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91.
Development of a molecular recognition ion gating membrane and estimation of its pore size control 总被引:5,自引:0,他引:5
Ito T Hioki T Yamaguchi T Shinbo T Nakao S Kimura S 《Journal of the American Chemical Society》2002,124(26):7840-7846
We have fabricated a molecular recognition ion gating membrane. This synthetic membrane spontaneously opens and closes its pores in response to specific solvated ions. In addition to this switching function, we found that this membrane could control its pore size in response to a known concentration of a specific ion. The membrane was prepared by plasma graft copolymerization, which filled the pores of porous polyethylene film with a copolymer of NIPAM (N-isopropylacrylamide) and BCAm (benzo[18]crown-6-acrylamide). NIPAM is well-known to have an LCST (lower critical solution temperature), at which its volume changes dramatically in water. The crown receptor of the BCAm traps a specific ion, and causes a shift in the LCST. Therefore, selectively responding to either K(+) or Ba(2+), the grafted copolymer swelled and shrank in the pores at a constant temperature between two LCSTs. The solution flux in the absence of Ba(2+) decreased by about 2 orders of magnitude over a solution flux containing Ba(2+). The pore size was estimated by the filtration of aqueous dextran solutions with various solute sizes. This revealed that the membrane changed its pore size between 5 and 27 nm in response to the Ba(2+) concentration changes. No such change was observed for Ca(2+) solutions. Furthermore, this pore size change occurred uniformly in all pores, as a clear cut-off value for a solute size that could pass through pores was always present. This membrane may be useful not only as a molecular recognition ion gate, but also as a device for spontaneously controlling the permeation flux and solute size. 相似文献
92.
Wasaburo Kawai Taichi Ichihashi 《Journal of polymer science. Part A, Polymer chemistry》1974,12(1):201-210
In order to examine effect of the carbonyl group in carbon monoxide–vinyl chloride copolymer, poly(CO–VC), photoirradiation with a high-pressure mercury lamp on the copolymer was carried out. Poly(CO–VC) had a rate of dehydrochlorination three times that of PVC, and the reaction involved a decrease in chlorine content. Also there was a marked change in the ultraviolet spectra of the photoirradiated films. However, no pronounced change of molecular weight was observed, but a change in Rf in TLC was observed clearly. These facts confirmed that photoirradiation of poly(CO–VC) produced a structural change by dehydrochlorination without serious decrease of molecular weight. In addition, photodehydrochlorination of the copolymer or PVC film was followed kinetically, and after ozonolysis of the dehydrochlorinated polymers, the number-average molecular weights were measured. From the results of degree of dehydrochlorination and molecular weight, the number average of conjugated double bonds or carbonyl groups was estimated. A mechanism for dehydrochlorination process by photo-irradiation is suggested. 相似文献
93.
Aika Takeshima Prof. Dr. Taichi Kano 《Angewandte Chemie (International ed. in English)》2023,62(8):e202217496
A novel route to synthesize 1,4-dicarbonyl compounds is described. α,α-Dibromoketones generate zinc enolates through a diethylzinc-mediated halogen-metal exchange and react with α-bromocarbonyl compounds to furnish 1,4-dicarbonyl compounds via a second generation of zinc enolates. This cross-coupling reaction is enabled by the chemoselective formation of zinc enolates from α,α-dibromoketones in the presence of α-bromocarbonyl compounds. Chiral 1,4-dicarbonyl compounds can be obtained via the enantioselective bromination of aldehydes using a chiral secondary amine catalyst and a subsequent cross-coupling reaction between the resulting chiral α-bromoaldehydes and α,α-dibromoacetophenones. 相似文献
94.
Saori Tsuzuki Prof. Dr. Taichi Kano 《Angewandte Chemie (International ed. in English)》2023,62(16):e202300637
Chiral sulfimides, the aza-analogues of sulfoxides, are valuable compounds in organic synthesis and medicinal chemistry. Herein, we report an efficient method for preparing chiral sulfimides from easily available enantioenriched sulfinamides. The key step of this method is a stereospecific oxygen-selective alkylation of enantioenriched sulfinamides, which is accomplished by using isopropyl iodide, K2CO3, and DMPU. The resulting chiral sulfinimidate esters are transformed to chiral sulfimides by the nucleophilic addition of the Grignard reagents under simple conditions. This transformation enables access to the enantioenriched diaryl or dialkyl sulfimides bearing two similar carbon substituents, which are difficult to synthesize by previous methods. 相似文献
95.
Hoshi T Nakazawa T Saitoh I Mori A Suzuki T Sakai J Hagiwara H 《Organic letters》2008,10(10):2063-2066
High activity in the palladium-catalyzed Suzuki-Miyaura reactions of aryl chlorides with arylboronic acids was furnished using biphenylene-substituted di- tert-butylruthenocenylphosphine (R-Phos) as a supporting ligand. Substrate combinations even for the construction of highly hindered tetra- ortho-substituted biaryls can be achieved in good to excellent yields with low catalyst loadings in short reaction times. 相似文献
96.
Masakatsu Matsumoto Masatoshi Tanimura Taichi Akimoto Nobuko Watanabe Hisako K. Ijuin 《Tetrahedron letters》2008,49(26):4170-4173
An aprotic polar solvent such as N-methylpyrrolidone (NMP) promoted the thermal decomposition of bicyclic dioxetane bearing a 4-(benzothiazol-2-yl)-3-hydroxyphenyl moiety 1 without the addition of any base. This solvent-promoted decomposition (SPD) gave light as effectively as the base-induced decomposition (BID) in an aprotic polar solvent. SPD caused intramolecular CT-induced chemiluminescence similar to BID, but, in contrast to BID, SPD proceeded through a pathway with a large negative entropy of activation. Dioxetane 1 was also shown to give light due to excited state intramolecular proton transfer (ESIPT) upon heating in p-xylene. 相似文献
97.
Taichi Kano 《Tetrahedron letters》2008,49(37):5369-5371
A binaphthyl-based amino sulfonamide (S)-2 was applied to the direct asymmetric aminoxylation of aldehydes with nitrosobenzene. The reaction catalyzed by (S)-2 proceeded smoothly to give the aminoxylated product in good yield with excellent enantioselectivity. This method represents a rare example of the highly enantioselective aminoxylation by a non-proline type catalyst with high catalytic performance. 相似文献
98.
A direct asymmetric iodination reaction of aldehydes with NIS was found to be catalyzed by the novel axially chiral bifunctional amino alcohol (S)-1d. This method represents the rare example of the catalytic and highly enantioselective synthesis of optically active alpha-iodoaldehydes. 相似文献
99.
Kusakabe T Kato K Motodate S Takaishi S Akita H 《Chemical & pharmaceutical bulletin》2008,56(10):1436-1437
A total synthesis of (+)-bakkenolide-A was carried out via the key intermediate 4, which was prepared based on an asymmetric cyclization-carbonylation reaction established in our laboratory. Diastereoselective construction of the spirolactone moiety was achieved using Mitsuhashi's protocol as a key step. 相似文献
100.
Masanobu Uchiyama Yasushi Takamatsu Kentaro Ogata Taichi Matsumoto Shiro Jimi Kazuo Tamura Shuuji Hara 《Biomedical chromatography : BMC》2013,27(7):818-820
A practical high‐performance liquid chromatography using a Cosmosil HILIC column and UV detection was developed for determining the concentrations of cytosine arabinoside (Ara‐C) and uracil arabinoside (Ara‐U), which is a major metabolite of Ara‐C, in human plasma. This method was used to determine the plasma concentrations of Ara‐C and Ara‐U in a patient treated with high‐dose Ara‐C therapy for end‐stage renal failure. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献