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131.
New p-benzoquinones were obtained by oxidation of catechin and epicatechin derivatives with the hydrogen peroxide/methyltrioxorhenium catalytic system. Reactions were carried out both in homogeneous and heterogeneous conditions and proceeded with high conversion and moderate yields. Polymer-supported methyltrioxorhenium systems were used as heterogeneous catalysts. After the first oxidation, the catalytic systems can be recovered and reused for five consecutive times without loss of stability and efficiency.  相似文献   
132.
The synthesis of the alkali metal salts of 3,4,5-tris(n-alkan-1-yloxy)benzoic acid [(3,4,5)nG1-CO(2)M, where n is the number of methylenic units in the alkane group for n=12, 14, 16, 18 and M=Li, Na, K, Rb, Cs] is described. The structural analysis of these AB(3) molecules by a combination of methods which includes X-ray diffraction experiments was performed. These experiments have demonstrated that (3,4,5)nG1-CO(2)M self-assemble at low temperatures into supramolecular cylinders and at high temperatures into spheres which subsequently self-organize into two-dimensional c2mm rectangular columnar, p6mm hexagonal columnar, three-dimensional Pm(-)3n and Im(-)3m cubic lattices. In addition a novel unidentified liquid crystalline lattice was also discovered. The dependence between the symmetry of the lattice and the molecular structure of (3,4,5)nG1-CO(2)M was established. (3,4,5)nG1-CO(2)M represents one of the AB(3) minidendrons (i.e., first-generation monodendron attached to the periphery of larger generation dendrons) that is responsible for the control of the three-dimensional structures created from libraries of larger generations of dendrimers. Therefore, the molecular structure-lattice dependence elaborated here will aid the rational design of the three-dimensional shapes from larger generations of supramolecular dendrimers and of their lattices. In addition, the temperature responsive shape change of these supramolecular objects may generate new supramolecular concepts and technological applications.  相似文献   
133.
The imidazo[4,5-d]-1,2,3-triazine and pyrazolo[3,4-d]-1,2,3-triazine analogues of the potent anticonvul-sant purine, BW 78U79 (9-(2-fluorobenzyl)-6-methylamino-9H-purine, 1 ), were synthesized and tested for anticonvulsant activity. The imidazo[4,5-d]-1,2,3-triazines 11–13 were prepared in four steps from 5-aminoimidazole-4-carboxamide (2) and the pyrazolo[3,4-d]-1,2,3-triazines 18–21 were synthesized starting with 5-amino-1-(2-fluorobenzyl)pyrazole-4-carbonitrile (14) . The intermediate 1,2,3-triazin-4-ones 6 and 16 were converted to the 4-substituted targets via the 4-(4-dimethylaminopyridinium) salts 10 and 17 . Imidazotriazine 11 had potent anticonvulsant activity against maximal electroshock-induced seizures, but its propensity to cause emesis precluded further development.  相似文献   
134.
This paper describes a novel polymerization reaction which consists of a sequence of hydroboration of a diolefin with 9-borabicyclo[3.3.1]nonane (9-BBN) followed by the intermolecular cross-coupling of the resulting 1,1′-bis(B-alkanediyl-9-borabicyclo[3.3.1]nonanes with dihaloarenes. The reaction is performed in the presence of dichloro[1,1′-bis(diphenylphosphino)ferrocene] palladium (II) [PdCl2 (dppf)], a base, and a phase transfer catalyst. Both steps are performed in the same reaction flask. Alternatively, this polymerization reaction can be applied to bifunctional monomers containing an olefin and a haloarene group, for example, p-bromostyrene.  相似文献   
135.
Bulk radical copolymerization of methyl acrylate (MeA, M1) with styrene (St, M2) in presence and absence of ZnCl2 as complexing agent was studied. 1H-NMR spectra were used to establish copolymer composition and sequence distribution. The methoxy group signal was observed to be split due to pentads, but the analysis of sequence distribution is possible only at triad level. Both composition and sequence distribution data confirmed that bulk radical copolymerization respects quite well the terminal addition model; the values of r1 = 0.14 ± 0.02 (from composition data) and r1 = 0.25 ± 0.03 (from sequence distribution data) and r2 = 0.83 ± 0.10 (from composition data) were found. The presence of ZnCl2 increases the probability of alternating addition, e.g., for [ZnCl2]/[MeA] = 0.2, r1 = 0.03 ± 0.02 and r2 = 0.17 ± 0.03. The radical copolymer obtained in bulk in the absence of ZnCl2 presents a coisotactic configuration with σ = 0.75 ± 0.03, but the presence of the complexing agent reduces the probability of coisotactic addition, e.g., for [ZnCl2]/[MeA] = 0.2, σ = 0.52 ± 0.03.  相似文献   
136.
A convenient method for the synthesis of 11-[(4-cyano-4′- trans-α-cyanostilbene) oxy]- undecanyl vinyl ether ( 6 ) which is the first member of a new class of mesogenic monomers is described. The polymerization of 6 initiated with CF3SO3H/S (CH3)2 in methylene chloride at 0°C proceeds through a living cationic mechanism leading to polymers with controllable molecular weights and polydispersities narrower than 1.10. The mesomorphic behavior of both 6 and poly( 6 )s with various molecular weights was determined by using a combination of thermal optical polarized microscopy and differential scanning calorimetry. 6 is only crystalline. Poly( 6 )s with degrees of polymerization from 4 to 30 exhibit an enatiotropic smectic A mesophase and side chain crystallization.  相似文献   
137.
The thermal cis–trans isomerization of cis‐transoidal polyphenylacetylene (PPA) synthesized with Noyori's catalyst [Rh(C?CPh)(norbornadiene)(PPh3)2] has been investigated under both ambient and inert atmospheres in solution and in bulk. In all cases, an intramolecular cyclization results in cis–trans isomerization, and subsequent chain cleavage produces 1,3,5‐triphenylbenzene. This reaction is accelerated by the presence of air, particularly when the reaction takes place in solution. Decreases in the cis content and molecular weight show that the intramolecular cyclization process takes place at 23 °C in solution. The mechanism of this reaction is identical to that reported previously for cis‐cisoidal and cis‐transoidal PPA synthesized with Ziegler–Natta catalysts. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3212–3220, 2002  相似文献   
138.
The synthesis of methacrylates and acrylates containing 4-methoxy-4′-hydroxy-α-methylstilbene and 4-hydroxy-4′-methoxy-α-methylstilbene constitutional isomers attached to the polymerizable group through flexible spacers containing 11, 8, 6, 3, and respectively 2 methylenic units is described. The radical copolymerization of a 1/2 or 2/1 mole ratio of the two constitutional isomeric monomers led to thermotropic side-chain liquid crystalline polymers in all cases. The synthesis of copolysiloxanes based on the same constitutional isomeric mesogens as side groups, and flexible spacers containing 11, 8, 6, 5, and respectively 3 methylenic units is also described. All polymers were characterized by differential scanning calorimetry and optical polarization microscopy. The polymers containing 11 methylenic units in the spacer exhibit Sc mesomorphism, while the other polymers are nematic. Copolymethacrylates do not undergo side-chain crystallization. Only the copolyacrylate containing 11 methylenic units in the spacer exhibits side-chain crystallization. All the copolysiloxanes display side-chain crystallization. The number of melting transitions seen for these polymers decreases with increasing spacer length. Copolysiloxanes containing dissimilar spacer length were also prepared. Only the copolymer synthesized with highly dissimilar spacer lengths, i.e., containing 3 and 11 methylenic units, does not undergo side-chain crystallization. These results have demonstrated that while the type of mesophase is dictated only by the spacer length, the degree of decoupling of the motion of the side-groups from the motion of the main chain is strongly dependent on the nature of the polymer backbone. For the same mesogenic unit and spacer length, the thermal stability of the mesophase is also dictated by the nature of the polymer backbone. The use of constitutional isomers of mesogenic units as side groups in liquid crystalline polymers provides at least qualitative information on the degree of decoupling of the side groups from the polymer main chain.  相似文献   
139.
A novel and convenient synthetic method for the preparation of α,ω-bis(2,6-dimethylphenol)–poly(2,6-dimethyl-1,4-phenylene oxide) (PPO-2OH) is presented. It is based on the oxidative copolymerization of 2,6-dimethylphenol (DMP) with 2,2′-di(4-hydroxy-3,5-dimethylphenyl propane) (TMBPA) in a mixture of water–methanol or chlorobenzene–methanol. By using a 4/1 mole ratio of DMP to TMBPA and different solvent mixtures, it was possible to obtain bifunctional PPO-2OHs with number average molecular weights between 1000 and 5000. A phase-transfer-catalyzed etherification of PPO-2OH chain ends with a mixture of m- and p-chloromethylstyrene was used to synthesize α,ω-bis(vinylbenzyl)-poly(2,6-dimethyl-1,4-phenylene oxide)s (PPO-2VBs). The thermal polymerization of the PPO-2VBs was studied by differential scanning calorimetry, and has demonstrated a very high thermal reactivity for this new class of reactive oligomers.  相似文献   
140.
The molecular structure of helical supramolecular dendrimers generated from self-assembling dendrons and dendrimers and from self-organizable dendronized polymers was elucidated for the first time by the simulation of the X-ray diffraction patterns of their oriented fibers. These simulations were based on helical diffraction theory applied to simplified atomic helical models, followed by Cerius2 calculations based on their complete molecular helical structures. Hundreds of samples were screened until a library containing 14 supramolecular dendrimers and dendronized polymers provided a sufficient number of helical features in the X-ray diffraction pattern of their oriented fibers. This combination of techniques provided examples of single-9(2) and -11(3) helices, triple-6(1), -8(1), -9(1), and -12(1) helices, and an octa-32(1) helix that were assembled from crownlike dendrimers, hollow and nonhollow supramolecular crownlike dendrimers, hollow and nonhollow supramolecular disklike dendrimers, and hollow and nonhollow supramolecular and macromolecular helicene-like architectures. The method elaborated here for the determination of the molecular helix structure was transplanted from the field of structural biology and will be applicable to other classes of synthetic helical assemblies. The determination of the molecular structure of helical supramolecular assemblies is expected to provide an additional level of precision in the design of helical functional assemblies resembling those from biological systems.  相似文献   
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