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   344篇
  免费   0篇
  国内免费   2篇
化学   261篇
晶体学   9篇
力学   25篇
综合类   2篇
数学   15篇
物理学   34篇
  2021年   4篇
  2015年   4篇
  2014年   3篇
  2013年   12篇
  2012年   13篇
  2011年   19篇
  2010年   5篇
  2009年   17篇
  2008年   21篇
  2007年   12篇
  2006年   9篇
  2005年   21篇
  2004年   15篇
  2003年   9篇
  2002年   8篇
  2001年   10篇
  2000年   10篇
  1999年   10篇
  1998年   11篇
  1997年   6篇
  1996年   8篇
  1995年   4篇
  1994年   8篇
  1993年   4篇
  1992年   5篇
  1991年   9篇
  1988年   3篇
  1987年   2篇
  1986年   3篇
  1985年   4篇
  1984年   4篇
  1982年   7篇
  1981年   3篇
  1980年   2篇
  1979年   2篇
  1978年   2篇
  1977年   6篇
  1976年   2篇
  1975年   2篇
  1974年   4篇
  1973年   3篇
  1972年   2篇
  1971年   2篇
  1968年   7篇
  1967年   2篇
  1966年   3篇
  1965年   2篇
  1962年   4篇
  1961年   2篇
  1960年   2篇
排序方式: 共有346条查询结果,搜索用时 15 毫秒
91.
The synthesis and polymerization of N-[1-(1-substituted-2-oxopropyl)]acrylamides and -methacrylamides are described. Seven new monomers were prepared by two kinds of synthetic procedure. The polymerization of these monomers was carried out. Monomer reactivity ratios in the polymerization of these monomers with styrene were determined and the Alfrey-Price Q and e values calculated. The effects of substituents on the reactivities in copolymerization were observed, and an interpretation of the results is given.  相似文献   
92.
Spinel iron oxide (Fe3O4-γ-Fe2O3) particles were supported on microbeads of silica gel by the calcination of the silica gel base adsorbing citric acid and Fe3+ ions. The X-ray diffraction patterns and the57Fe Mössbauer spectra measured for the spinel iron oxide indicated that the particle size of the oxide was regulated by the mean pore diameter (4–82 nm) of the silica gel support employed. In the case of α-Fe2O3 particles prepared by using the same silica gel beads, it was revealed by the Mössbauer spectra and the electron micrographs that there were relatively large particles of the oxide on the surface of the beads, in addition to the particles in the silica gel micropores.  相似文献   
93.
94.
95.
We used both localized and periodic calculations on a series of monovalent (Li+, Na+, K+, Rb+, Cs+) and divalent (Mg2+, Ca2+, Sr2+, Ba2+) cations to monitor their effect on the swelling of clays. The activity order obtained for the exchangeable cations among all the monovalent and divalent series studied: Ca2+ > Sr2+ > Mg2+ > Rb+ > Ba2+ > Na+ > Li+ > Cs+ > K+. We have shown that, in case of dioctahedral smectite, the hydroxyl groups play a major role in their interaction with water and other polar molecules in the presence of an interlayer cation. We studied both type of clays, with a different surface structure and with/without water using a periodic calculation. Interlayer cations and charged 2:1 clay surfaces interact strongly with polar solvents; when it is in an aqueous medium, clay expands and the phenomenon is known as crystalline swelling. The extent of swelling is controlled by a balance between relatively strong swelling forces and electrostatic forces of attraction between the negatively charged phyllosilicate layer and the positively charged interlayer cation. We have calculated the solvation energy at the first hydration shell of an exchangeable cation, but the results do not correspond directly to the experimental d-spacing values. A novel quantitative scale is proposed with the numbers generated by the relative nucleophilicity of the active cation sites in their hydrated state through Fukui functions within the helm of the hard soft acid base principle. The solvation effect thus measured show a perfect match with experiment, which proposes that the reactivity index calculation with a first hydration shell could rationalize the swelling mechanism for exchangeable cations. The conformers after electron donation or acceptance propose the swelling mechanism for monovalent and divalent cations.  相似文献   
96.
The problem of the robust stability of large-scale dynamical systems including delayed states and parameter perturbations in interconnections is considered. By using algebraic Riccati equations and some analytical methods, some sufficient conditions on linear decentralized state feedback controllers are derived so that the systems remain stable in the presence of delayed states and parameter perturbations. Such conditions give some bounds on the perturbations of interconnections with delayed states and uncertain parameters, and result in a quantitative measures of robustness for large-scale dynamical systems including delayed states and uncertain parameters in interconnections. The results obtained in this paper are applicable not only to large-scale systems with multiple time-varying delays, but also to large-scale systems without exact knowledge of the delays, i.e., large-scale systems with uncertain delays.  相似文献   
97.
    
Carbon and nitrogen stable isotope ratios were measured in hair samples of the Asiatic black bear (Ursus thibetanus) inhabiting the Northern Japanese Alps (NJA) (n?=?20) and the periphery of Nagano City (NC) (n?=?6), in Nagano Prefecture, Japan. The hair of NJA bears, which did not have access to anthropogenic foods, showed lower values of δ13C and δ15N than that of NC bears which had access to garbage and corn fields, especially during the summer. These results reflect somewhat differing diets between the NJA and NC bears. We attempted to assess the feeding history during the hair growth cycle using the growth section analysis method. Each hair sample had been cut into 3?mm lengths from root to tip, labeled, and analyzed along the hair growth. We measured the carbon and nitrogen stable isotope ratios of each 3?mm length of hair sample from one NC bear which had been killed while raiding a corn field. The sections showed wide ranges of isotope ratios, from ?23.2‰ to ?14.6‰ for δ13C, and from 0.3‰ to 4.6‰ for δ15N. It was shown that the diet of this bear shifted dramatically from principally C3 plants to more C4 plants and to foods of animal origin. An analysis of the whole hair reflects just the average feeding habit during hair growth, but the present method can trace its diet history. This method can contribute to obtain precise ecological information of wildlife.  相似文献   
98.
    
Solvolysis rates of 2‐(aryldimethylsilyl)‐1‐methylethyl and 2‐(aryldimethylsilyl)‐1‐tert‐butylethyl trifluoroacetates were determined conductimetrically in 60% (v/v) aqueous ethanol. The effects of aryl substituents at the silicon atom on the solvolysis rates at 50 °C were correlated with parameters of r+ = 0.15 with the Yukawa–Tsuno equation, giving ρ values of ?1.5 for both secondary α‐Me and αtert‐Bu systems. The ρ values for those secondary systems are less negative than ?1.75 for the 2‐(aryldimethylsilyl)ethyl system that proceeds by the Eaborn (non‐vertical) mechanism, while they are distinctly more negative than ?0.99 for 2‐(aryldimethylsilyl)‐1‐phenylethyl system that should proceed by the Lambert (vertical) mechanism. There was a fairly linear relationship between the reaction constants (ρ) for the β‐silyl substituent effects and the solvolysis reactivities for a series of β‐silyl substrates. The solvolyses of the α‐Me and tert‐Bu substrates proceed through the transition state (TS) with an appreciable degree of the β‐silyl participation, close to the Eaborn (non‐vertical) TS rather than to the Lambert (vertical) TS. Copyright © 2010 John Wiley & Sons, Ltd.  相似文献   
99.
    
Structures of α-hydroxybenzylic cations and their conjugate bases, which cover a wide variation of stability, were optimized by means of ab initio molecular orbital method at the RHF/6–31G* level. Total energies were calculated at the MP2/6–31G*//RHF/6–31G* + ZPE (scaled 0.9) level. Calculated relative proton affinities of the respective neutral molecules (benzoyl compounds; conjugate bases of α-hydroxybenzylic cations) agreed well with the corresponding basicities in the gas phase. The geometries of α-amino-α-hydroxybenzyl and α-hydroxy-α-dimethylaminobenzyl cations were also optimized at the fixed dihedral angles between the cationic 2pπ orbital and the benzene π orbital (ϕ), and between the cationic 2pπ orbital and lone pair electron orbital of the α-substituent (θ). The changes in Wiberg bond orders and the rotational potentials about ϕ and θ showed that the degree of resonance interaction between the cationic center and phenyl ring is balanced by the electronic effects of α-substituents in benzylic cations. The obtained theoretical indices of all parent cations such as Mulliken population, Wiberg bond order and bond lengths were correlated linearly with the resonance demand parameter (r value) which were given by the Yukawa–Tsuno substituent effect analysis in the gas phase and in aqueous solution. These relationships are consistent with those for other benzylic cations such as destabilized carbocations and sterically hindered cations studied previously. This confirms that the empirical r value has a definitive physical meaning, i.e. a measure of the resonance interaction between the cationic center and the aryl moiety. Copyright © 1998 John Wiley & Sons, Ltd.  相似文献   
100.
    
The substituent effects on the solvolysis of 1‐X‐phenyl‐1‐Y‐phenyl‐2,2,2‐trifluoroethyl tosylates were analyzed on the basis of the Yukawa–Tsuno equation. For the solvolysis of the symmetrically disubstituted X = Y subseries, an excellent linear correlation was obtained. However, in the solvolyses of series of varying X with a fixed‐Y subset, the substituent effects were found to give significantly concave Y–T correlations. The ρ value for the Y–T correlations changes significantly with the fixed Y substituent. There is a qualitative trend of a linear decrease in the ρ value as the fixed‐Y substituent of the respective subset becomes more electron donating. The non‐linearity of substituent effects was attributed to a substituent‐induced conformational change of the transition state, which could be simulated by calculation of the preferred conformation of the intermediate carbocation. A molecular orbital optimization method was applied to determine the preferred conformations of the α,α‐diarylcarbenium ions derived from the title systems. The symmetrical carbenium ions X = Y have a preferred propeller shape conformation with twist angles differing by 14° ( E conformation), whereas in the unsymmetrical systems X ≠ Y the two aryl rings are much more (>30°) differently twisted in the preferred conformation ( PT conformation). The linear correlation found for the symmetrical subseries is essentially an outcome of the E conformation of the transition state. In unsymmetrical cases, the substituent effect correlation in any Y subset should reflect the conformational arrangements, E X, P X and T X of the variable X‐aryl group, depending on relative σ values of X and Y. The substituent effects in the Y‐subsets were successfully treated by three different Y‐independent correlations for the preferred conformational arrangements: E correlation for substituents when (σ X − σ Y) ≅ 0, P X correlation when (σ X − σ Y) ≪0 and T X correlation for the (σ X − σ Y) ≫0 class, respectively. Copyright © 2002 John Wiley & Sons, Ltd.  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