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151.
Six 4-substituted quinolones 6-8, which bear an ω-iodoalkyl chain, were prepared and subjected to reductive radical cyclisation conditions employing BEt(3)/O(2) as the initiator and either Bu(3)SnH or TMS(3)SiH as hydride source. 4-(4-Iodobutyl)-quinolone (6a) and 4-(3-iodopropylthio)-quinolone (8a) gave the respective 6-endo-cyclisation products in good yields. 4-(3,3-Dimethyl-4-iodobutyl)-quinolone (6b) cyclised in a 5-exo-fashion, while the other substrates delivered only reduction products. The cyclisation reactions could be conducted in the presence of a chiral template (1) with high enantiomeric excess (94-99% ee). The association behaviour of substrate 6a to 1 was studied by NMR titration experiments. In the enantioselective cyclisation of 6b a significant nonlinearity was observed when comparing the product ee with the ee of the template. 相似文献
152.
Fuchs SW Proschak A Jaskolla TW Karas M Bode HB 《Organic & biomolecular chemistry》2011,9(9):3130-3132
Thirteen novel PAX (peptide-antimicrobial-Xenorhabdus) peptides were identified in Xenorhabdus nematophila HGB081. Their structures including the absolute configuration were elucidated using a combination of labeling experiments, detailed MS/MS experiments, the advanced Marfey's method, and a detailed analysis of the biosynthesis gene cluster, which was identified as well. 相似文献
153.
The synthesis and characterization of a new difunctional coupler (4) based on trimethylolpropane (TMP) are described. The coupler is used to connect biologically active N-acetylglucosamine (GlcNAc) on amino-reactive microtiter plates and on star-shaped poly[(ethylene oxide)-stat-(propylene oxide)] hydrogel layers in microtiter plates. The biological activity of immobilized carbohydrates is determined using an enzyme-linked lectin assay. 相似文献
154.
Thorsten Kattelans Wilhelm Heinrichs 《Journal of Computational and Applied Mathematics》2011,236(6):1193-1215
From the literature, it is known that the Least-Squares Spectral Element Method (LSSEM) for the stationary Stokes equations performs poorly with respect to mass conservation but compensates this lack by a superior conservation of momentum. Furthermore, it is known that the Least-Squares Spectral Collocation Method (LSSCM) leads to superior conservation of mass and momentum for the stationary Stokes equations. In the present paper, we consider mass and momentum conservation of the LSSCM for time-dependent Stokes and Navier-Stokes equations. We observe that the LSSCM leads to improved conservation of mass (and momentum) for these problems. Furthermore, the LSSCM leads to the well-known time-dependent profiles for the velocity and the pressure profiles. To obtain these results, we use only a few elements, each with high polynomial degree, avoid normal equations for solving the overdetermined linear systems of equations and introduce the Clenshaw-Curtis quadrature rule for imposing the average pressure to be zero. Furthermore, we combined the transformation of Gordon and Hall (transfinite mapping) with the least-squares spectral collocation scheme to discretize the internal flow problems. 相似文献
155.
Hartmann E Brendebach B Polly R Geckeis H Stumpf T 《Journal of colloid and interface science》2011,353(2):562-568
In order to assess the long-term safety of deep radioactive waste repositories, a precise characterization of the different sorption processes on a molecular basis and the exact definition of geochemical boundary conditions for their relevance are of immense importance. Through sorption on various minerals the migration of radionuclides will be hindered and their retention will be ensured. Using time-resolved laser fluorescence spectroscopy (TRLFS) and extended X-ray absorption fine structure (EXAFS) spectroscopy, it was possible to identify outer-sphere sorbed trivalent lanthanides and actinides onto different montmorillonites and illite. Furthermore, the quantification of Cm(III)/clay outer-sphere sorption in D(2)O at different ionic strengths was shown. The results were confirmed by ion exchange model calculations. Finally, the structural parameters of a Sm(III)/clay outer-sphere complex were obtained by EXAFS measurements. 相似文献
156.
Short-chain fatty acids are crucial intermediates in the conversion of biomass to methane. Due to the complexity of raw biomass, volatile fatty acids (including n- and branched-chain compounds) as well as arylacetic and arylpropionic acids arise from digestion of carbohydrates, proteins and lipids. The development of a simple extraction procedure in combination with internal standardization and facile 4-nitrophenyl-labelling via oxalylchloride-generated acylchlorides enabled robust separation and quantification of the target compounds in crude biological samples like raw cattle manure and biogas fermenter contents. Detection limits of <100 μM and error rates of less than 4% for the quantification of individual compounds in a concentration range up to 50 mM for non-diluted samples suggest that the novel method might be of general advantage for the routine quantification of short-chain fatty acids in complex biological samples including complex fermentation media. 相似文献
157.
The oxidation of carbon monoxide with nitrous oxide on mass-selected Au(3)(+) and Ag(3)(+) clusters has been investigated under multicollision conditions in an octopole ion trap experiment. The comparative study reveals that for both gold and silver cations carbon dioxide is formed on the clusters. However, whereas in the case of Au(3)(+) the cluster itself acts as reactive species that facilitates the formation of CO(2) from N(2)O and CO, for silver the oxidized clusters Ag(3)O(x)(+) (n=1-3) are identified as active in the CO oxidation reaction. Thus, in the case of the silver cluster cations N(2)O is dissociated and one oxygen atom is suggested to directly react with CO, whereas a second kind of oxygen strongly bound to silver is acting as a substrate for the reaction. 相似文献
158.
Zöller T Iovkova-Berends L Berends T Dietz C Bradtmöller G Jurkschat K 《Inorganic chemistry》2011,50(17):8645-8653
The syntheses and molecular structures of the intramolecularly coordinated tin(II) compounds {CH(2)N(Me)CH(Me)CH(Ph)O}(2)SnL (2, L = lone pair; 4, L = W(CO)(5); 5, L = Cr(CO)(5)) and of the related hydroxido-substituted tin(IV) compound [{CH(2)N(Me)CH(Me)CH(Ph)O}(2)Sn(OH)](2)O, 6a, are reported. Also reported are the molecular structures of the enantiopure N,N'-ethylenebis-(1R,2S)-ephedrine, {CH(2)N(Me)CH(Me)CH(Ph)OH}(2) (1), and its hydrobromide {CH(2)N(Me)CH(Me)CH(Ph)OH}(2)·HBr (1a). 相似文献
159.
Austin KA Herdtweck E Bach T 《Angewandte Chemie (International ed. in English)》2011,50(36):8416-8419
From simple to complex: Starting from easily accessible isoquinolones 1 (X=Br, OH), complex cyclobutane photoproducts such as compound 2 can be obtained with high enantioselectivity (88-96?%?ee) through the use of a chiral template. Compound 3, which was isolated in 53?%?ee starting from a racemic substrate, is the product of a unique, unprecedented kinetic resolution process. 相似文献
160.
Biskup T Hitomi K Getzoff ED Krapf S Koslowski T Schleicher E Weber S 《Angewandte Chemie (International ed. in English)》2011,50(52):12647-12651
Subtle differences in the local sequence and conformation of amino acids can result in diversity and specificity in electron transfer (ET) in proteins, despite structural conservation of the redox partners. For individual ET steps, distance is not necessarily the decisive parameter; orientation and solvent accessibility of the ET partners, and thus the stabilization of the charge-separated states, contribute substantially. 相似文献