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561.
Leary E Higgins SJ van Zalinge H Haiss W Nichols RJ Nygaard S Jeppesen JO Ulstrup J 《Journal of the American Chemical Society》2008,130(37):12204-12205
We demonstrate that the electrical "switching" behavior of single molecules connected between two electrode contacts can be controlled by altering their structure and electrochemical characteristics. The electrical properties of gold|molecule|gold single molecule junctions incorporating HS(CH2)6-X-(CH2)6SH, where X = viologen (4,4'-bipyridinium) or pyrrolotetrathiafulvalene, are determined using a scanning tunneling microscopy based technique. The switching behavior, controlled through a tuneable electrochemical gate, changes from an on-off response (viologen) to an off-on-off response (pyrrolotetrathiafulvalene) on changing the central redox group. In contrast, the electrical properties of junctions incorporating redox-inactive HS(CH2)6-1,4-C6H4-(CH2)6SH do not alter significantly as a function of applied potential. 相似文献
562.
Urban PL Goodall DM Carvalho AZ Bergström ET Van Schepdael A Bruce NC 《Journal of chromatography. A》2008,1206(1):52-63
Active pixel sensor UV area imaging and capacitively coupled contactless conductivity detection have been applied in an electrophoretically mediated microanalysis (EMMA) assay for substrate specificity of tyramine oxidase (Arthrobacter sp.). Use of the UV area imaging detector to monitor four windows in a capillary with three loops provided intrinsic self-referencing for all species and identified tyramine and 2-phenethylamine as the only reactive components in a multi-compound mixture. Continuous engagement EMMA experiments showed significant benefits by comparison with plug-plug EMMA, improving sensitivity by extending enzyme-substrate interaction times and allowing measurement of time-dependent reaction in the substrate zones passing the four windows. 相似文献
563.
The finite difference method is used to simulate chronoamperometry, linear sweep voltammetry, and cyclic voltammetry at conical electrodes and microelectrodes. Techniques for the numerical simulation of these processes at microdiscs are adapted and extended to accurately model diffusion to the electroactive cone surface. Simulated results are analyzed, and trends are rationalized in terms of the cone apex angle, alpha. The diffusion domain approximation is used to extend the theory to regular and random arrays of conical electrodes. 相似文献
564.
Poly (N-isopropylacrylamide) microgel based assemblies for organic dye removal from water: microgel diameter effects 总被引:1,自引:0,他引:1
Deepika Parasuraman Edmund Leung Michael J. Serpe 《Colloid and polymer science》2012,290(11):1053-1064
Poly (N-isopropylacrylamide)-co-acrylic acid (pNIPAm-co-AAc) microgel based assemblies (aggregates) were synthesized from microgels of various diameters via polymerization of the crosslinker N,N′-methylenebisacrylamide (BIS) in the presence of microgels in solution. We investigated the ability of the respective aggregates to remove the organic, azo dye molecule 4-(2-hydroxy-1-napthylazo) benzenesulfonic acid sodium salt (Orange II) from water at both room and elevated temperatures. The results from the microgel aggregates made from 1.1-μm-diameter [Parasuraman and Serpe. ACS Applied Materials & Interfaces, 2011] microgels were compared to aggregates synthesized from 321-nm and 1.43-μm-diameter microgels. Aggregates made from the same size microgels showed increased uptake efficiency as the concentration of BIS in the aggregates was increased, while for a given BIS concentration, the uptake efficiency increased with increasing microgel size in the aggregate. We attribute this to the “nature” of the aggregates; aggregates have void space between the microgels that can serve as reservoirs for Orange II uptake—the void spaces are hypothesized to increase with larger diameter microgels. By exploiting the thermoresponsive nature of the microgels, and microgel based aggregates, 85.3 % removal efficiencies can be achieved. Finally, all uptake trends for the aggregates, at room temperature, were fit with a Langmuir sorption isotherm model. 相似文献
565.
Lall MS Hoge G Tran TP Kissel W Murphy ST Taylor C Hutchings K Samas B Ellsworth EL Curran T Showalter HD 《The Journal of organic chemistry》2012,77(10):4732-4739
(S)-3-(methylamino)-3-((R)-pyrrolidin-3-yl)propanenitrile (1) is a key intermediate in the preparation of PF-00951966, (1) a fluoroquinolone antibiotic for use against key pathogens causing community-acquired respiratory tract infections including multidrug resistant (MDR) organisms. The current work describes the development of a highly efficient and stereoselective synthesis of 1 in 10 steps with an overall yield of 24% from readily available benzyloxyacetyl chloride. Two key transformations in the synthetic sequence involve (a) catalytic asymmetric hydrogenation with chiral DM-SEGPHOS-Ru(II) complex to afford β-hydroxy amide 11b in good yield (73%) and high stereoselectivity (de 98%, ee >99%) after recrystallization and (b) S(N)2 substitution reaction with methylamine to provide diamine 14 with inversion of configuration at the 1'-position in high yield (80%), after efficient purification using a simple acid/base extraction protocol. 相似文献
566.
567.
Current integer programming solvers fail to decide whether 12 unit cubes can be packed into a 1×1×11 box within an hour using the natural relaxation of Chen/Padberg. We present an alternative relaxation of the problem of packing boxes into a larger box, which makes it possible to solve much larger instances. 相似文献
568.
Singer PM Leu G Fordham EJ Sen PN 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2006,183(2):167-177
Pulsed field gradient NMR flow propagators for water flow in Bentheimer sandstone are measured at low fields (1H resonance 2 MHz), using both unipolar and bipolar variants of the pulsed gradient method. We compare with propagators measured at high fields (1H resonance 85 MHz). We show that (i) measured flow propagators appear to be equivalent, in this rock, and (ii) the lower signal to noise ratio at low fields is not a serious limitation. By comparing different pulse sequences, we study the effects of the internal gradients on the propagator measurement at 2 MHz, which for certain rocks may persist even at low fields. 相似文献
569.
Jacek Blazewicz Edmund K. Burke Marta Kasprzak Alexandr Kovalev Mikhail Y. Kovalyov 《Discrete Applied Mathematics》2009,157(17):3586-3592
In this paper, we analyse the computational complexity of an optimization version of the Simplified Partial Digest Problem (SPDP), which is a mathematical model for DNA mapping based on the results of a simplified partial digest experiment. We prove that recognizing 46.16% of the elements of the DNA map in the error-free simplified partial digest experiment is NP-hard in the strong sense. This implies that the problem of maximizing the number of correct elements of the DNA map in the error-free simplified partial digest experiment is pseudopolynomially non-approximable with the approximation ratio . 相似文献
570.
The acetyl-protected, thiol-terminated ethers AcS(CH(2))(4)O(CH(2))(4)SAc and AcS(CH(2))(2)O(CH(2))(2)O(CH(2))(2)SAc have been synthesised, and a range of related scanning tunnelling microscopy (STM)-based methods have been employed to fabricate and electrically characterise gold | single molecule | gold junctions involving these molecules. The single-molecule conductance values obtained are consistently found to be substantially higher (by a factor of 2-3) than the conductances of analogous alkanedithiols of similar length (HS(CH(2))(9)SH and HS(CH(2))(8)SH, respectively). A rationalisation of these findings is suggested, namely that the lone pair electrons on the oxygen atoms are substantially closer in energy to the Fermi energy of the gold leads than are the occupied and unoccupied states of methylene chains, so that the ether oxygens behave in a manner analogous to 'wells' in a double-tunnelling-barrier system. In agreement with this suggestion, the current-voltage behaviour of the monoether can be fitted using the Simmons approach, and the barrier height is found to be significantly lower than for alkanedithiols of approximately the same length. 相似文献