全文获取类型
收费全文 | 578篇 |
免费 | 12篇 |
专业分类
化学 | 417篇 |
晶体学 | 10篇 |
力学 | 2篇 |
数学 | 8篇 |
物理学 | 153篇 |
出版年
2021年 | 5篇 |
2020年 | 8篇 |
2019年 | 11篇 |
2018年 | 3篇 |
2017年 | 3篇 |
2016年 | 10篇 |
2015年 | 13篇 |
2014年 | 10篇 |
2013年 | 21篇 |
2012年 | 24篇 |
2011年 | 25篇 |
2010年 | 20篇 |
2009年 | 22篇 |
2008年 | 48篇 |
2007年 | 36篇 |
2006年 | 40篇 |
2005年 | 29篇 |
2004年 | 21篇 |
2003年 | 9篇 |
2002年 | 17篇 |
2001年 | 15篇 |
2000年 | 11篇 |
1999年 | 13篇 |
1998年 | 7篇 |
1997年 | 4篇 |
1996年 | 6篇 |
1995年 | 5篇 |
1994年 | 4篇 |
1993年 | 10篇 |
1992年 | 6篇 |
1991年 | 8篇 |
1990年 | 7篇 |
1989年 | 7篇 |
1988年 | 7篇 |
1987年 | 6篇 |
1986年 | 6篇 |
1985年 | 10篇 |
1984年 | 9篇 |
1982年 | 7篇 |
1981年 | 4篇 |
1980年 | 6篇 |
1979年 | 5篇 |
1978年 | 5篇 |
1975年 | 8篇 |
1973年 | 5篇 |
1972年 | 4篇 |
1971年 | 8篇 |
1970年 | 3篇 |
1969年 | 2篇 |
1968年 | 3篇 |
排序方式: 共有590条查询结果,搜索用时 15 毫秒
31.
A mononuclear five-coordinate molybdenum(IV) monosulfide complex, (Et4N)2[MoS(L)2] (L = cyclohexene-1,2-dithiolate) (1), was obtained and characterized by IR, UV-vis spectroscopic methods, and X-ray crystallography. 1 was oxidized by an equivalent ferrocenium cation to give the corresponding mononuclear molybdenum(V) complex, (Et4N)[MoS(L)2] (2), which was stable for a few minutes under a lower concentration than 0.3 mM and then further dimerized to (Et4N)2[Mo(L)2]2(mu-S)2 (3). 相似文献
32.
The enzymatic resolution products [(1R,4aR,8aR)-1,2,3,4,4a,5,6,7,8,8a-decahydro-5,5,8a-trimethyl-2-oxo-trans-naphthalene-1-methanol-2-ethylene acetal (8aR)-7 (98% ee) and {acetate of (1S,4aS,8aS)-1,2,3,4,4a,5,6,7,8,8a-decahydro-5,5,8a-trimethyl-2-oxo-trans-naphthalene-1-methanol-2-ethylene acetal} (8aS)-9 (>99% ee)] obtained by the lipase-catalyzed enantioselective acetylation of (±)-7 in the presence of vinyl acetate as an acyl donor were converted to the ,β-unsaturated ketones (8aR)-6 and (8aS)-6, respectively. Concise syntheses of (+)-totarol 1, (+)-podototarin 2 and (+)-sempervirol 3 were achieved based on Michael reactions between (8aS)-6 and the appropriate β-keto ester followed by aldol condensation. The first chiral syntheses of (+)-jolkinolides E 4 and D 5 were achieved from (5R,10R,12R)-12-hydroxypodocarpa-8(14)-en-13-one 15 derived from (8aR)-6. 相似文献
33.
In the present communication we would like to describe a novel method for the preparation of p-chloromethylstyrene and some reactions of this compound. 相似文献
34.
Cellulosic biomass is a promising alternative energy resource from the viewpoint of sustainability. The use of waste materials as cellulosic biomass could additionally contribute to a recycling society. It is thus essential to develop safer processes in order to expand utilization of cellulosic biomass as a useful resource in the future. For example, in some cases, construction wastes contain wood preservatives, including metal oxides that can act as catalysts for the oxidation of organic materials. Copper(II) oxide (CuO) is a major component in wood preservatives and is known to catalyze the oxidation of cellulose. There is, therefore, possibility for spontaneous ignition within large piles of wood chips from construction wastes. In this study, we focused on the thermal behavior of a cellulose/CuO mixture, measured using a Calvet-type heat flux calorimeter. In addition, Fourier transform infrared spectroscopy and gas chromatography were applied to analyze the oxidative decomposition gases of the cellulose/CuO mixture, and a reaction mechanism was proposed. It was revealed that CuO promotes the oxidative decomposition of cellulose and increases the quantity of the gases that evolved from cellulose with a catalytic cycle. The influence of CuO on oxidation of cellulose is greater at lower temperatures and spontaneous ignition, fires, and explosions are likely to increase when wood chips containing CuO are stored for long periods of time. 相似文献
35.
Shuhei Akahori Prof. Dr. Takahiro Sasamori Prof. Dr. Hiroshi Shinokubo Prof. Dr. Yoshihiro Miyake 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(31):8178-8184
Quadruply BN-fused tetrathia[8]circulenes were synthesized through four-fold electrophilic borylation. The single-crystal X-ray diffraction analysis revealed that the BN-fused tetrathia[8]circulene with peripheral phenyl groups exhibits crystal polymorphism, in which the circulene core adopts both planar and saddle conformations in the solid state. The experimental and theoretical studies revealed that the weaker aromaticity of azaborine compared with benzene renders the flexibility of the BN-fused tetrathia[8]circulenes. 相似文献
36.
37.
Shuhei Akahori Prof. Dr. Takahiro Sasamori Prof. Dr. Hiroshi Shinokubo Prof. Dr. Yoshihiro Miyake 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(18):5675-5682
Self-assembly of π-conjugated molecules in solution generally occurs owing to either an enthalpic or an entropic gain; however, designing π-conjugated systems that simultaneously exhibit enthalpically and entropically favorable self-assembly behavior is challenging. Herein, the self-assembly behavior of tetraazatetrathia[8]circulenes is disclosed, which is driven by both enthalpy and entropy. Single-crystal X-ray diffraction analysis demonstrated that molecules of these tetraazatetrathia[8]circulenes form face-to-face stacked dimers with a 1D columnar structure owing to the circularly arranged dipole moments. Importantly, concentration- and temperature-dependent 1H NMR spectra revealed that the formation of self-assemblies of tetraazatetrathia[8]circulenes in chloroform and methanol is favored by both enthalpic and entropic factors. The unique association behavior is due to the presence of sp2-hybridized nitrogen atoms, which weakly coordinate to the hydrogen atoms of these solvents and reduce the π-electron density of the circulene cores. 相似文献
38.
Junpei Miyake Keita Fukasawa Masahiro Watanabe Kenji Miyatake 《Journal of polymer science. Part A, Polymer chemistry》2014,52(3):383-389
Five kinds of ammonium groups functionalized partially fluorinated poly(arylene ether) block copolymer membranes were prepared for investigating the structure–property relationship as anion exchange membranes (AEMs). Consequently, the pyridine (PYR)‐modified membrane showed the highest alkaline and hydrazine stability in terms of the conductivity, water uptake, and dry weight. The chloromethylated precursor block copolymers were reacted with amines, such as trimethylamine, N‐butyldimethylamine, 1‐methylimidazole, 1,2‐dimethylimidazole, and PYR to provide the target quaternized poly(arylene ether)s. The structures of the polymers, as well as model compounds and oligomers were well characterized by 1H NMR spectra. The obtained AEMs were subjected to water uptake and hydroxide ion conductivity measurements and stabilities in aqueous alkaline and hydrazine media. The pyridinium‐functionalized quaternized polymers membrane showed the highest alkaline and hydrazine stability with minor losses in the conductivity, water uptake, and dry weight. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 383–389 相似文献
39.
40.