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排序方式: 共有72条查询结果,搜索用时 31 毫秒
1.
The photochemistry of 13 4,4-diphenylcyclohexenones, substituted at carbon-6, was investigated in solution and in the crystalline state. The stereoselectivity was of particular interest. In the solution photochemistry of C-6 monosubstituted enones in benzene, there was a unique preference for migration of the cis-phenyl group with formation of bicyclo[3.1.0]hexanone photoproducts, with the original 6-substituent having an endo configuration at carbon-3 of the product. In methanol the reaction was diverted to afford 3,4-diphenylcyclohex-2-enes understood as arising from a hydrogen-bonded zwitterionic intermediate. The solid-state photochemistry was also investigated. There was a dramatic absence of the 3,4-diphenylcyclohex-2-ene products in accord with the absence of the hydrogen bonding encountered in methanol. Further, the solid-state reactivity correlated with a vector analysis using X-ray atomic coordinates. This established that the migrating phenyl group required an orientation facing the enone beta-carbon. While the interesting preference for the cis-endo migration was not intuitively predicted, ab initio computations on the alternative phenyl-bridged triplet intermediates did lead to an understanding of the selectivity. 相似文献
2.
Origins of enantioselectivity in reductions of ketones on cinchona alkaloid modified platinum 总被引:2,自引:0,他引:2
A model to explain the stereoselectivities of reductions of activated ketones on cinchona alkaloid modified platinum is proposed and is supported by calculations by density functional and force field methods. The model involves nucleophilic catalysis by the cinchona alkaloid. The zwitterionic adduct between a cinchona alkaloid and ketone is adsorbed on Pt through the quinoline ring and two heteroatoms and is subsequently reduced with inversion. The model rationalizes the observed stereoselectivities for hydrogenation of carbonyl compounds. 相似文献
3.
Zauresh S. Nurkeeva Al-Sayed Abdel Aal Vitaliy V. Khutoryanskiy Grigoriy A. Mun Aida G. Beksyrgaeva 《Radiation Physics and Chemistry》2003,67(6):717-722
Gamma-radiation grafting of vinyl ether of monoethanolamine and vinyl ether of ethyleneglycol (VEEG) on polyethylene films has been studied from binary monomer mixtures. The effect of co-monomer composition and total exposure radiation dose on the grafting process is investigated. A combination of potentiometric and gravimetric techniques is applied to determine the grafting degree of each monomer in the final graft copolymer. The presence of more active monomer VEEG in the mixture was found to enhance the grafting of both monomers because the increasing of copolymerization rate which in turn increases the total grafting degree. The modification of the hydrophilic properties of the graft copolymer is studied by examining the grafted films for water- and copper (II) ions uptake. 相似文献
4.
A facile synthetic protocol for the synthesis of 2-aryl-1,3-benzothiazoles and 1,3-benzoxazoles has been demonstrated using ZnO nanoparticles as a mild and efficient heterogeneous catalyst. The reactions using ZnO nanoparticles were very fast (<8 min) and provided excellent yields (>90%) of the products. The catalyst was recycled and reused up to eight times without significant loss of catalytic activity. The potential application of 2-(4-hydroxyphenyl)-1,3-benzothiazole as new acid–base indicator has also been demonstrated in this Letter. 相似文献
5.
Tamara Borisova Sergey Fridrikh Yuli Gotlib Grigoriy Medvedev Natalja Nikonorova Sergey Skorokhodov Vjacheslav Zuev 《Macromolecular Symposia》1993,72(1):67-80
A series of thermotropic main chain polymers with extended dimethylsiloxane segments was investigated. The study of dielectric properties of polymers revealed the relationship between their ability to form a mesophase and their molecular mobility. The peculiar behaviour of dielectric α-relaxation parameters during the transition from mesomorphic to isotropic members of this polymeric series was shown. The theoretical approaches were developed for understanding macrochain dynamics of liquid crystalline polymers. The theoretical and experimental results are in good agreement. 相似文献
6.
The method of projections onto convex sets (POCS) is used to calculate the adsorption-energy distribution function from the adsorption integral (using a modified Langmuir local isotherm) for energetically heterogeneous surfaces. The POCS method, originally developed in the 1960s, has been successfully applied for many years to estimation problems, mainly in the fields of image processing, signal recovery, and optics. It allows one to incorporate into an iteration scheme available information about the experimental data and the measurement error as well as a priori constraints (such as nonnegativity) based on physical reasoning. It is important to note that the POCS method does not lead to a unique "optimum" solution. Rather, a feasible solution that is consistent with all imposed contraints is found within a "solution space". The "size" of this solution space depends on how large the measurement errors are; it also depends on the accuracy of the error statistics and the number and significance of a priori constraints used. In several examples, the POCS method is used to recover energy distributions from simulated adsorption data containing normally distributed errors. The excellent recoveries obtained demonstrate the value of the POCS method as a robust and reliable tool for adsorption-integral inversions. Copyright 2001 Academic Press. 相似文献
7.
Subhash Banerjee Hari KhatriVagulejan Balasanthiran Ranjit T. Koodali Grigoriy Sereda 《Tetrahedron》2011,67(32):5717-5724
Pd-MCM-48 has been employed as a heterogeneous catalyst for the synthesis of substituted acetylenes via Sonogashira reactions under copper and amine-free reaction conditions. In addition, the catalyst exhibited excellent regioselectivity for primary alcohols towards C-O coupling leading to formation of alkyl-aryl ethers in high yields. A green procedure for the stereoselective synthesis of 2-alkene-4-ynoates and nitriles from the reactions of vic-(E)-diiodoalkenes with activated alkenes has also been demonstrated using Pd-MCM-48 catalyst. The catalyst was easily recovered from the reaction mixture by filtration and reused for at least six times with minimal loss of activity. 相似文献
8.
Alexey A. Kostenko Grigoriy I. Khlopov 《International Journal of Infrared and Millimeter Waves》1996,17(10):1593-1605
Main features of the development of quasi-optical ferrite devices, using Faraday effect, are considered. Properties of a polarizing divider and a ferrite rotator of a polarization plane are analysed with standpoint of minimum losses. A matching method, based on an utilization of the rotator element in a form of the multilayers ferrite structure, which can be adjusted independently for right-handed and left-handed cyrcularly polarized waves, is suggested. It is shown, that this method allows to obtain a total matching in a quasi-optical transmission line. Results of an investigation of quasi-optical ferrite devices for the oversized round waveguide withH
11 mode are presented. 相似文献
9.
Tasić U Alexeev Y Vayner G Crawford TD Windus TL Hase WL 《Physical chemistry chemical physics : PCCP》2006,8(40):4678-4684
Ab initio calculations at the CCSD(T)/aug-cc-pVTZ level of theory were used to characterize the Ar-CH(3)OH intermolecular potential energy surface (PES). Potential energy curves were calculated for four different Ar + CH(3)OH orientations and used to derive an analytic function for the intermolecular PES. A sum of Ar-C, Ar-O, Ar-H(C), and Ar-H(O) two-body potentials gives an excellent fit to these potential energy curves up to 100 kcal mol(-1), and adding an additional r(-n) term to the Buckingham two-body potential results in only a minor improvement in the fit. Three Ar-CH(3)OH van der Waals minima were found from the CCSD(T)/aug-cc-pVTZ//MP2/aug-cc-pVTZ calculations. The structure of the global minimum is in overall good agreement with experiment (X.-C. Tan, L. Sun and R. L. Kuczkowski, J. Mol. Spectrosc., 1995, 171, 248). It is T-shaped with the hydroxyl H-atom syn with respect to Ar. Extrapolated to the complete basis set (CBS) limit, the global minimum has a well depth of 0.72 kcal mol(-1) with basis set superposition error (BSSE) correction. The aug-cc-pVTZ basis set gives a well depth only 0.10 kcal mol(-1) smaller than this value. The well depths of the other two minima are within 0.16 kcal mol(-1) of the global minimum. The analytic Ar-CH(3)OH intermolecular potential also identifies these three minima as the only van der Waals minima and the structures predicted by the analytic potential are similar to the ab initio structures. The analytic potential identifies the same global minimum and the predicted well depths for the minima are within 0.05 kcal mol(-1) of the ab initio values. Combining this Ar-CH(3)OH intermolecular potential with a potential for a OH-terminated alkylthiolate self-assembled monolayer surface (i.e., HO-SAM) provides a potential to model Ar + HO-SAM collisions. 相似文献
10.
Zhunuspayev DE Mun GA Hole P Khutoryanskiy VV 《Langmuir : the ACS journal of surfaces and colloids》2008,24(23):13742-13747
The formation of hydrogen-bonded interpolymer complexes between poly(acrylic acid) and poly(N-vinyl pyrrolidone) as well as amphiphilic copolymers of N-vinyl pyrrolidone with vinyl propyl ether has been studied in aqueous and organic solutions. It was demonstrated that introduction of vinyl propyl ether units into the macromolecules of the nonionic polymer enhances their ability to form complexes in aqueous solutions due to more significant contribution of hydrophobic effects. The complexation was found to be a multistage process that involves the formation of primary polycomplex particles, which further aggregate to form spherical nanoparticles. Depending on the environmental factors (pH, solvent nature), these nanoparticles may either form stable colloidal solutions or undergo further aggregation, resulting in precipitation of interpolymer complexes. In organic solvents, the intensity of complex formation increases in the following order: methanol < ethanol < isopropanol < dioxane. The multilayered coatings were developed using layer-by-layer deposition of interpolymer complexes on glass surfaces. It was demonstrated that the solvent nature affects the efficiency of coating deposition. 相似文献