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51.
Highly fluorescent polymer particles were prepared with Eu beta-diketonates complex as a fluorophore by miniemulsion polymerization technique. Eu beta-diketonates complex has a long decay time, a large Stokes shift, and very narrow emission bands in comparison with other organic fluorescent compounds. Aqueous miniemulsion was prepared by mixing monomer, crosslinker, hydrophobe, and Eu beta-diketonates complex and then putting the mixture into an aqueous solution of surfactant, followed by ultrasonication. An aqueous solution of initiator was added to the miniemulsion to obtain fluorescent polymer particles, which were monodispersed without aggregation. Particle size was decreased to deca-nano scale by increasing the amount of surfactant. Fluorescent intensity was increased by using Eu beta-complex coordinated with additional ligand. Further fluorescence quantum yields and fluorescent properties in the presence of DNA were investigated to the confirm superiority of Eu beta-diketonates complexes in polymer particles. 相似文献
52.
The (15)N-labeled diammine(mu-oxo)ruthenium complex cis,cis-[(bpy)(2)(H(3)(15)N)Ru(III)ORu(III)((15)NH(3))(bpy)(2)](4+) ((2-(15)N)(4+)) was synthesized from cis,cis-[(bpy)(2)(H(2)O)Ru(III)ORu(III)(H(2)O)(bpy)(2)](4+) by using ((15)NH(4))(2)SO(4) and isolated as its perchlorate salt in 17% yield. A 1:1 mixture of (2-(15)N)(4+) and nonlabeled cis,cis-[(bpy)(2)(H(3)(14)N)Ru(III)ORu(III)((14)NH(3))(bpy)(2)](4+) were electrochemically oxidized in aqueous solution. The gaseous products (14)N(2) and (15)N(2) were formed in equimolar amounts with only a small amount of (14)N(15)N detected. This demonstrates that dinitrogen formation by oxidation of the diammine complex proceeds by intramolecular N---N coupling. 相似文献
53.
Volume changes accompanying the protonation of mono-, di- and poly-carboxylates in water were measured at 25° using the circulation dilatometer. The carboxylates include alkali metal and tetra-alkylammonium (TAA) salts of acetic, pivalic, glutaric acid and samples of poly(methacrylic acid) (PMA) having various molecular weights and degrees of stereoregularity. It was found that TAA counter-cation exerts specific influence on the differential molar volume change on protonation of the pivalate and PMA in contrast to the absence of such specificity in the corresponding alkali metal salts. These results were interpreted by the proposed association of the hydrophobic ammonium cation with the carboxylate anions. Volume contraction is accompanied by the association. It was also proposed, on the basis of these findings, that alkali metal counter-ion is not likely to be ‘site bound’ by the respective charges of PMA. PMA configuration has a minor effect on the volume change. 相似文献
54.
Jungui DaiShujun Zhang Jun-ichi SakaiJiao Bai Yoshiki OkuMasayoshi Ando 《Tetrahedron letters》2003,44(5):1091-1094
Three C-14 oxygenated taxanes, 2α,5α,10β,14β-tetraacetoxytaxa-4(20),11-diene (1), 2α,5α,10β-triacetoxy-14β-(2-methylbutyryloxy)taxa-4(20),11-diene (2), and yunanaxane (3), major products of callus cultures of Taxus spp., were regio- and stereoselectively hydroxylated at the 7β position by a fungus, Absidia coerulea IFO 4011. Intriguingly, when 1 was co-administered with β-cyclodextrin and incubated with the fungus cell cultures, three other compounds 5α,9α,10β,13α-tetraacetoxytaxa-4(20),11-dien-14β-ol (7), 5α,9α,10β,13α-tetraacetoxytaxa-4(20),11-dien-1β-ol (8) and 5α,9α,10β,13α-tetraacetoxy-11(15→1) abeotaxa-4(20),11-dien-15-ol (9) were obtained. 相似文献
55.
Yoshihiko Ohishi Tomonori Kawabata Tetsuya Shishido Ken Takaki Qinghong Zhang Ye Wang Katsuomi Takehira 《Journal of molecular catalysis. A, Chemical》2005,230(1-2):49-58
M-MCM-41 catalysts (M: V, Cr, Fe, and Ga) prepared by direct hydrothermal synthesis (DHT) have been tested for dehydrogenation of ethylbenzene with CO2. The synthesized materials were characterized by X-ray diffraction (XRD), N2 adsorption (77 K), and diffuse reflectance UV–vis spectroscopic measurements. Cr-MCM-41 showed the highest activity among M-MCM-41 catalysts tested, resulting in the production of styrene with the conversion of 65% and the selectivity above 90%. The rate of styrene formation increased with increasing Cr loading up to 1.7 wt.%. It is suggested that Cr(VI)O4 in tetrahedral coordination is formed as an active monochromate species and reduced to Cr(III)O6 in octahedral coordination as a less active polychromate species during the reaction. Deactivated catalyst was regenerated by a treatment with gaseous oxygen or CO2, during which redistribution as well as reoxidation of polymeric Cr(III)O6 octahedra to monomeric Cr(VI)O4 tetrahedra was observed. The rate of CO formation increased together with that of styrene formation, while the rate of H2 formation decreased, with increasing partial pressure of CO2. It was confirmed that reverse water-gas shift reaction took place over Cr-MCM-41 by a separate experiment. The rate of CO formation during the dehydrogenation of ethylbenzene with CO2 over Cr-MCM-41 was well accounted for by assuming parallel occurrence of two reactions, i.e., direct oxidative dehydrogenation of ethylbenzene with CO2 and simple dehydrogenation of ethylbenzene thermodynamically assisted by reverse water-gas shift reaction. 相似文献
56.
Yoshihiko Ito Yoshinori Inubushi Toru Sugaya Takeo Saegusa 《Journal of organometallic chemistry》1977,137(1):1-9
Reaction of carboxamides with Cu2O in the presence of t-butyl isocyanide gave new chelated copper(I) complexes, which probably are formed by the insertion of t-butyl isocyanide into the coppernitrogen bond of copper(I) amide isonitrile complexes, which were initially produced from the carboxamides and Cu2Ot-butyl isocyanide complex. The same chelated copper(I) complexes were prepared more readily by the reaction of the corresponding N-trimethylsilyl-carboxamides with Cu2Ot-butyl isocyanide complex. Reactions of the copper(I) complexes thus obtained with alkylating agents, such as alkyl halides, alkyl tosylates and triethyloxonium tetrafluoroborate, also were described. 相似文献
57.
Suginome M Ohmura T Miyake Y Mitani S Ito Y Murakami M 《Journal of the American Chemical Society》2003,125(37):11174-11175
Enantioenriched beta-borylallylsilanes were synthesized by palladium-catalyzed enantioface-selective addition of the silicon-boron bond to terminal allenes using a palladium catalyst possessing a chiral monodentate phosphine ligand. Use of a silylborane bearing a chiral auxiliary on the boron atom was beneficial to gain enantioface selectivities as high as 96% de. 相似文献
58.
Ando K Tsuji E Ando Y Kunitomo J Kobayashi R Yokomizo T Shimizu T Yamashita M Ohta S Nabe T Kohno S Ohishi Y 《Organic & biomolecular chemistry》2005,3(11):2129-2139
Variable benzo[b]furan derivatives having (E)- and (Z)-2-alkylcarbamoyl-1-methylvinyl groups at the 2-, 4- and 5-positions and a carboxylpropoxy or (1-phenyl)ethoxy group at the 7-position were prepared to find novel and selective leukotriene B4(LTB4) receptor antagonists. (E)-2-(2-diethylcarbamoyl-1-methylvinyl)-7-(1-phenylethoxy)benzo[b]furan (4v) showed selective inhibition to the human BLT2 receptor (hBLT2). On the other hand, (E)-2-acetyl-4-(2-diethylcarbamoyl-1-methylvinyl)-7-(1-phenylethoxy)benzo[b]furan (7v) inhibited both human BLT(1) receptor (hBLT1) and hBLT2. The (E)-2-(2-diethylcarbamoyl-1-methylvinyl) group lay on approximately the same plane as the benzo[b]furan ring, whereas the (E)-4-(2-diethylcarbamoyl-1-methylvinyl) group had the torsion angle (45.7 degree) from the benzo[b]furan ring plane. However, the (Z)-(2-alkylcarbamoyl-1-methylvinyl)benzo[b]furans were inactive. The inhibitory activity depended on the conformation of the 2-diethylcarbamoyl-1-methylvinyl group. 相似文献
59.
Photosensitized oxygenation of diethyl sulfide in the presence of α-keto carboxylic acids caused oxidative decarboxylation of the acids by persulfoxide and gave carboxylic acids, carbon dioxide, diethyl sulfoxide and diethyl sulfone. 相似文献
60.
Photooxygenation of 1,1,3,3-tetramethyl-2-indanone triphenyl-phosphazine afforded, in addition to the parent indanone and triphenylphosphine oxide, 2,2,5,5-tetramethyl-3,4-benzo-3-penten-5-olide from a carbonyl oxide intermediate and also gave light emission. 相似文献