全文获取类型
收费全文 | 405篇 |
免费 | 27篇 |
专业分类
化学 | 363篇 |
晶体学 | 2篇 |
力学 | 1篇 |
数学 | 13篇 |
物理学 | 53篇 |
出版年
2023年 | 3篇 |
2021年 | 6篇 |
2020年 | 13篇 |
2019年 | 11篇 |
2018年 | 2篇 |
2017年 | 2篇 |
2016年 | 11篇 |
2015年 | 19篇 |
2014年 | 4篇 |
2013年 | 22篇 |
2012年 | 20篇 |
2011年 | 39篇 |
2010年 | 15篇 |
2009年 | 12篇 |
2008年 | 30篇 |
2007年 | 30篇 |
2006年 | 31篇 |
2005年 | 26篇 |
2004年 | 28篇 |
2003年 | 18篇 |
2002年 | 10篇 |
2001年 | 5篇 |
2000年 | 4篇 |
1999年 | 5篇 |
1998年 | 4篇 |
1997年 | 5篇 |
1995年 | 1篇 |
1994年 | 2篇 |
1993年 | 2篇 |
1992年 | 5篇 |
1991年 | 3篇 |
1990年 | 4篇 |
1989年 | 3篇 |
1988年 | 2篇 |
1987年 | 2篇 |
1986年 | 2篇 |
1985年 | 1篇 |
1983年 | 1篇 |
1982年 | 1篇 |
1981年 | 1篇 |
1980年 | 5篇 |
1979年 | 2篇 |
1976年 | 4篇 |
1975年 | 3篇 |
1974年 | 5篇 |
1973年 | 1篇 |
1972年 | 1篇 |
1967年 | 3篇 |
1964年 | 1篇 |
1890年 | 1篇 |
排序方式: 共有432条查询结果,搜索用时 31 毫秒
11.
Kenji Kojima Kusuo Nishiyama Kanetada Nagamine Hironobu Ikeda 《Hyperfine Interactions》1993,78(1-4):429-433
The site diluted finite spin cluster system Rb2CO
x
Mg1–x
F4 (x=0.15, 0.4, 0.5) has been investigated by the +SR technique. Muon spin relaxation was observed in these diluted magnetic systems in a weak longitudinal field of 100 G. By reducing temperature below 100 K, the experimental data show features of slowing down phenomena of the Co electron moments in the finite spin clusters. 相似文献
12.
Naruki Tahara 《Tetrahedron letters》2004,45(26):5117-5120
Sequential treatment of 4,4-dimethyl-2-(o-tolyl)oxazoline in THF with sec-BuLi, aromatic or aliphatic aldehydes, sec-BuLi, B(OMe)3, and H2O2 produced the laterally alkylated and ortho-hydroxylated oxazolines in one-pot. Treatment of these products with TFA in aqueous THF provided 3-substituted 8-hydroxy-3,4-dihydroisocoumarins in 44-75% overall yields. This procedure allowed the short synthesis of (±)-hydrangenol and (±)-phyllodulcin, naturally occurring 3,4-dihydroisocoumarins of pharmacological interest. A more economical synthesis of (±)-phyllodulcin via the trianion intermediate is also described. 相似文献
13.
T Kawakita T Kuroita M Yasumoto M Sano K Inaba T Fukuda T Tahara 《Chemical & pharmaceutical bulletin》1992,40(3):624-630
A series of 3,4-dihydro-3-oxo-1,4-benzoxazine-8-carboxamide derivatives was synthesized and evaluated for serotonin-3 (5-HT3) receptor antagonistic activity assessed by their ability to antagonize the von Bezold-Jarish (BJ) effect in rats. Derivatives bearing 1-azabicyclo[2.2.2]oct-3-yl moiety as a basic function attached to the carboxamide at position 8 showed more potent antagonistic activity than those bearing the other three basic moieties. Structure-activity relationships of this series showed that methyl and chloro groups were more effective as substituents at positions 4 and 6, respectively. The representative compound 15 (Y-25130) in this series showed potent antagonistic activity on the BJ effect (ED50 = 1.3 micrograms/kg i.v.), high affinity for 5-HT3 receptor (Ki = 2.9 nM) and complete protection against cisplatin-induced emesis in dogs at a dose of 0.1 mg/kg i.v. 相似文献
14.
Takahasi H Yanagi K Ueda M Nakade K Fukuyama Y 《Chemical & pharmaceutical bulletin》2003,51(12):1377-1381
The methanol extract of the seeds of Phytolacca americana was reinvestigated to yield three new 1,4-benzodioxane-type compounds, americanoic acid methyl ester (1), isoamericanoic acid A methyl ester (2), and 9'-O-methylamericanol A (3) along with the previously isolated neolignans 6-9. The structures of 1-3 were characterized by 2D NMR and long-range selective proton-decoupling (LSPD) techniques. The neuritogenic effects of compounds 1-3, and dicarboxilic acids 4 and 5, which had been previously synthesized with horseradish peroxidase-catalyzed oxidative coupling of caffeic acid, were examined in primary cultured rat cortical neurons. Americanoic acid A methyl ester (1) exhibited neurite outgrowth-promoting activity at concentration of 0.01-1.0 microM, whereas dicarboxilic acids 4 and 5 were found to induce neuritogenesis dose dependently at the concentrations from 0.1 microM to 10 microM. 相似文献
15.
Hironobu Tahara Yudai Tanaka Shoko Yamamoto Shigeki Yonemori Bun Chan Hiroto Murakami Takamasa Sagara 《Chemical science》2021,12(13):4872
Redox-active ionic liquids (RAILs) are gaining attention as a material that can create a wide range of functions. We herein propose a charge-transfer (CT) RAIL by mixing two RAILs, specifically a carbazole-based ionic liquid ([CzC4ImC1][TFSI]) as a donor and a viologen-based ionic liquid ([C4VC7][TFSI]2) as an acceptor. We investigated the effect of CT interaction on the physicochemical properties of the CT ionic liquid (CT-IL) using the results of temperature-dependent measurements of UV-vis absorption, viscosity, and ionic conductivity as well as cyclic voltammograms. We employed the Walden analysis and the Grunberg–Nissan model to elucidate the effect of the CT interaction on the viscosity and ionic conductivity. The CT interaction reduces the viscosity by reducing the electrostatic attraction between the dicationic viologen and TFSI anion. It also reduces the ionic conductivity by the CT association of the dicationic viologen and carbazole. The electrochemically reversible responses of the viologens in [C4VC7][TFSI]2 and CT-IL are consistent with the Nernstian and the interacting two-redox site models. Notably, the transport and electrochemical properties are modulated by CT interaction, leading to unique features that are not present in individual component ILs. The inclusion of CT interaction in RAILs thus provides a powerful means to expand the scope of functionalized ionic liquids.A redox-active ionic liquid (RAIL) consisting of a carbazole and viologen shows charge transfer (CT) interaction. The physicochemical properties are modulated by the CT interaction by comparison with the individual RAILs. 相似文献
16.
Hironobu Hojo 《Tetrahedron letters》2007,48(1):25-28
A new method for the preparation of peptide thioester by the post-solid phase peptide synthesis (SPPS) approach was developed. A series of N-alkyl cysteine derivatives were prepared and used as the C-terminus residue of the peptides prepared by the Fmoc SPPS. The synthetic peptides released from resin by TFA were readily converted to the peptide thioester in aqueous 3-mercaptopropionic acid (MPA) without significant side reactions. 相似文献
17.
Nobuo Tanaka Hironobu Iwasaki Takeshi Fukutome Ken Hosoya Takeo Araki 《Journal of separation science》1997,20(10):529-538
Pseudo-stationary phases for electrokinetic chromatography were prepared by the alkylation of starburst dendrimers (SBDs). The SBD-supported pseudo-stationary phase with dodecyl groups showed higher efficiency than short-akyl derivatives, and maintained the hydrophobic property inthe presence of methanol. The dodecyl-modified SBD provided wide migration time windows ar high methanol content to effect the separation of sixteen aromatic hydrocarbons, the priority pollutants designated by EPA, in 65% methanol. The selectivity of polymer-supported pseudo-stationary phase can be varied simply by changing the length of the alkyl groups. The dodecyl SBD showed relatively similar selectivity as sodium dodecyl culfate micelle, whereas short alkyl derivatives showed preference towards rigid and planar compounds based on the rigid and planar compounds based on the rigid polymer backbones. The selectivity of SBD-supported pseudo-stationary phases was dominated by the chain length of the alkyl groups, with the minor effect of the structure of the core and the generation of SBD where alkyl groups were attached. 相似文献
18.
Hino S Ichikawa T Ogita N Udagawa M Fujii H 《Chemical communications (Cambridge, England)》2005,(24):3038-3040
The partial pressure of NH3 gas estimated by Raman spectroscopy indicates that approximately 0.1% NH3 inevitably contaminates the H2 desorbed from a hydrogen storage material composed of LiH and LiNH2 at any temperature up to 400 degrees C in a closed system. 相似文献
19.
Homoleptic cyclometalated iridium complexes with highly efficient red phosphorescence and application to organic light-emitting diode 总被引:7,自引:0,他引:7
Tsuboyama A Iwawaki H Furugori M Mukaide T Kamatani J Igawa S Moriyama T Miura S Takiguchi T Okada S Hoshino M Ueno K 《Journal of the American Chemical Society》2003,125(42):12971-12979
Phosphorescence studies of a series of facial homoleptic cyclometalated iridium(III) complexes have been carried out. The complexes studied have the general structure Ir(III)(C-N)(3), where (C-N) is a monoanionic cyclometalating ligand: 2-(5-methylthiophen-2-yl)pyridinato, 2-(thiophen-2-yl)-5-trifluoromethylpyridinato, 2,5-di(thiophen-2-yl)pyridinato, 2,5-di(5-methylthiophen-2-yl)pyridinato, 2-(benzo[b]thiophen-2-yl)pyridinato, 2-(9,9-dimethyl-9H-fluoren-2-yl)pyridinato, 1-phenylisoquinolinato, 1-(thiophen-2-yl)isoquinolinato, or 1-(9,9-dimethyl-9H-fluoren-2-yl)isoquinolinato. Luminescence properties of all the complexes at 298 K in toluene are as follows: quantum yields of phosphorescence Phi(p) = 0.08-0.29, emission peaks lambda(max) = 558-652 nm, and emission lifetimes tau = 0.74-4.7 micros. Bathochromic shifts of the Ir(thpy)(3) family [the complexes with 2-(thiophen-2-yl)pyridine derivatives] are observed by introducing appropriate substituents, e.g., methyl, trifluoromethyl, or thiophen-2-yl. However, Phi(p) of the red emissive complexes (lambda(max) > 600 nm) becomes small, caused by a significant decrease of the radiative rate constant, k(r). In contrast, the complexes with the 1-arylisoquinoline ligands are found to have marked red shifts of lambda(max) and very high Phi(p) (0.19-0.26). These complexes are found to possess dominantly (3)MLCT (metal-to-ligand charge transfer) excited states and have k(r) values approximately 1 order of magnitude larger than those of the Ir(thpy)(3) family. An organic light-emitting diode (OLED) device that uses Ir(1-phenylisoquinolinato)(3) as a phosphorescent dopant produces very high efficiency (external quantum efficiency eta(ex) = 10.3% and power efficiency 8.0 lm/W at 100 cd/m(2)) and pure-red emission with 1931 CIE (Commission Internationale de L'Eclairage) chromaticity coordinates (x = 0.68, y = 0.32). 相似文献
20.