全文获取类型
收费全文 | 1800篇 |
免费 | 66篇 |
国内免费 | 9篇 |
专业分类
化学 | 1486篇 |
晶体学 | 19篇 |
力学 | 23篇 |
数学 | 113篇 |
物理学 | 234篇 |
出版年
2024年 | 3篇 |
2023年 | 16篇 |
2022年 | 19篇 |
2021年 | 24篇 |
2020年 | 17篇 |
2019年 | 44篇 |
2018年 | 30篇 |
2017年 | 21篇 |
2016年 | 58篇 |
2015年 | 46篇 |
2014年 | 46篇 |
2013年 | 97篇 |
2012年 | 130篇 |
2011年 | 134篇 |
2010年 | 58篇 |
2009年 | 62篇 |
2008年 | 122篇 |
2007年 | 109篇 |
2006年 | 122篇 |
2005年 | 125篇 |
2004年 | 93篇 |
2003年 | 96篇 |
2002年 | 71篇 |
2001年 | 16篇 |
2000年 | 32篇 |
1999年 | 17篇 |
1998年 | 6篇 |
1997年 | 21篇 |
1996年 | 20篇 |
1995年 | 4篇 |
1994年 | 9篇 |
1993年 | 10篇 |
1992年 | 22篇 |
1991年 | 6篇 |
1990年 | 10篇 |
1989年 | 6篇 |
1987年 | 5篇 |
1985年 | 24篇 |
1984年 | 14篇 |
1983年 | 6篇 |
1982年 | 9篇 |
1981年 | 21篇 |
1980年 | 9篇 |
1979年 | 6篇 |
1978年 | 10篇 |
1977年 | 8篇 |
1976年 | 16篇 |
1975年 | 12篇 |
1973年 | 2篇 |
1968年 | 2篇 |
排序方式: 共有1875条查询结果,搜索用时 15 毫秒
11.
12.
[reaction: see text] A newly developed strategy for construction of eight-membered carbocycles via [6 + 2] annulation that involves the combination of beta-alkenoyl acylsilanes and a vinyllithium derivative is described. A unique feature of this annulative approach is that it enables in one operation and a stereoselective manner construction of eight-membered ring systems containing useful functionalities for further synthetic elaboration from readily available six- and two-carbon components. 相似文献
13.
The complete structure of palytoxin (1) was elucidated by us in 1982.1 Our continuous interests in palytoxin led us to examine minor constituents of Okinawan Palythoa tuberculosa. In this paper, we describe successful isolation and structural elucidation of four minor toxins, which were named homopalytoxin (2), bishomopalytoxin (3), neopalytoxin (4) and deoxypalytoxin (5). 相似文献
14.
Photoreaction of 2,3-benzo-1,1-diphenyl(or dimethyl)-1-sila-2-cyclobutene with an aldehyde or ketone results in 1:1 cycloadduct of [4+2] type, the formation of which is accountd for in terms of SH2 process, i.e., attack of a triplet carbonyl compound on the silicon of the benzosilacyclobutene. 相似文献
15.
Kosuke Katagiri Yukina Yamamoto Yuui Takahata Ryoga Kishibe Naoki Fujimoto 《Tetrahedron letters》2019,60(30):2026-2029
Anthracenyl(diphenyl)phosphine oxide and dianthracenylphenylphosphine oxide as photoactive compounds have been synthesized. Anthracenyl group of these compounds indicate the multi-functional roles such as an emission component, a photodimerization component, and a leaving group. When the light irradiation was performed under an oxygen atmosphere, photo-oxidative PC bond cleavage to leave the antharacenyl group was observed. Moreover, phosphonyl radical was produced and then PP bond formation to form diphosphane was observed. 相似文献
16.
Naoki KakusawaYoshinori Tobiyasu Shuji YasuikeKentaro Yamaguchi Hiroko SekiJyoji Kurita 《Tetrahedron letters》2003,44(47):8589-8592
The reaction of 12-arylethynyl-6-methyl-5,6,7,12-tetrahydrodibenzo[c,f][1,5]-azastibocines with organic halides such as acyl halides and aryl halides in the presence of PdCl2(PPh3)2 as a catalyst led to the formation of cross-coupling products, alkynyl ketones and diaryl acetylenes, in good yields. The reactivity of the ethynyl group on the 1,5-azastibocines was far superior to that on diphenyl(phenylethynyl)stibane, which brought about marked improvement in the reaction conditions (lower temperature and shorter reaction time) and in the yields of the cross-coupling products. Single-crystal X-ray analysis of the ethynyl-1,5-azastibocine showed the presence of intramolecular Sb?N interaction which should be responsible for the remarkable reactivity enhancement of the 1,5-azastibocines for this type of reaction. 相似文献
17.
Osamu Sangen Singo Masuda Hidehiko Nakano Kazusige Yamana Kenichi Sasaki Naoki Ikeda 《Journal of polymer science. Part A, Polymer chemistry》1992,30(6):1171-1175
A new synthetic pathway of A–B–A tri-block copolyether which is composed of a hydrophilic poly(oxyethylene) unit as an A part and a hydrophobic poly(oxy-2-methyl-trimethylene) unit as a B part is proposed. Telechelic α-tosyl-ω-tosyloxypoly(oxy-2-methyl-trimethylene) derived from tosylation of poly(oxy-2-methyl-trimethylene glycol) (PMTG) was allowed to react with poly(ethylene glycol) (PEG) in the presence of sodium hydroxide. Tg of the resulting A–B–A tri-block copolyether (PEMG) (M?n = 1600) was ?72°C and its specific gravity [D415] was 1.055. 相似文献
18.
Toru Takagishi Naoki Matsui 《Journal of polymer science. Part A, Polymer chemistry》1987,25(9):2511-2520
The extent of binding of chrome violet, which is a monoazo dye and involves two hydroxyl groups in o and o′ positions to azo group, by polyvinylpyrrolidone is markedly enhanced in the presence of Co2+ ion. The amount of binding in the presence of 1 × 10?4 mol/L of Co2+ ion increases by a factor of about 10 compared to that in the absence of the metal ion. Ni2+ and Zn2+ ions do not perceptively influence the binding affinity of the dye. Cu2+ ion, in contrast, suppresses the binding. To investigate further the action of added metal ions, a cobalt–complex dye was prepared and its binding property for the polymer was compared to that of chrome violet in the presence of metal ions. Some possible mechanisms for the enhancement of chrome violet binding by the addition of Co2+ ion are described. 相似文献
19.
Matsumura Y Nishimura M Hiu H Watanabe M Kise N 《The Journal of organic chemistry》1996,61(8):2809-2812
Oxidative coupling of phenylacetic acid esters was easily achieved by treating the esters with TiCl(4) and then adding Et(3)N to the resulting solution. The products consisted of dl- and meso-2,3-diphenylsuccinic acid esters with the Claisen condensation product, and the ratio of these products depended on the reaction conditions. Reaction conditions suitable for high dl selectivity were determined, and a dimer of titanium enolate was postulated as an intermediate responsible for the high dl selectivity. The selectivities were compared with those in known oxidative couplings in which titanium enolate intermediates are prepared through lithium enolates and silyl enol ethers. The results suggest that the reactivities of titanium enolates intermediates depend on how they are generated. 相似文献
20.
Ichikawa K Shimomura N Yamada M Ohkubo N 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(14):3235-3241
In vitro biomimetic mineralization by means of nanotechnology allows the formation of calcium carbonate polymorphs at low temperatures (<25 degrees C) under a CO(2) atmosphere of 500-1500 ppm. A two-dimensional zinc-ion ordered array (zinc array), which acts as an active-site mimic of carbonic anhydrase, has been prepared by immersing the self-organized monolayer of 3-(2-imidazolin-1-y)propyltriethosilane on mica (ImSi substrate) into aqueous zinc solution. The zinc array mounted on the ImSi substrate catalyzed the conversion from CO(2) to HCO(3) (-), and accelerated the formation of calcium carbonate. In situ X-ray diffraction data of the formed calcium carbonate on the poly(L-aspartate)-coated chitin substrate (pAsp substrate), with calcium ion-recognition sites, demonstrated that the interaction between the zinc array and pAsp substrates formed both vaterite and calcite at low temperature (15 degrees C) and mainly vaterite at 25 degrees C; this interaction also controlled the morphology of calcium carbonate formed on pAsp substrate. 相似文献