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41.
R-5-Methylcyclohex-2-enone 1 reacts successively with the phenyldimethylsilylzincate reagent and acetaldehyde to give with regiocontrol the aldols 7, dehydration of which creates the E-exocyclic double bond of the alpha,beta-unsaturated ketone 2. Conjugate addition of the ethylcuprate reagent to this compound takes place with high (96:4) selectivity in favour of the R stereoisomer 12, hydrolysis of which gives (2R,3R,5S,2'R)-2-(but-2'-yl)-3-dimethyl(phenyl)silyl-5-methylcyclohexanone 3. The oxime acetate of this ketone undergoes fragmentation in the presence of trimethylsilyl trifluoromethanesulfonate to give 3R,7R,5E-3,7-dimethylnon-5-enonitrile 4, in which an open-chain 1,5-stereochemical relationship is set up with a high level of stereocontrol. A similar sequence adding 4-methylpentylcuprate to the enone 2, and fragmentation gives 3R,7R,5E-3,7,11-trimethyldodec-5-enonitrile 20. Reduction and hydrogenation of this nitrile gives 3R,7R-3,7,11-trimethyldodecanal 22, which can be converted into phytol 25. The ketoaldehyde 29 reacts with samarium iodide to give only the alcohol 30, in which the radical anion has attacked from the top surface just like the cuprate reagents in their reactions with the ketone 2. 相似文献
42.
Yang UK Adams T Alton A Arroyo CG Avvakumov S de Barbaro L de Barbaro P Bazarko AO Bernstein RH Bodek A Bolton T Brau J Buchholz D Budd H Bugel L Conrad J Drucker RB Fleming BT Formaggio JA Frey R Goldman J Goncharov M Harris DA Johnson RA Kim JH King BJ Kinnel T Koutsoliotas S Lamm MJ Marsh W Mason D McFarland KS McNulty C Mishra SR Naples D Nienaber P Romosan A Sakumoto WK Schellman H Sciulli FJ Seligman WG Shaevitz MH Smith WH Spentzouris P Stern EG Suwonjandee N Vaitaitis A Vakili M Yu J 《Physical review letters》2001,86(13):2742-2745
We report on the extraction of the structure functions F2 and DeltaxF(3) = xF(nu)(3)-xF(nu;)(3) from CCFR nu(mu)-Fe and nu;(mu)-Fe differential cross sections. The extraction is performed in a physics model-independent (PMI) way. This first measurement of DeltaxF(3), which is useful in testing models of heavy charm production, is higher than current theoretical predictions. The ratio of the F2 (PMI) values measured in nu(mu) and mu scattering is in agreement (within 5%) with the predictions of next-to-leading-order parton distribution functions using massive charm production schemes, thus resolving the long-standing discrepancy between the two sets of data. 相似文献
43.
Thomas Fleming 《Topology and its Applications》2008,155(12):1297-1305
Link-homotopy has been an active area of research for knot theorists since its introduction by Milnor in the 1950s. We introduce a new equivalence relation on spatial graphs called component-homotopy, which reduces to link-homotopy in the classical case. Unlike previous attempts at generalizing link-homotopy to spatial graphs, our new relation allows analogues of some standard link-homotopy results and invariants.In particular we can define a type of Milnor group for a spatial graph under component-homotopy, and this group determines whether or not the spatial graph is splittable. More surprisingly, we will also show that whether the spatial graph is splittable up to component-homotopy depends only on the link-homotopy class of the links contained within it. Numerical invariants of the relation will also be produced. 相似文献
44.
45.
Esmail Mohamadian Samin Hamidi Fleming Martínez 《Physics and Chemistry of Liquids》2017,55(6):805-816
Experimental solubility of deferiprone (DFP) in N-methyl-2-pyrrolidone (NMP) + ethanol (EtOH) mixtures at 293.2, 298.2, 303.2 and 308.2 K was determined and mathematically represented using various models. The trained versions of the van’t Hoff equation, its combined version with log-linear model, Jouyban–Acree model and a combination of van’t Hoff + Jouyban–Acree model were reported to simulate DFP solubility in the binary mixture compositions at various temperatures. The mean percentage deviation (MPD) was used as an accuracy criterion. The obtained overall MPDs for back-calculated and predicted solubility of DFP in NMP + EtOH mixtures varied from 1.1% to 3.2% and 2.6% to 6.6%, respectively. Some of apparent thermodynamic quantities for the dissolution processes of DFP are also reported. 相似文献
46.
William E. AcreeJr. Abolghasem Jouyban Fleming Martinez 《Journal of solution chemistry》2017,46(3):734-737
Mathematical representations reported by Yu et al. for the CNIBS/R–K model and a hybrid model are carefully examined in regards to the model’s ability to predict the solubility of hexaquocobalt(II) bis(p-toluenesulfonate). The equation coefficients reported by Yu et al. were found to give calculated mole fraction solubilities in ethanol that exceed unity for both models. 相似文献
47.
Güneş Y Polat MF Sahin E Fleming FF Altundas R 《The Journal of organic chemistry》2010,75(21):7092-7098
Quaternary oxonitriles are stereoselectively generated from the union of five-, six-, and seven-membered 2-chloroalkenecarbonitriles with chiral alcohols via a Claisen rearrangement. The strategy rests on a new conjugate addition-elimination of allylic alkoxides to 2-chlorocycloalkenecarbonitriles to afford substituted 2-alkoxyalkenenitriles. Subsequent thermolysis unmasks a cyclic oxonitrile while selectively forming a new quaternary center with enantiomeric ratios typically greater than 9:1. The overall alkylation strategy addresses the challenge of enantioselectively generating hindered, quaternary centers while simultaneously installing ketone, nitrile, and olefin functionalities. 相似文献
48.
49.
The structure of 0.35 monolayers of platinum deposited onto Cu(110) has been investigated using medium energy ion scattering. Quantitative analysis of the data has been performed using the VEGAS routine. It was found that platinum atoms mostly occupy the second layer with a first interlayer distance of d12 = 123 ± 4 pm and a separation of first and third layers of d13= 142? 10+ 4 pm. These represent a contraction of 4% and an expansion of 11% respectively from the ideal termination of the Cu(110) surface. There is clear evidence of the presence of some platinum in the third layer. 相似文献
50.
A new design is presented for Bragg fibers that allows low-loss propagation for linearly polarized light. Predictions based on a simple ray model show that approximately doubling the thickness of the first wall layer results in low losses at TM-like boundaries while keeping TE-like boundary losses manageable. This contrasts sharply with conventional quarter-wave designs that are extremely low loss for TE01 modes but very high loss for linear polarization. We fabricate Bragg fibers based on this design concept in a Si/SiO2 system and verify experimentally that they propagate linearly polarized light with losses less than 6 dB/cm over a 60-nm spectral range. 相似文献