volume tensiometry will be affected under certain experimental conditions by the formation of a neck between the drop and the capillary tip. This phenomenon must be accounted for to obtain accurate values of interfacial tension. In this work, neck formation for a water–mineral oil system is studied under conditions where hydrodynamic effects can be neglected. A model originally developed for the determination of the surface tension of a suspended drop is modified for application to dynamic interfacial tensions of surfactant-containing liquids. The model relates apparent values of interfacial tension calculated from drops possessing necks to actual values. Experiments with Span 80 (sorbitan monooleate) and sodium dodecyl sulfate (SDS) surfactants in a mineral oil–water system are used to test the validity of the developed model. For the small tip diameter used, good agreement is obtained for Span 80 up to the critical micelle concentration, and for low concentrations of SDS, when the surfactant adsorption is diffusion-limited. In both cases, the neck diameter of the growing drop can be considered constant over the range of dynamic interfacial tensions tested.  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