全文获取类型
收费全文 | 821篇 |
免费 | 12篇 |
国内免费 | 1篇 |
专业分类
化学 | 653篇 |
晶体学 | 15篇 |
力学 | 2篇 |
数学 | 58篇 |
物理学 | 106篇 |
出版年
2021年 | 5篇 |
2019年 | 9篇 |
2016年 | 9篇 |
2015年 | 10篇 |
2014年 | 7篇 |
2013年 | 60篇 |
2012年 | 25篇 |
2011年 | 39篇 |
2010年 | 16篇 |
2009年 | 27篇 |
2008年 | 43篇 |
2007年 | 32篇 |
2006年 | 27篇 |
2005年 | 42篇 |
2004年 | 29篇 |
2003年 | 41篇 |
2002年 | 48篇 |
2001年 | 7篇 |
2000年 | 10篇 |
1999年 | 11篇 |
1998年 | 14篇 |
1997年 | 7篇 |
1996年 | 15篇 |
1995年 | 4篇 |
1994年 | 5篇 |
1993年 | 4篇 |
1992年 | 6篇 |
1991年 | 7篇 |
1990年 | 5篇 |
1989年 | 8篇 |
1988年 | 6篇 |
1987年 | 6篇 |
1986年 | 4篇 |
1985年 | 18篇 |
1984年 | 18篇 |
1983年 | 11篇 |
1982年 | 18篇 |
1981年 | 17篇 |
1980年 | 27篇 |
1979年 | 23篇 |
1978年 | 21篇 |
1977年 | 23篇 |
1976年 | 6篇 |
1975年 | 14篇 |
1974年 | 6篇 |
1973年 | 9篇 |
1972年 | 3篇 |
1971年 | 3篇 |
1960年 | 2篇 |
1958年 | 3篇 |
排序方式: 共有834条查询结果,搜索用时 437 毫秒
31.
32.
Kobayashi J Sekiguchi M Shimamoto S Shigemori H Ishiyama H Ohsaki A 《The Journal of organic chemistry》2002,67(18):6449-6455
Three novel quaternary indole alkaloids with an unprecedented 1-azoniatricyclo[4.3.3.0(1,5)]undecane moiety, subincanadines A-C (1-3), as well as two new indole alkaloids with a 1-azabicyclo[5.2.2]undecane moiety, subincanadines D (4) and E (5), and a new indole alkaloid with a 1-azabicyclo[4.3.1]decane moiety, subincanadine F (6), have been isolated from the barks of Aspidosperma subincanum Mart, and the structures of 1-6 and the stereochemistry of 1-3 were elucidated by spectroscopic data and chemical means. 相似文献
33.
Naoki Noma Saori Yamazaki Noboru Tohge 《Journal of Sol-Gel Science and Technology》2004,31(1-3):253-256
ZrO2 gel films were prepared from zirconium tetra-n-butoxide chemically modified with one of hydroxyl-substituted aromatic ketones and 1′-hydroxy-2′-acetonaphthone, by the sol-gel method. The obtained gel film showed an absorption band, characteristic of the π-π* transition of chelate ring, at around 410 nm. The band was shifted to longer wavelength region than those for the gel films using β-diketones. The reason is thought that the hydroxyl-substituted aromatic ketone has π-electron system to form the condensed chelate ring. The absorption band associated with the chelate ring gradually decreased in intensity with UV-irradiation using a high pressure mercury lamp. This indicates that the chelate ring dissociates by the UV-irradiation and that the gel film exhibits photosensitivity. Utilizing the photosensitivity, fine patterns (about 1 μm) could be fabricated by UV-irradiation through a mask and leaching. 相似文献
34.
Noboru Yamazaki Tadao Iguchi Fukuji Higashi 《Journal of polymer science. Part A, Polymer chemistry》1975,13(4):785-795
Polyureas of high molecular weight were obtained by the direct polycondensation reaction of carbon dioxide with diamines at 40°C for several hours under a pressure of carbon dioxide (below 30 atm) by use of diphenyl phosphite in pyridine. Optimal temperature and pressure were 40°C and 20 atm of carbon dioxide. The polycondensation reaction was also affected by solvents and type and amounts of tertiary amines. Pyridine was most effective as tertiary amine and solvent as well. Of the phosphorous compounds used, triaryl phosphites and diphenyl phosphite were most effective, but trialkyl phosphites failed to give polymer. The reaction was assumed to proceed via a carbamyl N-phosphonium salt of pyridine formed by dephenoxylation of phosphites. Similarly, polythioureas were prepared by heating a mixture of carbon disulfide, diamines, and diphenyl phosphite in pyridine at 40°C for 6 hr under nitrogen. 相似文献
35.
36.
Noboru Oyama Takeo Ohsaka Takeyoshi Okajima Tomoaki Hirokawa Tsuyoshi Maruyama Yukio Ohnuki 《Journal of Electroanalytical Chemistry》1985,187(1):79-96
Liquid crystalline/polymer composite membrane-coated electrodes were prepared by casting a 1,2-dichloroethane solution of N-(4-ethoxybenzylidene)-4′-n-butylaniline (EBBA) and polycarbonate (PC) on an electrode surface. The temperature-dependence of the permeability of the EBBA/PC composite membrane on electrodes to Fe(CN)3?6 ion as a solution-phase redox ion was investigated by means of hydrodynamic voltammetry at a rotating disk electrode. The permeability changed with temperature over the range of the crystalline-nematic-phase transition temperature of EBBA. It is demonstrated that the observed temperature-dependence of the permeability reflects the thermotropic properties of EBBA in the EBBA/PC composite membrane. Furthermore, the dependence of the limiting current of the steady-state current-potential curves for the reduction of Fe(CN)—6 at the EBBA/PC composite membrane-coated electrode upon the membrane thickness, the blend ratio of EBBA and PC and the concentration of Fe(CN)3?6 in a bulk solution was examined in order to understand the transport process of Fe(CN)?36 through the EBBA/PC composite membrane from the membrane/solution interface to the electrode/membrane interface. The transport process of Fe(CN)3?6 within the membrane was found to obey Fick's Law. 相似文献
37.
Noboru Yamazaki Makoto Matsumoto Fukuji Higashi 《Journal of polymer science. Part A, Polymer chemistry》1975,13(6):1373-1380
Poly-p-benzamide of high molecular weight (ηinh = ~ in H2SO4) was obtained by the direct polycondensation reaction of p-aminobenzoic acid (p-ABA) by means of diphenyl and triaryl phosphites in N-methylpyrrolidone (NMP)-pyridine solution containing lithium and calcium chlorides. Molecular weight of polymer varied with the amount of these salts, showing maximum values at the concentration of about 4 wt-% of LiCl or about 8 wt-% of CaCl2 in the reaction mixture. The reaction temperature at around 80°C gave a polymer of the highest viscosity. The polycondensation reaction was also affected by monomer concentration, solvents, and tertiary amines like pyridine. Similarly, aromatic polyamides with high molecular weight (ηinh values up to 1.34 in H2SO4) were prepared from isophthalic acid and aromatic diamines, whereas terephthalic acid gave only low-viscosity polymers. 相似文献
38.
Boller TM Murphy JM Hapke M Ishiyama T Miyaura N Hartwig JF 《Journal of the American Chemical Society》2005,127(41):14263-14278
This paper describes mechanistic studies on the functionalization of arenes with the diboron reagent B(2)pin(2) (bis-pinacolato diborane(4)) catalyzed by the combination of 4,4'-di-tert-butylbipyridine (dtbpy) and olefin-ligated iridium halide or olefin-ligated iridium alkoxide complexes. This work identifies the catalyst resting state as [Ir(dtbpy)(COE)(Bpin)(3)] (COE = cyclooctene, Bpin = 4,4,5,5-tetramethyl-1,3,2-dioxaborolanyl). [Ir(dtbpy)(COE)(Bpin)(3)] was prepared by independent synthesis in high yield from [Ir(COD)(OMe)](2), dtbpy, COE, and HBpin. This complex is formed in low yield from [Ir(COD)(OMe)](2), dtbpy, COE, and B(2)pin(2). Kinetic studies show that this complex reacts with arenes after reversible dissociation of COE. An alternative mechanism in which the arene reacts with the Ir(I) complex [Ir(dtbpy)Bpin] after dissociation of COE and reductive elimination of B(2)pin(2) does not occur to a measurable extent. The reaction of [Ir(dtbpy)(COE)(Bpin)(3)] with arenes and the catalytic reaction of B(2)pin(2) with arenes catalyzed by [Ir(COD)(OMe)](2) and dtbpy occur faster with electron-poor arenes than with electron-rich arenes. However, both the stoichiometric and catalytic reactions also occur faster with the electron-rich heteroarenes thiophene and furan than with arenes, perhaps because eta(2)-heteroarene complexes are more stable than the eta(2)-arene complexes and the eta(2)-heteroarene or arene complexes are intermediates that precede oxidative addition. Kinetic studies on the catalytic reaction show that [Ir(dtbpy)(COE)(Bpin)(3)] enters the catalytic cycle by dissociation of COE, and a comparison of the kinetic isotope effects of the catalytic and stoichiometric reactions shows that the reactive intermediate [Ir(dtbpy)(Bpin)(3)] cleaves the arene C-H bond. The barriers for ligand exchange and C-H activation allow an experimental assessment of several conclusions drawn from computational work. Most generally, our results corroborate the conclusion that C-H bond cleavage is turnover-limiting, but the experimental barrier for this bond cleavage is much lower than the calculated barrier. 相似文献
39.
In the Sc2O3---Ga2O3---CuO, Sc2O3---Ga2O3---ZnO, and Sc2O3---Al2O3---CuO systems, ScGaCuO4, ScGaZnO4, and ScAlCuO4 with the YbFe2O4-type structure and Sc2Ga2CuO7 with the Yb2Fe3O7-type structure were obtained. In the In2O3---A2O3---BO systems (A: Fe, Ga, or Al; B: Mg, Mn, Fe, Ni, or Zn), InGaFeO4, InGaNiO4, and InFe3+MgO4 with the spinel structure, InGaZnO4, InGaMgO4, and InAlCuO4 with the YbFe2O4-type structure, and In2Ga2MnO7 and In2Ga2ZnO7 with the Yb2Fe3O7-type structure were obtained. InGaMnO4 and InFe2O4 had both the YbFe2O4-type and spinel-type structures. The revised classification for the crystal structures of AB2O4 compounds is presented, based upon the coordination numbers of constituent A and B cations. 相似文献
40.
Du YZ Hiratsuka Y Taira S Eguchi M Uyeda TQ Yumoto N Kodaka M 《Chemical communications (Cambridge, England)》2005,(16):2080-2082
A new nano-biomachine has been created from microtubules (MTs) and hetero-bifunctional polymer particles bearing pyruvate kinase, which is propelled on glass surfaces coated with kinesin by use of self-supplying ATP. 相似文献