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71.
Hsieh CS Campen RK Vila Verde AC Bolhuis P Nienhuys HK Bonn M 《Physical review letters》2011,107(11):116102
We report the real-time measurement of the ultrafast reorientational motion of water molecules at the water-air interface, using femtosecond time- and polarization-resolved vibrational sum-frequency spectroscopy. Vibrational excitation of dangling OH bonds along a specific polarization axis induces a transient anisotropy that decays due to the reorientation of vibrationally excited OH groups. The reorientation of interfacial water is shown to occur on subpicosecond time scales, several times faster than in the bulk, which can be attributed to the lower degree of hydrogen bond coordination at the interface. Molecular dynamics simulations of interfacial water dynamics are in quantitative agreement with experimental observations and show that, unlike in bulk, the interfacial reorientation occurs in a largely diffusive manner. 相似文献
72.
Angel Alberola Celia Andrs Alfonso Gonzlez Ortega Rafael Pedrosa Martina Vicente 《Journal of heterocyclic chemistry》1986,23(6):1781-1783
The trimethylsilyl derivative of formonometine reacts sequentially with two different organometallic derivatives to afford regiospecifically and with good yield 2,4-dialkylisoflavenes unsymmetrically substituted. 相似文献
73.
Lulu Healy Celia Hoyles 《International Journal of Computers for Mathematical Learning》2002,6(3):235-256
Dynamic geometry software provides tools for students to construct and experiment with geometrical objects and relationships. On the basis of their experimentation, students make conjectures that can be tested with the tools available. In this paper, we explore the role of software tools in geometry problem solving and how these tools, in interaction with activities that embed the goals of teachers and students, mediate the problem solving process. Through analysis of successful student responses, we show how dynamic software tools can not only scaffold the solution process but also help students move from argumentation to logical deduction. However, by reference to the work of less successful students, we illustrate how software tools that cannot be programmed to fit the goals of the students may prevent them from expressing their (correct) mathematical ideas and thus impede their problem solution.This revised version was published online in September 2005 with corrections to the Cover Date. 相似文献
74.
Mercedes Blanco M. Gabriela Lorenzo Isabel Perillo Celia B. Schapira 《Journal of heterocyclic chemistry》1996,33(2):361-366
The reaction of N-substituted quinolinimides 1a-d with sodium alkoxides afforded a mixture of 1,6-naphthyridines 2 and 1,7-naphthyridines 3 which were isolated by chromatographic methods. Structure assignment for each pair of isomers was made by comparison of their 1H nmr spectra with those of picolinamide and nicotinamide. When esters 1a -c were treated with alkoxides from primary alcohols, other than that of the ester, total transesterification took place. Experimental results suggest that transesterification occurs in open intermediary species. 相似文献
75.
76.
Cabaleiro-Lago C Quinlan-Pluck F Lynch I Lindman S Minogue AM Thulin E Walsh DM Dawson KA Linse S 《Journal of the American Chemical Society》2008,130(46):15437-15443
Copolymeric NiPAM:BAM nanoparticles of varying hydrophobicity were found to retard fibrillation of the Alzheimer's disease-associated amyloid beta protein (Abeta). We found that these nanoparticles affect mainly the nucleation step of Abeta fibrillation. The elongation step is largely unaffected by the particles, and once the Abeta is nucleated, the fibrillation process occurs with the same rate as in the absence of nanoparticles. The extension of the lag phase for fibrillation of Abeta is strongly dependent on both the amount and surface character of the nanoparticles. Surface plasmon resonance studies show that Abeta binds to the nanoparticles and provide rate and equilibrium constants for the interaction. Numerical analysis of the kinetic data for fibrillation suggests that binding of monomeric Abeta and prefibrillar oligomers to the nanoparticles prevents fibrillation. Moreover, we find that fibrillation of Abeta initiated in the absence of nanoparticles can be reversed by addition of nanoparticles up to a particular time point before mature fibrils appear. 相似文献
77.
Altman MD Ali A Reddy GS Nalam MN Anjum SG Cao H Chellappan S Kairys V Fernandes MX Gilson MK Schiffer CA Rana TM Tidor B 《Journal of the American Chemical Society》2008,130(19):6099-6113
The acquisition of drug-resistant mutations by infectious pathogens remains a pressing health concern, and the development of strategies to combat this threat is a priority. Here we have applied a general strategy, inverse design using the substrate envelope, to develop inhibitors of HIV-1 protease. Structure-based computation was used to design inhibitors predicted to stay within a consensus substrate volume in the binding site. Two rounds of design, synthesis, experimental testing, and structural analysis were carried out, resulting in a total of 51 compounds. Improvements in design methodology led to a roughly 1000-fold affinity enhancement to a wild-type protease for the best binders, from a Ki of 30-50 nM in round one to below 100 pM in round two. Crystal structures of a subset of complexes revealed a binding mode similar to each design that respected the substrate envelope in nearly all cases. All four best binders from round one exhibited broad specificity against a clinically relevant panel of drug-resistant HIV-1 protease variants, losing no more than 6-13-fold affinity relative to wild type. Testing a subset of second-round compounds against the panel of resistant variants revealed three classes of inhibitors: robust binders (maximum affinity loss of 14-16-fold), moderate binders (35-80-fold), and susceptible binders (greater than 100-fold). Although for especially high-affinity inhibitors additional factors may also be important, overall, these results suggest that designing inhibitors using the substrate envelope may be a useful strategy in the development of therapeutics with low susceptibility to resistance. 相似文献
78.
Aslund I Cabaleiro-Lago C Söderman O Topgaard D 《The journal of physical chemistry. B》2008,112(10):2782-2794
The size of the anisotropic domains in a lyotropic liquid crystal is estimated using a new protocol for diffusion NMR. Echo attenuation decays are recorded for different durations of the displacement-encoding gradient pulses, while keeping the effective diffusion time and the range of the wave vectors constant. Deviations between the sets of data appear if there are non-Gaussian diffusion processes occurring on the time-scale defined by the gradient pulse duration and the length-scale defined by the wave vector. The homogeneous length-scale is defined as the minimum length-scale for which the diffusion appears to be Gaussian. Simulations are performed to show that spatial variation of the director orientation in an otherwise homogeneous system is sufficient to induce non-Gaussian diffusion. The method is demonstrated by numerical solutions of the Bloch-Torrey equation and experiments on a range of lamellar liquid crystals with different domain sizes. 相似文献
79.
Amelia Bilbao-Terol Mar Arenas-Parra Verónica Cañal-Fernández Celia Bilbao-Terol 《Annals of Operations Research》2016,247(2):549-580
The current economic crisis fuels the financial social responsibility after an epoch of many excesses with damaging effects. This work tackles two emerging streams in the financial literature: the behavioral portfolio theory with mental accounting and the socially responsible investment (SRI). Promoting SRI is regarded by a lot of financial experts, policymakers and researchers from the field of economic and social sciences, as one of the potential solutions in order to avoid future crises. Therefore, new models for this investment approach are necessary. We try to support the class of investors that select their investments under a mental accounting framework and also they want to achieve a certain level of SR quality in their portfolios. In order to reconcile the two choice frames, avoiding unnecessary sacrifices in financial performance, we have designed a model based on goal programming that integrates the two cornerstones of the investor. Furthermore, we propose a fuzzy inference system to determine the amount of money allocated to each mental account as well as the confidence level assigned to each mental account. This tool is based on expert knowledge modeled by fuzzy if–then rules. 相似文献
80.
We show that for a locally \(\sigma \)-finite measure \(\mu \) defined on a \(\delta \)-ring, the associate space theory can be developed as in the \(\sigma \)-finite case, and corresponding properties are obtained. Given a saturated \(\sigma \)-order continuous \(\mu \)-Banach function space E, we prove that its dual space can be identified with the associate space \(E ^\times \) if, and only if, \(E^\times \) has the Fatou property. Applying the theory to the spaces \(L^p (\nu )\) and \(L_w^p (\nu )\), where \(\nu \) is a vector measure defined on a \(\delta \)-ring \(\mathcal {R}\) and \(1 \le p < \infty \), we establish results corresponding to those of the case when the vector measure is defined on a \(\sigma \)-algebra. 相似文献