全文获取类型
收费全文 | 113篇 |
免费 | 16篇 |
专业分类
化学 | 103篇 |
晶体学 | 1篇 |
力学 | 1篇 |
数学 | 2篇 |
物理学 | 22篇 |
出版年
2023年 | 1篇 |
2022年 | 1篇 |
2021年 | 3篇 |
2020年 | 5篇 |
2019年 | 5篇 |
2018年 | 6篇 |
2017年 | 3篇 |
2016年 | 7篇 |
2015年 | 7篇 |
2014年 | 9篇 |
2013年 | 7篇 |
2012年 | 12篇 |
2011年 | 14篇 |
2010年 | 8篇 |
2009年 | 1篇 |
2008年 | 6篇 |
2007年 | 10篇 |
2006年 | 5篇 |
2005年 | 3篇 |
2004年 | 1篇 |
2003年 | 1篇 |
2002年 | 1篇 |
2001年 | 1篇 |
2000年 | 1篇 |
1994年 | 1篇 |
1993年 | 1篇 |
1991年 | 3篇 |
1989年 | 1篇 |
1988年 | 1篇 |
1982年 | 3篇 |
1981年 | 1篇 |
排序方式: 共有129条查询结果,搜索用时 15 毫秒
21.
Aratake S Itoh T Okano T Usui T Shoji M Hayashi Y 《Chemical communications (Cambridge, England)》2007,(24):2524-2526
A small organic molecule, Pro-NH(2), catalyzing the enantioselective aldol reaction "in water" not merely "in the presence of water" with good enantioselectivity has been discovered for the first time. 相似文献
22.
Aratake S Itoh T Okano T Nagae N Sumiya T Shoji M Hayashi Y 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(36):10246-10256
Proline-based organocatalysts have been developed for a highly enantioselective, direct aldol reaction of aldehydes and ketones in the presence of water. While several surfactant-proline combined catalysts have proved effective, proline derivatives with a hydrophobic moiety such as trans-siloxy-L-proline and cis-siloxy-D-proline, both of which are easily prepared from the same commercially available 4-hydroxy-L-proline, have been found to be the most effective organocatalysts examined in this study, affording the aldol product with excellent diastereo- and enantioselectivities, these two catalysts generating opposite enantiomers. Water affects the selectivity, and poor results are obtained under neat reaction conditions or in dry organic solvents. More than three equivalents of water are required for the best diastereo- and enantioselectivities, while three equivalents is the recommended amount from a synthetic point of view. The reaction proceeds in the organic phase, and also proceeds in the presence of a large amount of water. The large-scale preparation of aldols with the minimal use of an organic solvent, including in the purification step, is described. 相似文献
23.
24.
Kobayashi A Hara H Yonemura T Chang HC Kato M 《Dalton transactions (Cambridge, England : 2003)》2012,41(6):1878-1888
Reactions of a Pt(II)-diimine-based metalloligand Na(2)[Pt(CN)(2)(4,4'-dcbpy)] (4,4'-H(2)dcbpy = 4,4'-dicarboxy-2,2'-bipyridine) with alkaline-earth metal salts Mg(NO(3))(2)·6H(2)O, CaCl(2), SrCl(2)·6H(2)O, and BaBr(2)·2H(2)O in aqueous solution gave luminescent complexes formulated as [Mg(H(2)O)(5)][Pt(CN)(2)(4,4'-dcbpy)]·4H(2)O (MgPt-4·9H(2)O), {[Ca(H(2)O)(3)][Pt(CN)(2)(4,4'-dcbpy)]·3H(2)O}(∞) (CaPt-4·6H(2)O), {[Sr(H(2)O)(2)][Pt(CN)(2)(4,4'-dcbpy)]·H(2)O}(∞) (SrPt-4·3H(2)O), and {[Ba(H(2)O)(2)][Pt(CN)(2)(4,4'-dcbpy)]·3H(2)O}(∞) (BaPt-4·5H(2)O), respectively. The crystal structures of all MPt-4 complexes were determined by X-ray crystallography. In these structures, the alkaline-earth metal ions are commonly coordinated to the carboxyl groups of the [Pt(CN)(2)(4,4'-dcbpy)](2-) metalloligand. In the case of MgPt-4·9H(2)O, the Mg(II) ion is bound by five water molecules and one oxygen atom of a carboxyl group to form a neutral complex molecule [Mg(H(2)O)(5)][Pt(CN)(2)(4,4'-dcbpy)]. In contrast, the alkaline-earth metal ion and metalloligand form two-dimensional (CaPt-4·6H(2)O) and three-dimensional (SrPt-4·3H(2)O and BaPt-4·5H(2)O) coordination networks, respectively. All fully hydrated complexes exhibited a strong phosphorescence from the triplet π-π* transition state. Luminescence spectroscopy revealed that MgPt-4·9H(2)O exhibited interesting multichromic (i.e., thermo-, mechano-, and vapochromic) luminescence, whereas CaPt-4·6H(2)O showed only thermochromic luminescence. The other two complexes did not exhibit any chromic behaviour. Combination analysis of powder X-ray diffraction, thermogravimetry, and IR spectroscopy suggests that the dimensionality of the coordination network contributes considerably to both the structural flexibility and luminescence properties; that is, the low-dimensional flexible coordination network formed in MPt-4 complexes with smaller alkaline-earth metal ions enables a structural rearrangement induced by thermal and mechanical stimuli and vapour adsorption, resulting in the observed multichromic behaviour. 相似文献
25.
Ken Watanabe Kenji Matsumoto Yutaka Adachi Takeshi Ohgaki Tsubasa Nakagawa Naoki Ohashi Hajime Haneda Isao Sakaguchi 《Solid State Communications》2012,152(20):1917-1920
Isotopic ZnO thin films were deposited on the c-plane of ZnO single crystals by pulsed laser deposition. The isotopic abundance of Zn in the films was determined with a secondary ion mass spectrometry before and after the films was diffusion annealed. The diffusion profiles across the film/substrate interface behaved smooth features. The zinc diffusion coefficient (DZn) was obtained by analyzing the slope of the profile in the annealed sample. The temperature dependence of DZn was determined to be DZn(cm2/s)=8.0×104exp(?417[kJ/mol])/RT, where R and T are gas constant and temperature. The zinc ion diffusion coefficients were of the same order as that in a ZnO single crystal. A comparison of the experimental and theoretical values indicated that the zinc ions diffused in the thin film and the single crystal through a vacancy mechanism. 相似文献
26.
Dr. Tsubasa Hatanaka Prof. Dr. Yasuhiro Ohki Dr. Takashi Kamachi Dr. Tomonori Nakayama Prof. Dr. Kazunari Yoshizawa Prof. Dr. Motomi Katada Prof. Dr. Kazuyuki Tatsumi 《化学:亚洲杂志》2012,7(6):1231-1242
The reactions of the half‐sandwich iron(II) complex [FeCl(Cp*)(tmeda)] ( 1 ; Cp*=η5‐C5Me5, TMEDA=N,N,N′,N′‐tetramethylethylenediamine) with potassium naphthalenide or potassium anthracenide gave the diamagnetic complexes [(Cp*)Fe(μ‐polyarene)Fe(Cp*)] (polyarene=naphthalene ( 2 ), anthracene ( 3a )), which have two {(Cp*)Fe} units bound to opposite faces of the polyarene. One of two {(Cp*)Fe} units in 3a is located over the central ring of anthracene while the other is positioned over an outer ring. The {(Cp*)Fe} unit bound to the central ring of 3a migrates to the outer ring upon heating in the solid state to give the isomer 3b . The electrochemical potential separations between successive one‐electron redox events for complexes 2 and 3b are large. The mixed valence complexes [ [2]+ ]+ and [ [3b]+ ]+ were synthesized by chemical oxidation. The mixed‐valence complex [ [3b]+ ]+ is charge delocalized on the Mössbauer timescale at 78 K, and its absorption spectrum shows an intervalence charge‐transfer band. Complex [ [2]+ ]+ exhibits two absorption bands in the near‐IR region and a slightly broadened doublet in the Mössbauer spectrum. DFT calculations were carried out to examine the electronic structures of these dinuclear iron(I) complexes to elucidate the factors responsible for their diamagnetism and to determine the degree of charge delocalization in the mixed‐valence complexes. 相似文献
27.
Dr. Tsubasa Nakashima Haruka Fujimori Dr. Kohsuke Ohmatsu Prof. Takashi Ooi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(36):9253-9256
Intermediary radical cations, generated through single-electron oxidation of enol silyl ethers by excited Ir-based photocatalysts, can be exploited as Brønsted acids for the activation of heteroarylcyanides. This strategy enables the direct allylic C−H heteroarylation of enol silyl ethers under visible-light irradiation. 相似文献
28.
Nanami Uemura Tsubasa Kobayashi Shintaro Yoshida Ya-xin Li Karel Goossens Xiangbing Zeng Go Watanabe Takahiro Ichikawa 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(22):8523-8528
We report a new molecular-design principle for creating double-gyroid nanostructured molecular assemblies based on atropisomerization. Ionic amphiphiles containing two imidazolium rings close to each other were designed and synthesized. NMR data revealed that the rotation of the imidazolium rings is restricted, with an activation energy as high as 63 kJ mol−1 in DMSO-d6 solution (DFT prediction for a model compound in the vacuum: 90–100 kJ mol−1). Due to the restricted rotation, the amphiphiles feature “double” atropisomeric axes in their ionic segments and form three stable atropisomers: meso, R, and S. These isomers co-organize into -type bicontinuous cubic liquid-crystalline mesophases through nanosegregation of the ionic and non-ionic parts. Considering the intrinsic characteristic of -type bicontinuous cubic structures that they are composed of intertwined right- and left-handed single gyroids, we propose that the simultaneous presence of both R- and S-atropisomers is an important contributor to the formation of double-gyroid structures. 相似文献
29.
S. Kubono Y. Funatsu N. Ikeda M. Yasue T. Nomura Y. Fuchi H. Kawashima S. Kato H. Orihara H. Miyatake T. Kajino 《Zeitschrift für Physik A Hadrons and Nuclei》1989,334(4):511-512
More than ten new levels have been identified just above the proton threshold in21Mg. The lowest s-wave resonant state assumed previously for the calculation of the stellar reaction rate in the rp-process is found to be a bound state, suggesting a serious change for the early stage of the rp-process. 相似文献
30.
Heterologous Expression,Biosynthetic Studies,and Ecological Function of the Selective Gq‐Signaling Inhibitor FR900359 下载免费PDF全文
Dr. Max Crüsemann Raphael Reher Isabella Schamari Dr. Alexander O. Brachmann Dr. Tsubasa Ohbayashi Markus Kuschak Dr. Davide Malfacini Alexander Seidinger Marta Pinto‐Carbó René Richarz Tatjana Reuter Dr. Stefan Kehraus Dr. Asis Hallab Misty Attwood Prof. Dr. Helgi B. Schiöth Dr. Peter Mergaert Dr. Yoshitomo Kikuchi Prof. Dr. Till F. Schäberle Prof. Dr. Evi Kostenis Prof. Dr. Daniela Wenzel Prof. Dr. Christa E. Müller Prof. Dr. Jörn Piel Prof. Dr. Aurélien Carlier Prof. Dr. Leo Eberl Prof. Dr. Gabriele M. König 《Angewandte Chemie (International ed. in English)》2018,57(3):836-840
The cyclic depsipeptide FR900359 (FR), isolated from the tropical plant Ardisia crenata, is a strong and selective inhibitor of Gq proteins, making it an indispensable pharmacological tool to study Gq‐related processes, as well as a promising drug candidate. Gq inhibition is a novel mode of action for defense chemicals and crucial for the ecological function of FR, as shown by in vivo experiments in mice, its affinity to insect Gq proteins, and insect toxicity studies. The uncultured endosymbiont of A. crenata was sequenced, revealing the FR nonribosomal peptide synthetase (frs) gene cluster. We here provide a detailed model of FR biosynthesis, supported by in vitro enzymatic and bioinformatic studies, and the novel analogue AC‐1, which demonstrates the flexibility of the FR starter condensation domains. Finally, expression of the frs genes in E. coli led to heterologous FR production in a cultivable, bacterial host for the first time. 相似文献