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71.
72.
Sr4Mn2Cu5O4S5 contains manganese oxide sheets separated by unusual antifluorite-type Cu3S3 layers in which copper(I) ions are distributed over three- and four-coordinates sites in a similar fashion to in alpha-Cu2-xS and suggestive of high two-dimensional copper ion mobility. 相似文献
73.
Development of a multiplexed microbioreactor system for high-throughput bioprocessing 总被引:1,自引:0,他引:1
A multiplexed microbioreactor system for parallel operation of multiple microbial fermentation is described. The system includes miniature motors for magnetic stirring of the microbioreactors and optics to monitor the fermentation parameters optical density (OD), dissolved oxygen (DO), and pH, in-situ and in real time. The microbioreactors are fabricated out of poly(methylmethacrylate)(PMMA) and poly(dimethylsiloxane)(PDMS), and have a working volume of 150 microl. Oxygenation of the cells occurs through a thin PDMS membrane at the top of the reactor chamber. Stirring is achieved with a magnetic spin bar in the reactor chamber. Parallel microbial fermentations with Escherichia coli are carried out in four stirred microbioreactors and demonstrate the reproducible performance of the multiplexed system. The profiles for OD, DO, and pH compare favourably to fermentations performed in bioreactor systems with multiple bench-scale reactors. Finally, the multiplexed system is used to compare two different reactor designs, demonstrating that the reproducibility of the system permits the quantification of microbioreactor performance. 相似文献
74.
Ketteler G Ogletree DF Bluhm H Liu H Hebenstreit EL Salmeron M 《Journal of the American Chemical Society》2005,127(51):18269-18273
Using a photoemission spectroscometer that operates close to ambient conditions of pressure and temperature we have determined the Pd-O phase diagram and the kinetic parameters of phase transformations. We found that on the (111) surface oxidation proceeds by formation of stable and metastable structures. As the chemical potential of O2 increases chemisorbed oxygen forms followed by a thin surface oxide. Bulk oxidation is a two-step process that starts with the metastable growth of the surface oxide into the bulk, followed by a first-order transformation to PdO. 相似文献
75.
Torrent-Sucarrat M Luis JM Solà M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(20):6024-6031
The vibrational motions that disobey the minimum polarizability principle (MPP) in pi-conjugated molecules are distortions of the equilibrium geometry that produce a reduction in the polarizability due to the localization of pi electrons. For aromatic species, this electronic localization is responsible for the subsequent reduction in the aromaticity of the system. In the present work, we diagonalize the Hessian matrix of the polarizability with respect to the vibrational nontotally symmetric normal coordinates, to calculate the nontotally symmetric distortions that produce the maximum breakdown of the MPP in a series of twenty polycyclic aromatic hydrocarbons. It is shown that the nuclear displacements that break the MPP have larger components in those rings that possess the highest local aromaticity. Thus, these vibrational motions can be used as an indicator of local aromaticity. 相似文献
76.
Substituted cyclopenta[b]indoles are selectively brominated in good yields with excess pyridine ‐ Br2 charge‐transfer complex (PyBr2) in a one‐pot reaction to provide 5 and/or 7‐bromoindoles. The mechanism involves the formation of an adduct (addition of bromine on the central double bond) which is subsequently reduced in situ with Zn and AcOH. A variety of functional groups in the cyclopentyl and the benzenoid rings are tolerated. 相似文献
77.
Nicolas Eugster Henrik Jensen David J. Fermín Hubert H. Girault 《Journal of Electroanalytical Chemistry》2003,560(2):143-149
The self-organisation of a variety of dyes at the water|1,2-dichloroethane interface was studied by admittance measurements, photocurrent–potential curves and light polarisation anisotropy of the photocurrent. The heterogeneous photo-oxidation of ferrocene was studied at interfaces sensitised by Sn(IV) meso-tetra-(4-carboxyphenyl) porphyrin dichloride (SnTPPC), chlorin e-6, protoporphyrin IX (protoIX) and Fe(III) protoporphyrin IX chloride (Fe-protoIX). Cyclic voltammograms and capacitance voltage curves exhibit different features associated with the self-assembly of the dye species at the liquid|liquid boundary. In the case of SnTPPC, the capacitance curves displayed the characteristic responses commonly associated with the specific adsorption of ionic species. On the other hand, chlorin e-6, protoIX and Fe-protoIX show rather complex behaviour suggesting not only changes in the excess charge but also in the dielectric permittivity of the interface. Differences in the photocurrent efficiency were also observed under the same experimental conditions. The relative magnitude of the photocurrent responses were rationalised in terms of the phenomenological electron transfer rate constant, the photon capture cross-sections and the lifetime of the triplet state as obtained from nanosecond flash photolysis. Finally, the average molecular orientation of the adsorbed photoactive species was estimated from the photocurrent dependence on the angle of light polarisation in total internal reflection. The results show a clear correlation between the orientation of the transition dipole and the distribution of the peripheral carboxyl groups responsible for the hydrophilic nature of the dyes. 相似文献
78.
Juan Manuel Ortiz-Sánchez Ricard Gelabert Miquel Moreno José M Lluch 《Chemphyschem》2007,8(8):1199-1206
The two isoelectronic bipyridyl derivatives, [2,2'-bipyridyl]-3,3'-diamine and [2,2'-bipyridyl]-3,3'-diol, are experimentally known to undergo very different excited-state double-proton-transfer processes, which result in fluorescence quantum yields that differ by four orders of magnitude. Herein, density functional theory (DFT), time-dependent DFT (TDDFT), and complete active space self-consistent field (CASSCF) calculations are used to study the double-proton-transfer processes in the ground and first singlet pi-->pi* excited state. The quantum-chemistry calculations indicate 1) the existence of only one energy minimum in the ground electronic state corresponding to reactants (thus avoiding the possibility of a fast fluorescent relaxation process from the photoproducts region), 2) an endoergic process of the complete double proton transfer, and 3) the presence of a conical intersection in the excited intermediate region of [2,2'-bipyridyl]-3,3'-diamine. These facts explain the very low fluorescence quantum yield in [2,2'-bipyridyl]-3,3'-diamine compared to [2,2'-bipyridyl]-3,3'-diol. 相似文献
79.
Various approaches to the syntheses of 5-substituted-3-carbomethoxy-2,5-dihydrothiophenes and their product sulfolenes, required as synthetic precursors for tangutorine, are described. An efficient route to 3,5-disubstituted-4,5-dihydrothiophenes and hence 3,5-disubstituted-2-sulfolenes by radical chemistry is also described. 相似文献
80.
Baurin N Aboul-Ela F Barril X Davis B Drysdale M Dymock B Finch H Fromont C Richardson C Simmonite H Hubbard RE 《Journal of chemical information and computer sciences》2004,44(6):2157-2166
We have designed four generations of a low molecular weight fragment library for use in NMR-based screening against protein targets. The library initially contained 723 fragments which were selected manually from the Available Chemicals Directory. A series of in silico filters and property calculations were developed to automate the selection process, allowing a larger database of 1.79 M available compounds to be searched for a further 357 compounds that were added to the library. A kinase binding pharmacophore was then derived to select 174 kinase-focused fragments. Finally, an additional 61 fragments were selected to increase the number of different pharmacophores represented within the library. All of the fragments added to the library passed quality checks to ensure they were suitable for the screening protocol, with appropriate solubility, purity, chemical stability, and unambiguous NMR spectrum. The successive generations of libraries have been characterized through analysis of structural properties (molecular weight, lipophilicity, polar surface area, number of rotatable bonds, and hydrogen-bonding potential) and by analyzing their pharmacophoric complexity. These calculations have been used to compare the fragment libraries with a drug-like reference set of compounds and a set of molecules that bind to protein active sites. In addition, an analysis of the overall results of screening the library against the ATP binding site of two protein targets (HSP90 and CDK2) reveals different patterns of fragment binding, demonstrating that the approach can find selective compounds that discriminate between related binding sites. 相似文献