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31.
Three novel triosmium complexes with unusual coordination characteristics are reported. Treatment of the hydridotriosmium cluster (mu-H)2Os3(CO)10 with CNNPPh3 in CH2Cl2 gave complexes (mu-H)Os3(CO)(10)(mu2-eta2-C(H)NNPPh3) (1) and (mu-H)Os3(CO)10(mu2-eta1-CHPPh3) (2). Complex 1 represents the first example of the existence of a coordinated phosphinazine ligand. An in-situ 1H NMR study showed that the reaction of (mu-H)2Os3(CO)10 with CNNPPh3 produced complex 1 as the initial product in 100% conversion. The latter is not stable in solution and slowly eliminates nitrogen to form an unusual ylide complex 2 in quantitative yield. The thermolysis of 2 in refluxing toluene afforded (mu-H)3Os3(CO)9(mu3-eta1-CCO2CH2Ph) (3) as a colorless compound. Complexes 1-3 were characterized by spectroscopic methods and single-crystal X-ray diffraction analysis. The interesting feature of structure 3 is the presence of a mu3-alkylidyne ligand where the symmetrically triply bridged CCO2CH2Ph fragment lies perpendicular to and above the triosmium triangle. 相似文献
32.
An already well-established recognition motif-namely one in which the NH2+ centers in the rod sections of the dumbbell components of rotaxanes are encircled by macrocyclic polyether components-has been turned simultaneously outside-in and inside-out, a fact that has been proved beyond any doubt by the stoppering of both ends of a [2]pseudorotaxane to give a stable [2]rotaxane. The [2]pseudorotaxane is formed in nitromethane when a benzylic dibromide, obtained after reacting an excess of 1,4-bis(bromomethyl)benzene with hexaethylene glycol, is added to an equimolar amount of a dicationic cyclophane in which two -CH2OCH2- chains link a pair of dibenzylammonium ions through the para positions on their phenyl rings. When the [2]pseudorotaxane is reacted in nitromethane with triphenylphosphine, a [2]rotaxane and the corresponding free dumbbell compound are isolated in 58 and 31% yields, respectively. The structure of the [2]rotaxane is established by using mass spectrometry (FABMS and ESMS) and NMR (1H and 13C) spectroscopy in nitromethane-d3. The [2]rotaxane exhibits quite dramatic changes in the 1H chemical shifts of the signals for its CH2N+ and CH2O protons compared with those in the free dumbbell compound. The 1H NMR spectrum of the [2]pseudorotaxane shows many similar features. Titration experiments with three of the six different CH2O probes give an average Ka value of 2900 +/- 750 M-1 in nitromethane-d3. The new recognition motif for the template-directed synthesis of rotaxanes can now be exploited at both the molecular and macromolecular levels of structure with numerous potential applications in sight. 相似文献
33.
[structure: see text] Post-assembly covalent modification using Wittig chemistry of [2]rotaxane ylides, wherein NH(2)(+) centers in the dumbbell-shaped components are recognized by dibenzo[24]crown-8 (DB24C8) rings, has afforded a [3]catenane and a [3]rotaxane with a precise and synthetically prescribed shortage of DB24C8 rings. The nondegenerate pairs of translational isomers present in both of these interlocked molecular compounds provide the fundamental platform on which to construct sensory devices and nanochemomechanical systems. 相似文献
34.
Ming-Chang P. Yeh Chi-Fen Jou Wei-Tzou Yeh Da-Yu Chiu N. Ravi Kumar Reddy 《Tetrahedron》2005,61(2):493-500
Intramolecular 1,3-dipolar cycloaddition of cyclo-1,3-diene- and -1,3,5-triene-tethered nitrile oxides gave tricyclic isoxazolines as a single stereoisomer in most cases. The relative stereochemistry of tricycle-fused isoxazolines resulting from 1,3-dipolar cycloaddition of cyclo-1,3-diene-tethered nitrile oxides is cis-cis, whereas from cyclohepta-1,3,5-triene-tethered nitrile oxides the cis-trans isomer predominates. 相似文献
35.
Hon Man Lee Chi Ying Lu Chih Yuan Chen Wen Ling Chen Hung Ching Lin Pei Ling Chiu Pi Yun Cheng 《Tetrahedron》2004,60(27):5807-5825
A series of new ethylene-bridged bis(imidazolium) halides with various N-substitutions were synthesized. Complexation of these imidazolium halides with Pd(OAc)2 produced new Pd(II) ethylene-bridged bis(carbene) complexes. Crystallographic analyses of some of the new imidazolium salts and Pd(II) complexes were determined. Applications of these seven-member palladacycles in Suzuki and Heck coupling reactions produced comparable catalytic activities to those of six-member analogs. 相似文献
36.
37.
[reactions: see text] [(Ph3P)CuH]6 effectively catalyzes the hydrostannation of activated alkynes with exclusive regioselectivity for alpha-stannation. Syn hydrostannation is observed exclusively for alkynoates. Anti or syn hydrostannation adducts are obtained as products for alkynone substrates. 相似文献
38.
Ging-ho Hsiue Ying-Ling Liu Yie-Shun Chiu 《Journal of polymer science. Part A, Polymer chemistry》1994,32(11):2155-2159
Novel energetic thermoplastic elastomers (TPEs) based on tetrahydrofuran (THF) and 3,3-bis (azidomethyl) oxetane (BAMO) were prepared in this present study by cationic living polymerization. A bifunctional catalyst, triflic anhydride [(CF3SO2)2)O] was selected to be an initiator for the polymerization THF and BAMO. The resulting polymers were characterized by IR, NMR, and DSC, which demonstrated that triblock copolymers with A-B-A type were formed. The polymers were indicated from thermogravimetric analysis (TGA) to have decomposed at approximately 243°C. The decomposition enthalpies were determined by DSC. These enthalpies were varied with the poly-BAMO contents of the copolymers. The synthesized polymers exhibited relatively good mechanical properties and thermoplastic characteristics at room temperature. © 1994 John Wiley & Sons, Inc. 相似文献
39.
Twenty-two isomers/conformers of C3H6S+√ radical cations have been identified and their heats of formation (ΔHf) at 0 and 298 K have been calculated using the Gaussian-3 (G3) method. Seven of these isomers are known and their ΔHf data are available in the literature for comparison. The least energy isomer is found to be the thioacetone radical cation (4+) with C2v symmetry. In contrast, the least energy C3H6O+√ isomer is the 1-propen-2-ol radical cation. The G3 ΔHf298 of 4+ is calculated to be 859.4 kJ mol−1, ca. 38 kJ mol−1 higher than the literature value, ≤821 kJ mol−1. For allyl mercaptan radical cation (7+), the G3 ΔHf298 is calculated to be 927.8 kJ mol−1, also not in good agreement with the experimental estimate, 956 kJ mol−1. Upon examining the experimental data and carrying out further calculations, it is shown that the G3 ΔHf298 values for 4+ and 7+ should be more reliable than the compiled values. For the five remaining cations with available experimental thermal data, the agreement between the experimental and G3 results ranges from fair to excellent.
Cation CH3CHSCH2+√ (10+) has the least energy among the eleven distonic radical cations identified. Their ΔHf298 values range from 918 to 1151 kJ mol−1. Nevertheless, only one of them, CH2=SCH2CH2+√ (12+), has been observed. Its G3 ΔHf298 value is 980.9 kJ mol−1, in fair agreement with the experimental result, 990 kJ mol−1.
A couple of reactions involving C3H6S+√ isomers CH2=SCH2CH2+√ (12+) and trimethylene sulfide radical cation (13+) have also been studied with the G3 method and the results are consistent with experimental findings. 相似文献
40.
In this study, microemulsion electrokinetic chromatography (MEEKC) and micellar electrokinetic chromatography (MEKC) were compared for their abilities to separate and detect thirteen phenolic compounds (syringic acid, p-coumaric acid, vanillic acid, caffeic acid, gallic acid, 3,4-dihydroxybenzoic acid, 4-hydroxybenzoic acid, (+)-catechin, (-)-epigallocatechin, (-)-epicatechin gallate, (-)-epigallocatechin gallate, (-)-epicatechin, and (-)-gallocatechin), and two other ingredients (caffeine and theophylline) in teas and grapes. Separation of phenolic compounds was improved by changing the SDS concentration for MEEKC, but the SDS concentration rarely affected the resolution for MEKC. Organic modifier (acetonitrile or methanol) was found to markedly influence the resolution and selectivity for both MEEKC and MEKC systems. In addition, a higher voltage and a higher column temperature improved the separation efficiency without any noticeable reduction in resolution for MEEKC whereas they caused a poor resolution for the MEKC system. Although separations with baseline resolution were achieved by the optimized MEEKC and MEKC methods, the separation selectivity resulting from the proposed MEEKC method was completely different from that of MEKC. 相似文献