全文获取类型
收费全文 | 4263篇 |
免费 | 378篇 |
国内免费 | 420篇 |
专业分类
化学 | 3374篇 |
晶体学 | 60篇 |
力学 | 219篇 |
综合类 | 28篇 |
数学 | 340篇 |
物理学 | 1040篇 |
出版年
2024年 | 7篇 |
2023年 | 42篇 |
2022年 | 81篇 |
2021年 | 88篇 |
2020年 | 103篇 |
2019年 | 97篇 |
2018年 | 82篇 |
2017年 | 85篇 |
2016年 | 106篇 |
2015年 | 119篇 |
2014年 | 151篇 |
2013年 | 326篇 |
2012年 | 197篇 |
2011年 | 185篇 |
2010年 | 175篇 |
2009年 | 255篇 |
2008年 | 248篇 |
2007年 | 268篇 |
2006年 | 236篇 |
2005年 | 215篇 |
2004年 | 204篇 |
2003年 | 162篇 |
2002年 | 469篇 |
2001年 | 154篇 |
2000年 | 138篇 |
1999年 | 100篇 |
1998年 | 111篇 |
1997年 | 88篇 |
1996年 | 77篇 |
1995年 | 76篇 |
1994年 | 62篇 |
1993年 | 63篇 |
1992年 | 49篇 |
1991年 | 42篇 |
1990年 | 28篇 |
1989年 | 27篇 |
1988年 | 21篇 |
1987年 | 13篇 |
1986年 | 22篇 |
1985年 | 22篇 |
1984年 | 13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5061条查询结果,搜索用时 218 毫秒
101.
V. P. Lebedev V. V. Chironov A. N. Kizin I. F. Falyahov I. Sh. Saifullin O. R. Klyuchnikov Yu. D. Orlov Yu. A. Lebedev 《Russian Chemical Bulletin》1995,44(4):639-641
The enthalpies of combustion of some pyridine derivatives in the solid state have been measured by precision bomb calorimetry, and their enthalpies of formation have been calculated. The enthalpies of sublimation of these compounds have been determined from the experimental temperature dependences of saturated vapor pressure using the Clausius-Clapeyron equation. The enthalpies of combustion, formation, and sublimation are the following (kJ mol–1): -3360.9±2.1, -0.5±2.1, and 79.1±1.3, respectively, for 4-methylpyridine 1-oxide; -2551.0±1.7, 11.7±1.7, and 89.1±2.5, respectively, for 4-nitropyridine 1-oxide;-2355.6±1.3, 102.1±1.3, and 106.3±2.9 for 2,4,6-trinitropyridine 1-oxide; and -2287.6±1.3, 34.3±1.3, and 101.7±2.9 for 2,4,6-trinitropyridine. The enthalpies of formation in the solid state and the enthalpies of sublimation of pyridine derivatives obtained together with the literature data allowed the energies of dissociation of the donor-acceptor N—O bonds in pyridine 1-oxides to be calculated.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 660–662, April, 1995. 相似文献
102.
The use of H-point curve isolation (HPCIM) and H-point standard addition methods (HPSAM) for spectrophotometric studies of complex formation equilibria are proposed. One step complex formation, two successive stepwise and mononuclear complex formation systems, and competitive complexation systems are studied successfully by the proposed methods. HPCIM is used for extracting the spectrum of complex or sum of complex species and HPSAM is used for calculation of equilibrium concentrations of ligand for each sample. The outputs of these procedures are complete concentration profiles of equilibrium system, spectral profile of intermediate components, and good estimation of conditional formation constants. The reliability of the method is evaluated using model data. Spectrophotometric studies of murexide-calcium, dithizone-nickel, methyl thymol blue (MTB)-copper, and competition of murexide and sulfate ions for complexation with zinc, are used as experimental model systems with different complexation stoichiometries and spectral overlapping of involved components. 相似文献
103.
Clovis Peppe Paola de Azevedo Mello Rafael Pavão das Chagas 《Journal of organometallic chemistry》2006,691(11):2335-2339
The organoindium compound derived from indium monobromide and dibromoacetonitrile reacts with carbonyl compounds to afford the corresponding 2-bromo-2-cyano-indium(III) alkoxide. The action of a second equivalent of indium monobromide onto the alkoxides derived from aldehydes promotes the Boord elimination of the β-related oxygen and bromine atoms leading to 2-alkenenitriles. 相似文献
104.
S. Kallus A. Hahn G. Golemme C. Algieri P. Timmins J.D.F. Ramsay 《Journal of Sol-Gel Science and Technology》2003,26(1-3):721-725
The synthesis of zeolite membranes and thin films using the secondary growth process is briefly described. In this process colloidal zeolite particles (sols) are prepared hydrothermally and then subsequently deposited on substrates to produce uniform layers of controlled thickness, as illustrated with silicalite and zeolite-A. The formation and growth of the zeolite sols has been investigated in situ by small angle neutron scattering (SANS). SANS measurements on silicalite sols at progressively higher concentrations have provided details of the colloid interactions which lead to zeolite gel-layer structures which are uniform and free of defects. 相似文献
105.
协调政府与社会资本合作的利益分歧,进而实现个体理性向集体理性的趋同,这是纾解PPP项目合作困境的切入点之一。基于合作博弈理论,本文构建PPP项目非完全利益群体的合作形成机制,分析政府与社会资本间“合作共赢”的必要因素。研究表明,由政府与社会资本组成的PPP项目非完全利益群体,可在“理性-效用转移-有效协商”机制的协同作用下主动采取最优合作策略。其中,理性机制验证了政府与社会资本达成合作意向的前提,效用转移机制可实现二者之间的风险-收益对等,有效协商机制将达成政府与社会资本合作的帕累托均衡。 相似文献
106.
We study a nonlinear fourth order evolution equation arising in the context of sand ripple dynamics. We analyse the set of stationary solutions and travelling waves in order to recover the observed phenomenology such as different wavelengths ripples, travelling waves, coarsening and time scales. Moreover, we construct an approximate solution which describes the early stages of the dynamics and which suggests the existence of coarsening and of time scales with different dynamical behaviour. 相似文献
107.
Highly efficient kinetic resolution of racemic secondary alkyl diazoacetates in intramolecular carbon-hydrogen insertion reactions has been achieved using chiral dirhodium(ii) carboxamidates. Products formed from catalytic diazo decomposition of racemic 2-octyl diazoacetate and, separately, its (2R)- and (2S)-enantiomeric forms, as well as bothcis- andtrans-2-methylcyclohexyl diazoacetates, have been systematically evaluated. Enantioselectivities up to 99 %ee have been obtained for -lactone formation. -Lactone production has been observed and, although minor with cyclohexyl diazoacetates, is the major insertion pathway for diazo decomposition of 2-octyl diazoacetate.Dedicated to Academician of the RAS N. S. Zefirov (on his 60th birthday).Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1798–1803, September, 1995.Financial support for this research from the National Institutes of Health (GM 46503) and the National Science Foundation of the United States is gratefully acknowledged. We thank D. A. Pierson for her preparation of 2-methylcyclohexyl diazoacetates and preliminary studies of their diazo decomposition and A. Melekhov from the Higher College of Chemistry for his preparation and catalytic studies of rac-2-octyl diazoacetate. 相似文献
108.
Phase transitions and hysteresis in a cellular automata-based model of opinion formation 总被引:1,自引:0,他引:1
A particular case of a cellular automata-based model of two-state opinion formation in social groups with a strong leader is studied. We consider a 2D Euclidian geometry of social space and mutual interactions 1/r
n
. The model shows an interesting dynamics which can be analytically calculated. There are two stable states of the system: a cluster around the leader and unification. Unstable clusters may also appear. A variation in parameters such as the leader's strength or the social temperature can change the size of a cluster or, when they reach some critical values, make the system jump into another state. For a certain range of parameters the system exhibits bistability and hysteresis phenomena. We obtained explicit formulas for the cluster size, critical leader's strength, and critical social temperature. These analytical results are verified by computer simulations. 相似文献
109.
Contrary to the informations in the literature our results of equilibrium and kinetic measurements indicate that Al(III) and Pyridine-2,6-dicarboxylic Acid in the range ofpH=(3...5) only formed the complexes AlHL
2+ (log=7.44±0.2) and AlL
+ (log=11.37±0.06). 相似文献
110.
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