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911.
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914.
Dieter Hofmann Lydia Fritz Jens Ulbrich Claudia Schepers Martin Bhning 《Macromolecular theory and simulations》2000,9(6):293-327
Atomistic molecular modeling techniques have proven to be a very useful tool for the investigation of the structure and dynamics of dense amorphous membrane polymers and of transport processes in these materials. As illustrations, the results of extensive atomistic molecular dynamics investigations on the transport of different small molecules in flexible chain rubbery and stiff chain glassy polymers are discussed. For this purpose bulk polymer models and interface models for liquid feed mixtures in contact with the upstream site of the respective membrane have been employed. A comparison between the static structure and the dynamic behavior of the free volume in the simulated flexible chain rubbery polymers and stiff chain glassy polymers reveals qualitative differences which are decisive for experimentally observable differences in the diffusion of small molecules in these materials. The simulation results for the interface models reflect important features of experimentally well characterized pervaporation processes. 相似文献
915.
Heinz‐Georg Nothofer Andreas Meisel Tzenka Miteva Dieter Neher Michael Forster Masao Oda Günter Lieser Dessislava Sainova Akio Yasuda Donald Lupo Wolfgang Knoll Ullrich Scherf 《Macromolecular Symposia》2000,154(1):139-148
A series of 9,9‐dialkyl‐poly(fluorene‐2,7‐diyl)s containing linear and branched alkyl substituents with a Mn of up to 200000 g/mol has been synthesized. Moreover, some of the polymers were end capped with a suitable hole transport functionality, such as a triphenylamine derivative, to improve their charge transport properties and to control the molecular weight. The thermal alignment of these novel polymers on a rubbed polyimide layer led to highly anisotropic film formation with dichroic ratios (absorption parallel and perpendicular to the rubbing direction) of up to 26 in absorption and 21 in emission. 相似文献
916.
917.
918.
The 4-isopropyl-5,5-diphenyloxazolidinone ( 1 ) is readily prepared from (R)- or (S)-valine ester, PhMgBr, and ethyl chlorocarbonate. It has a melting point of ca. 250°, a low solubility in most organic solvents, and a C=O group which is sterically protected from nucleophilic attack. Thus, the soluble N-acyl-oxazolidinones ( 7 – 16 ) can be prepared from 1 with BuLi at temperatures around 0° instead of −78° (Scheme 3), their Li enolates can be generated with BuLi, rather than with LDA, and deacylation in the final step of the procedure can be achieved with NaOH at ambient temperatures (Scheme 12), with facile recovery of the precipitating auxiliary 1 (filtering, washing, and drying). The following reactions of N-acyl-oxazolidinones from 1 have been investigated: alkylations (Scheme 4), aminomethylations and hydroxymethylations (Scheme 5), aldol additions (Schemes 6 and 7), Michael additions (Schemes 9 and 10), and a (4+2) cycloaddition (Scheme 11). The well-known features of reactions following the Evans methodology (yield, diastereoselectivity, dependence on conditions, counter ions, additives etc.) prevail in these transformations. Most products, however, have higher melting points and a much more pronounced crystallization tendency than those derived from conventional oxazolidinones, and can thus be purified by recrystallization, avoiding chromatography (Table 1). The disadvantage of 1 having a higher molecular weight (ca. 150 Da) than the non-phenyl-substituted auxiliary is more than compensated by the ease of its application, especially on large scale. A number of crystal structures of oxazolidinones derived from 1 and a TiCl4 complex of an oxazolidinone are described and discussed in view of the diastereoselective-reaction mechanisms. 相似文献
919.
Matthias Driess Christian Mons Roland Boese Dieter Blser 《Angewandte Chemie (International ed. in English)》1998,37(16):2257-2259
Inversion-symmetric pairs, each with two weak P–H⋅⋅⋅P interactions, form molecules of Si(PH2)4 in the crystal (see drawing). The title compounds are formed from ECl4 (E=Si,Ge) on reaction with [LiAl(PH2)4] and could serve as single-source CVD precursors for phosphides. 相似文献
920.
Dietmar Leipert Peter Heiduschka Jürgen Mack Hans-Joachim Egelhaaf Dieter Oelkrug Günther Jung 《Angewandte Chemie (International ed. in English)》1998,37(17):2337-2340
Microstructuring of surfaces: Electrochemical polymerization after removal of a photolabile protecting group (nitrobenzyl group) represents a new method for spatially resolved immobilization of ligands or receptors. Thus, the electropolymerization of 3-hydroxyphenylacetyl peptides such as 1 on electrodes can be controlled by light 相似文献