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We investigate the statistical and dimensional properties of uniform star polymers attached by the branching vertex of degreef in a wedge geometry in three dimensions and described by the wedge angles and. We show that the growth constant is equal to
f
, where is the self-avoiding walk limit. Thef and (, ) dependences of the corresponding critical exponent
f
(, ) are studied using Monte Carlo techniques. In the casef=1, our results are compared with existing predictions obtained from series expansion and renormalization group methods. We have also estimated the amplitudes for the mean square radius of gyration and the mean square end-to-end branch length. Our results for the ratio of the mean square radius of gyration of anf-star to that of a linear polymer of the same degree of polymerization attached in a similar wedge, and the analogous ratio for the mean square end-to-end branch length, are consistent with these ratios being lattice-independent quantities. 相似文献
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Smith AB Pitram SM Gaunt MJ Kozmin SA 《Journal of the American Chemical Society》2002,124(49):14516-14517
High chemoselectivity can be achieved in the addition of lithium dithiane anions to vinyl epoxides exploiting the steric nature of the dithiane substituent. Unencumbered dithiane anions afford SN2 adducts, whereas sterically encumbered anions lead primarily to SN2' adducts. Furthermore, the SN2' addition occurs syn to the vinyl epoxide. 相似文献
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Gaunt AJ May I Helliwell M Richardson S 《Journal of the American Chemical Society》2002,124(45):13350-13351
The reaction between PW9O349- and NpO2+ has yielded the first structurally characterized neptunyl(V) polyoxometalate complex, [Na2(NpO2)2(A-PW9O34)2]14-. This complex is isostructural with the uranyl(VI) analogue, and there is also spectroscopic evidence for its existence in solution. The complex is readily extracted into toluene, and this may have significance in the sequestering and/or separation of the neptunyl ion in terms of nuclear waste management. 相似文献
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An experimental study of the thermal decomposition of a β‐hydroxy alkene, 3‐methyl‐3‐buten‐1‐ol, in m‐xylene solution, has been carried out at five different temperatures in the range of 513.15–563.15 K. The temperature dependence of the rate constants for the decomposition of this compound in the corresponding Arrhenius equation is given by ln k (s?1) = (25.65 ± 1.52) ? (17,944 ± 814) (kJ·mol?1)·T?1. A computational study has been carried out at the M05–2X/6–31+G(d,p) level of theory to calculate the rate constants and the activation parameters by the classical transition state theory. There is a good agreement between the experimental and calculated rate constants and activation Gibbs energies. The bonding characteristics of reactant, transition state, and products have been investigated by the natural bond orbital analysis, which provides the natural atomic charges and the Wiberg bond indices. Based on the results obtained, the mechanism proposed is a one‐step process proceeding through a six‐membered cyclic transition state, being a concerted and slightly asynchronous process. The results have been compared with those obtained previously by us (Struct Chem 2013, 24, 1811–1816) for the thermal decomposition of 3‐buten‐1‐ol, in m‐xylene solution. We can conclude that in the compound studied in this work, 3‐methyl‐3‐buten‐1‐ol, the effect of substitution at position 3 by a weakly activating CH3 group is the stabilization of the transition state formed in the reaction and therefore a small increase in the rate of thermal decomposition. 相似文献
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Abstract Due to the wide use of polymers in medicine, researchers are required to solve a very important problem–to understand the interaction between materials of nonphysiological origin and the surrounding biological liquids, and tissues, particularly blood. 相似文献
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Gram‐Scale Enantioselective Formal Synthesis of Morphine through an ortho–para Oxidative Phenolic Coupling Strategy
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Dr. Matthieu Tissot Dr. Robert J. Phipps Dr. Catherine Lucas Dr. Rafael M. Leon Dr. Robert D. M. Pace Dr. Tifelle Ngouansavanh Prof. Matthew J. Gaunt 《Angewandte Chemie (International ed. in English)》2014,53(49):13498-13501
A gram‐scale catalytic enantioselective formal synthesis of morphine is described. The key steps of the synthesis involve an ortho–para oxidative phenolic coupling and a highly diastereoselective “desymmetrization” of the resulting cyclohexadienone that generates three of the four morphinan ring junction stereocenters in one step. The stereochemistry is controlled from a single carbinol center installed through catalytic enantioselective hydrogenation. These transformations enabled the preparation of large quantities of key intermediates and could support a practical and scalable synthesis of morphine and related derivatives. 相似文献
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