全文获取类型
收费全文 | 2129篇 |
免费 | 78篇 |
国内免费 | 9篇 |
专业分类
化学 | 1771篇 |
晶体学 | 16篇 |
力学 | 26篇 |
数学 | 69篇 |
物理学 | 334篇 |
出版年
2023年 | 9篇 |
2022年 | 14篇 |
2021年 | 22篇 |
2020年 | 31篇 |
2019年 | 35篇 |
2018年 | 29篇 |
2017年 | 22篇 |
2016年 | 54篇 |
2015年 | 47篇 |
2014年 | 55篇 |
2013年 | 88篇 |
2012年 | 106篇 |
2011年 | 170篇 |
2010年 | 73篇 |
2009年 | 86篇 |
2008年 | 169篇 |
2007年 | 154篇 |
2006年 | 147篇 |
2005年 | 129篇 |
2004年 | 121篇 |
2003年 | 101篇 |
2002年 | 86篇 |
2001年 | 20篇 |
2000年 | 29篇 |
1999年 | 31篇 |
1998年 | 25篇 |
1997年 | 23篇 |
1996年 | 25篇 |
1995年 | 13篇 |
1994年 | 18篇 |
1993年 | 15篇 |
1992年 | 13篇 |
1991年 | 10篇 |
1990年 | 13篇 |
1989年 | 10篇 |
1988年 | 10篇 |
1987年 | 14篇 |
1986年 | 8篇 |
1985年 | 19篇 |
1984年 | 26篇 |
1983年 | 13篇 |
1982年 | 24篇 |
1981年 | 18篇 |
1980年 | 9篇 |
1979年 | 12篇 |
1978年 | 9篇 |
1977年 | 7篇 |
1976年 | 7篇 |
1975年 | 10篇 |
1973年 | 15篇 |
排序方式: 共有2216条查询结果,搜索用时 0 毫秒
141.
Selective Generation of Formamides through Photocatalytic CO2 Reduction Catalyzed by Ruthenium Carbonyl Compounds 下载免费PDF全文
Dr. Katsuaki Kobayashi Dr. Takashi Kikuchi Prof. Susumu Kitagawa Prof. Koji Tanaka 《Angewandte Chemie (International ed. in English)》2014,53(44):11813-11817
The selective formation of dialkyl formamides through photochemical CO2 reduction was developed as a means of utilizing CO2 as a C1 building block. Photochemical CO2 reduction catalyzed by a [Ru(bpy)2(CO)2]2+ (bpy: 2,2′‐bipyridyl)/[Ru(bpy)3]2+/Me2NH/Me2NH2+ system in CH3CN selectively produced dimethylformamide. In this process a ruthenium carbamoyl complex ([Ru(bpy)2(CO)(CONMe2)]+) formed by the nucleophilic attack of Me2NH on [Ru(bpy)2(CO)2]2+ worked as the precursor to DMF. Thus Me2NH acted as both the sacrificial electron donor and the substrate, while Me2NH2+ functioned as the proton source. Similar photochemical CO2 reductions using R2NH and R2NH2+ (R=Et, nPr, or nBu) also afforded the corresponding dialkyl formamides (R2NCHO) together with HCOOH as a by‐product. The main product from the CO2 reduction transitioned from R2NCHO to HCOOH with increases in the alkyl chain length of the R2NH. The selectivity between R2NCHO and HCOOH was found to depend on the rate of [Ru(bpy)2(CO)(CONR2)]+ formation. 相似文献
142.
Koji Naoda Young Mo Sung Jong Min Lim Prof. Dr. Dongho Kim Prof. Atsuhiro Osuka 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(25):7698-7705
A cross‐conjugated hexaphyrin that carries two meso‐oxacyclohexadienylidenyl (OCH) groups 9 was synthesized from the condensation of 5,10‐bis(pentafluorophenyl)tripyrrane with 3,5‐di‐tert‐butyl‐4‐hydroxybenzaldehyde. The reduction of 9 with NaBH4 afforded the Möbius aromatic [28]hexaphyrin 10 . Bis‐rhodium complex 11 , prepared from the reaction of 10 with [{RhCl(CO)2}2], displays strong Hückel antiaromatic character because of the 28 π electrons that occupy the conjugated circuit on the enforced planar structure. The oxidation of 11 with 2,3‐dichloro‐5,6‐dicyano‐1,4‐benzoquinone (DDQ) yielded complexes 12 and 13 depending upon the reaction conditions. Both 12 and 13 are planar owing to bis‐rhodium metalation. Although complex 12 bears two meso‐OCH groups at the long sides and is quinonoidal and nonaromatic in nature, complex 13 bears 3,5‐di‐tert‐butyl‐4‐hydroxyphenyl and OCH groups and exhibits a moderate diatropic ring current despite its cross‐conjugated electronic circuit. The diatropic ring current increases upon increasing the solvent polarity, most likely due to an increased contribution of an aromatic zwitterionic resonance hybrid. 相似文献
143.
144.
145.
146.
Koji Takagi Tsuyoshi Nakagawa Hidenobu Takao 《Journal of polymer science. Part A, Polymer chemistry》2010,48(1):91-98
Two arylenevinylene compounds bearing the cyano group at α‐position ( 6 ) and β‐position ( 9 ) from the dialkoxylphenylene unit were synthesized, in which the molecular termini were functionalized with 3‐bromocarbazole. The Suzuki coupling copolymerization of these compounds with 1,4‐bis[(3′‐bromocarbazole‐9′‐yl)methylene]‐2,5‐didecyloxybenzene and 9,9‐dihexylfluorene‐2,7‐bis(boronic acid) was carried out to obtain copolymers ( cp67 and cp97 ) containing the cyano‐substituted arylenevinylene fluorophore of 7 mol %. Model compounds ( 6 ′ and 9 ′) corresponding to the arylenevinylene fluorophore were also prepared. The UV spectra of copolymers resembled that of homopolymer hp with no arylenevinylene segment in both CHCl3 solution and thin film. The emission maxima of copolymers in CHCl3 (394 nm) agreed with that of homopolymer indicating that the emission bands originated from the carbazole‐fluorene‐carbazole segment. The emission maximum wavelength of copolymer cp67 in thin film (477 nm) indicated fluorescence from the cyano‐substituted arylenevinylene fluorophore because of the occurrence of fluorescence resonance electron transfer. In contrast, copolymer cp97 showed fluorescence at 528 nm to suggest the formation of a new emissive species such as a charge‐transfer complex (exciplex). © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 91–98, 2010 相似文献
147.
The polymer microspheres were synthesized by dispersion copolymerization of divinylbenzene (DVB) with two vinylbenzyl-terminated poly(ethylene glycol methylether) (PEG)/poly(t-butyl methacrylate) (PBMA) macromonomer blends in methanol. In these systems of two macromonomer blends as the emulsifier, the polymer microspheres formed had a very narrow particle size distribution. Two macromonomers formed comicelles with DVB monomer and acted not only as the comonomer but also as the stabilizer. Such polymer microspheres were stabilized sterically with two-component grafted chains, such as PEG and PBMA, in methanol. 相似文献
148.
An insoluble and assembled catalyst of palladium and a non-cross-linked amphiphilic polymer were developed. In the presence of 50-500 ppm mol equiv of catalyst, the Suzuki-Miyaura reaction proceeded efficiently under organic solvent-free conditions. The catalyst was reused 10 times without any decrease in activity and was recycled without any special treatment.[structure: see text] 相似文献
149.
The memory effect upon glassification is studied in the glass-to-rubber transition of vulcanized rubber with the strain as a controlling parameter. A phenomenological model is proposed, taking the history of the temperature and the strain into account, by which the experimental results are interpreted. The data and the model demonstrate that the glassy state memorizes the time course of strain upon glassification, not as a single parameter but as the history itself. The data also show that the effect of irreversible deformation in the glassy state is beyond the scope of the present model. 相似文献
150.
We demonstrate chlorine-induced modification of Si(100)-(2 x 1) under conditions where Cl is recycled rather than desorbed as SiCl2. A dimer with 2 Cl atoms, 2SiCl, converts to SiCl2+Si, allowing the bare Si atom to escape onto the terrace. At temperatures below the desorption threshold, the SiCl2 unit decays through Cl diffusion, allowing the second Si atom to escape. The result is a dimer vacancy, terrace regrowth structures, and Cl that is able to participate in another pitting event. Access to this unexpected roughening pathway is controlled by the Cl concentration and temperature. This previously overlooked process represents an important component of Si(100) surface processing. 相似文献