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961.
Norifusa Satoh Takeshi Watanabe Yoshinori Iketaki Takashige Omatsu Masaaki Fujii Kimihisa Yamamoto 《先进技术聚合物》2004,15(4):159-163
The phenylazomethine dendrimer (DPA) is associated with Rhodamine 6G in chloroform, which results in the chemical shift attributed to the aromatic protons of phenylazomethine being moved upfield in the 1H‐NMR spectrum by increasing the Rhodamine 6G. The shift is saturated at the ratio of 1 : 1. On the basis of the NMR analysis, the association constant K of phenylazomethine with Rhodamine 6G was determined to be 1.4 × 104 (l/mol) in CDCl3 at 20°C. The association is also confirmed by UV‐vis spectroscopy, in which the absorption around 450 and 527 nm changes during the addition of Rhodamine 6G. The fluorescence intensity of the 1 : 1 complex of Rhodamine 6G and DPA G4 is stronger than that of the solution dissolved only in Rhodamine 6G at greater than 1 mM though it is generally known that the intermolecular interaction quenches the dye fluorescence in a concentrated solution. The association of DPA G4 with Rhodamine 6G suppresses the quenching at higher concentrations. Homogenous nano‐dots were observed on mica by casting the DPA G4 complex with Rhodamine 6G, in which the height and average area were 1.5–3 nm and 1.6 × 103 nm2 (the standard deviation σ = 3.7 nm2), respectively. Copyright © 2004 John Wiley & Sons, Ltd. 相似文献
962.
Treatment of 1-chlorovinyl p-tolyl sulfoxides, which were synthesized from ketones and chloromethyl p-tolyl sulfoxide, with ethylmagnesium chloride or isopropylmagnesium chloride at below -78 degrees C gave magnesium alkylidene carbenoids in about 90% yields. The reaction of the generated carbenoids with lithium alpha-sulfonyl carbanions was found to afford tri- and tetra-substituted allenes. Both cyclic ketones and acyclic ketones were useful in this procedure. However, the 1-chlorovinyl p-tolyl sulfoxides derived from aldehydes gave only rearranged products, acetylenes, under the reaction conditions. The magnesium alkylidene carbenoid derived from an optically active 1-chlorovinyl p-tolyl sulfoxide was treated with lithium alpha-carbanion of 1-naphthyl phenyl sulfone; however, the obtained allene was found to be racemic. The mechanism of this reaction is also discussed. 相似文献
963.
Kobayashi S Kobayashi J Ishitani H Ueno M Ishiani H 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(18):4185-4190
Optically active anti-alpha-methyl-beta-amino acid derivatives have been prepared based on catalytic enantioselective addition of propionate units to simple and inert imines using a chiral zirconium complex. High reactivity and selectivity with wide substrate scope were attained by using a new chiral ligand, (R)-6,6'-bis(pentafluoroethyl)-1,1'-bi-2-naphthol ((R)-6,6'-C(2)F(5)BINOL). The reactions using geometrically isomeric ketene silyl acetals gave excellent anti-selectivity with high enantiomeric excess in both cases. Synthetic utility of this reaction has been demonstrated by the preparation of various anti-alpha-methyl-beta-amino acid and trans-3,4-disubstituted beta-lactam derivatives. 相似文献
964.
Changqi Sun Yoh Sano Hiroshi Kashiwagi Masaharu Ueno 《Colloid and polymer science》2002,280(10):900-907
The aggregate structures formed during vesicle solubilization by sodium cholate, and their properties, were characterized by static laser light scattering (SLS) and electrophoretic light scattering (ELS) methods. The change in dissymmetry value Z45 was observed by examining the regions of vesicles and micelles. The angular light scattering intensity data could be fitted with a modified shell model for the vesicles and a hollow cylinder model for the mixed micelles. In the case of the vesicles, the scattering curves were fitted with a spherical shell model by introducing the interparticle scattering factor S(q) and taking into account the intervesicle positional correlations, which is a function of the fractal dimension (D) and the interparticle correlation length (L). On the basis of the physical meanings of the fractal dimension and interparticle correlation length, the molecular packings of the membrane and the repulsive interaction between the vesicles were analyzed. Furthermore, using electrophoretic light scattering (ELS) the zeta potentials on the mixed vesicles were found to increase with the molar ratio (Re) of sodium cholate to egg yolk phosphatidylcholine (EggPC) in the membrane. It is suggested that the electrostatic properties of the vesicles result in repulsive interaction which is responsible for no fusion of the mixed vesicles. In addition, in the transition from vesicles to micelles, a cylinder-like micelle appeared as an intermediate structure. 相似文献
965.
Shintaro Mitsunaga Tohru Ohbayashi Shimpei Sugiyama Takahito Saitou Makoto Tadokoro Tsuyoshi Satoh 《Tetrahedron: Asymmetry》2009,20(14):1697-1708
The synthesis of pipecolic acid and homopipecolic acid derivatives was developed from ω-(2-aminophenyl)-1-chloroalkyl p-tolyl sulfoxides by treatment with i-PrMgCl. An intramolecular nucleophilic substitution reaction of a magnesium carbenoid with an N-magnesio arylamine is the key step of this reaction. Proline and pipecolic acid derivatives were also synthesized from ω-(arylamino)-1-chloroalkyl p-tolyl sulfoxides by the same chemistry. Starting from enantiomerically pure (1S,RS)-1-chloro-3-[2-(N-methylamino)phenyl]propyl p-tolyl sulfoxide, enantiomerically pure (R)-pipecolic acid derivative was obtained. The intramolecular nucleophilic substitution reaction of the magnesium carbenoid with N-magnesio arylamine was proven to take place with inversion of the carbenoid carbon. The stereochemistry of these reactions is also discussed. 相似文献
966.
Keiji Yashio Kentaro Yamaguchi Masaharu Nakamura Tsuneo Imamoto 《Journal of organometallic chemistry》2009,694(1):97-143
The treatment of optically P-chiral tetraphosphine, (3S,6R,9R,12S)-6,9-di-tert-butyl-2,2,3,12,13,13-hexamethyl-3,6,9,12-tetraphosphatetradecane (1), with rhodium(I), palladium(II), and ruthenium(II) complex precursors led to the selective formation of mono-, di-, or trinuclear homo- or heterometallic complexes, [Rh(1)]SbF6 (4), [{Rh(nbd)}2(1)](SbF6)2 (3), [{Pd(η3-allyl)}2(1)](SbF6)2 (5), [{RuCl(η5-C5(CH3)5)}2(1)] (6), and [{RuCl2(η6-benzene)}2(PdCl2)(1)] (8). These complexes were characterized by NMR and X-ray crystallographic analysis. 相似文献
967.
Kotaro Satoh Masami Kamigaito Mitsuo Sawamoto 《Journal of polymer science. Part A, Polymer chemistry》2000,38(15):2728-2733
Aqueous sulfonic acids (HOSO2R; R = CH3, Ph‐p‐CH3, and Ph‐p‐NO2), coupled with a water‐tolerant Lewis acid, ytterbium triflate [Yb(OTf)3; OTf = OSO2CF3], initiate the cationic suspension polymerization of p‐methoxystyrene (pMOS) in heterogeneous aqueous media. They induce controlled polymerization of pMOS at 30 °C, and the molecular weights of the polymers (weight‐average molecular weight/number‐average molecular weight ∼ 1.7) increase with conversion. These suspension polymerizations are initiated by the entry of sulfonic acid from the aqueous phase into the organic phase and proceed via reversible activation of the sulfonyl terminus by the Lewis acid. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2728–2733, 2000 相似文献
968.
Osamu Kikuchi Toshio Watanabe Yusuke Satoh Yuichi Inadomi 《Journal of Molecular Structure》2000,507(1-3):53-62
Ab initio MO GB theory which includes the continuum model of solvent effect using generalized Born formula has been applied to the dimerization reaction of HCN in aqueous solution which is the starting step in prebiotic synthesis of purine precursors from aqueous hydrogen cyanide. Three steps considered were: (i) the reaction of HCN and H2O to produce the CN− anion, (ii) the reaction of CN− with HCN to give the NC–CH=N− anion, and (iii) the addition of a proton to the anion to give iminoacetonitrile. The formation of CN− ion from HCN in aqueous solution requires 15.1 kcal/mol (the experimental value estimated from the dissociation constant of HCN in water is 14.8 kcal/mol). The reaction of CN− with HCN requires the activation energy of 32.2 kcal/mol (MP2/6-31++G**//HF/6-31++G**) to give the dimer. This barrier height is reduced to 26.1 kcal/mol when HCN is associated with H3O+. In the presence of NH3 in aqueous solution, CN− is produced easily by the reaction of HCN and NH3 with a low activation energy of 4.3 kcal/mol. It was shown that the formation of CN− becomes easier in ammoniacal solution, and the dimerization occurs efficiently in aqueous solutions which contain NH3. 相似文献
969.
Two efficient and practical methods of synthesis of the C-10 substituent of DV-7751 (1), a novel quinolone carboxylic acid, were established. The first method utilizes an optical resolution of racemic 8-amino-6-benzyl-6-azaspiro[3.4]octane (13), while the second employs an enantioselective microbial reduction of 6-benzyl-5,8-dioxo-6-azaspiro[3.4]octane (8b). The enantiomeric excess of (S)-8-amino-6-benzyl-6-azaspiro[3.4]octane (11) with each method of synthesis is greater than 96%. 相似文献
970.
1,1-Disubstituted 3-aryl-2-propyn-1-ols undergo regio- and stereoselective cross-coupling on treatment with bis(trimethylsilyl)acetylene in the presence of a rhodium catalyst via cleavage of C(sp)-C(sp3) and C(sp)-Si bonds to produce the corresponding 2-hydroxymethyl-(E)-enynes. The subsequent desilylative Sonogashira coupling followed by base-promoted cyclization affords fluorescent dihydrofuran derivatives. 相似文献