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31.
Platinum is known to have a very high chlorine overpotential, about 0.8 V, in fused lithium chloride + potassium chloride eutectic. The high overpotential can be ascribed to the formation of the thick passivation film of platinum chlorides. The high chlorine overpotential was decreased by the addition of alkali metal oxides and a reversible chlorine evolution was revealed in a similar manner as the graphite electrode. The reversible chlorine evolution was ascribed to the formation of the oxide passivation film. The chlorine overpotential at the oxide film was increased stepwise as the applied potential was made more positive. The stepped transitions of the chlorine overpotential was ascribed to the valence change of the oxide film. Platinum shows a typical N-shaped passivation at +0.65 V versus Ag/AgCl(0.1) which has been ascribed to the dissolution of platinum into Pt(II) ions and following formation of the passivation film of supersaturated Pt(II) chloride. Platinum was found to show another passivation phenomenon at high temperatures, above 450°C. The N-shaped current-potential curve was observed at +1.8 V which was far more positive than the potential of the standard chlorine electrode. The dissolution of platinum prior to the passivation was found to occur due to the formation of high valence platinum ions such as Pt6+ and Pt8+. 相似文献
32.
Jeffry D. Madura Yasushi Nakajima Rodney M. Hamilton Andrzej Wierzbicki Arieh Warshel 《Structural chemistry》1996,7(2):131-138
The interactions between biologically important enzymes and drugs are of great interest. In order to address some aspects of these interactions we have initiated a program to investigate enzymedrug interactions. Specifically, the interactions between one of the isozymes of carbonic anhydrase and a family of drugs known as sulfonamides have been studied using computational methods. In particular the electrostatic free energy of binding of carbonic anhydrase II with acetazolamide, methazolamide,p-chlorobenzenesulfonamide,p-aminobenzenesulfonamide and three new compounds (MK1, MK2, and MK3) has been computed using finite-difference Poisson-Boltzmann (FDPB) [1] method and the semimacroscopic version [2, 3] of the protein dipole Langevin dipole (PDLD) method [4]. Both methods, FDPB and PDLD, give similar results for the electrostatic free energy of binding even though different charges and different treatments were used for the protein. The calculated electrostatic binding free energies are in reasonable agreement with the experimental data. The potential and the limitation of electrostatic models for studies of binding energies are discussed. 相似文献
33.
Duanjun Xu Kunio Miki Yasushi Kai Nobutami Kasai Masanori Wada 《Journal of organometallic chemistry》1985,287(2):265-273
The structure of a nickel(II) complex, trans-[Ni(C6Cl5)(PMe2Ph)2{C(OMe)Me}]BF4, containing the simplest alkyl(alkoxy)carbene ligand has been determined by X-ray crystallography (R = 0.091). The geometry around the nickel atom is square-planar. The comparatively short NiC(1) bond length of 1.843(10) Å showed the presence of π-bonding in the nickel-carbene bond. 相似文献
34.
[reaction: see text]. The zirconium-mediated intramolecular ester transfer reaction of N-alkenyl carbamate derivatives proceeded to give alpha-substituted gamma-aminobutyric acid (GABA) derivatives in good to excellent yields. Quenching experiments of the reaction mixture with iodine or O2 indicated the presence of a cyclopropane intermediate. The resulting iodide was converted to 2-substituted pyrrolidine-3-carboxylate and/or alpha-alkylidene-gamma-aminobutyric acid derivatives in a stereospecific manner. 相似文献
35.
Microcolumns with self-assembled particle frits for proteomics 总被引:1,自引:0,他引:1
LC-MS-MS experiments in proteomics are usually performed with packed microcolumns employing frits or outlets smaller than the particle diameter to retain the packing material. We have developed packed microcolumns using self-assembled particles (SAPs) as frits that are smaller than the size of the outlet. A five to one ratio of outlet size to particle diameter appears to be the upper maximum. In these situations the particles assembled into an arch over the outlet like the stones in a stone bridge. When 3 microm particles were packed into a tapered column with an 8 microm outlet, two particles bridged the outlet with 0.3 pl dead volume and perfect success rate. In peptide analysis by LC-MS, the peak width at half height was normally less than 6 s, compared to 12 s without SAPs. The LC-MS-MS system provided 37% sequence coverage (21 matched peptides) for a tryptically-digested sample of 10 fmol bovine serum albumin. We also describe application of the SAP principle to make disposable pipette tip columns with short pieces of fused-silica capillary as the outlet. 相似文献
36.
Jun-Ichiro Makiura Takuma Higo Yutaro Kurosawa Kota Murakami Shuhei Ogo Hideaki Tsuneki Yasushi Hashimoto Yasushi Sato Yasushi Sekine 《Chemical science》2021,12(6):2108
Efficient activation of CO2 at low temperature was achieved by reverse water–gas shift via chemical looping (RWGS-CL) by virtue of fast oxygen ion migration in a Cu–In structured oxide, even at lower temperatures. Results show that a novel Cu–In2O3 structured oxide can show a remarkably higher CO2 splitting rate than ever reported. Various analyses revealed that RWGS-CL on Cu–In2O3 is derived from redox between Cu–In2O3 and Cu–In alloy. Key factors for high CO2 splitting rate were fast migration of oxide ions in the alloy and the preferential oxidation of the interface of alloy–In2O3 in the bulk of the particles. The findings reported herein can open up new avenues to achieve effective CO2 conversion at lower temperatures.Efficient activation of CO2 at low temperature was achieved by reverse water–gas shift via chemical looping (RWGS-CL) by virtue of fast oxygen ion migration in a Cu–In structured oxide, even at lower temperatures. 相似文献
37.
38.
Takashi Mino Kohei Watanabe Takumu Akiyama Yuki Mizutani Kazuki Miura Masatoshi Hashimoto Yasushi Yoshida Masami Sakamoto 《Tetrahedron》2018,74(28):3871-3878
We previously reported the synthesis of BICMAP (1a) via 6-diphenylphosphino-2,3-dihydrobenzofuran as a key intermediate. However, we did not successfully synthesize BICMAP analogues via a similar synthetic route. Herein we report the second-generation synthesis of BICMAP and its derivatives via diethylphosphonate as a key intermediate. 相似文献
39.
Steric Effect of Carboxylate Ligands on Pd‐Catalyzed Intramolecular C(sp2)–H and C(sp3)–H Arylation Reactions 下载免费PDF全文
Yutaka Tanji Naoya Mitsutake Prof. Dr. Tetsuaki Fujihara Prof. Dr. Yasushi Tsuji 《Angewandte Chemie (International ed. in English)》2018,57(32):10314-10317
A bulky carboxylic acid bearing three cyclohexylmethyl substituents at the α‐position, namely, tri(cyclohexylmethyl)acetic acid, is demonstrated to act as an efficient ligand source in Pd‐catalyzed intramolecular C(sp2)?H and C(sp3)?H arylation reactions. The reactions proceed smoothly under mild reaction conditions, even at room temperature due to the steric bulk of the carboxylate ligands, which accelerates the rate‐determining C?H bond activation step in the catalytic cycle. 相似文献
40.
Hiroshi Masai Dr. Jun Terao Dr. Tetsuaki Fujihara Dr. Yasushi Tsuji 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(19):6624-6630
We describe a new concept for rotaxane synthesis through intramolecular slippage using π‐conjugated molecules as rigid axles linked with organic soluble and flexible permethylated α‐cyclodextrins (PM α‐CDs) as macrocycles. Through hydrophilic–hydrophobic interactions and flipping of PM α‐CDs, successful quantitative conversion into rotaxanes was achieved without covalent bond formation. The rotaxanes had high activation barrier for their de‐threading, so that they were kinetically isolated and derivatized even under conditions unfavorable for maintaining the rotaxane structures. 1H NMR spectroscopy experiments clearly revealed that the restricted motion of the linked macrocycle with the rigid axle made it possible to control the kinetic stability by adjusting the length of the rigid axle in the precursor structure rather than the steric bulkiness of the stopper unit. 相似文献