全文获取类型
收费全文 | 176篇 |
免费 | 12篇 |
专业分类
化学 | 163篇 |
数学 | 14篇 |
物理学 | 11篇 |
出版年
2023年 | 1篇 |
2022年 | 1篇 |
2020年 | 3篇 |
2019年 | 5篇 |
2018年 | 1篇 |
2017年 | 1篇 |
2016年 | 4篇 |
2015年 | 6篇 |
2014年 | 8篇 |
2013年 | 7篇 |
2012年 | 8篇 |
2011年 | 13篇 |
2010年 | 5篇 |
2009年 | 1篇 |
2008年 | 10篇 |
2007年 | 18篇 |
2006年 | 12篇 |
2005年 | 12篇 |
2004年 | 18篇 |
2003年 | 7篇 |
2002年 | 7篇 |
2001年 | 9篇 |
2000年 | 5篇 |
1998年 | 3篇 |
1997年 | 2篇 |
1996年 | 4篇 |
1995年 | 4篇 |
1994年 | 4篇 |
1993年 | 3篇 |
1992年 | 1篇 |
1985年 | 2篇 |
1984年 | 1篇 |
1982年 | 1篇 |
1977年 | 1篇 |
排序方式: 共有188条查询结果,搜索用时 78 毫秒
21.
22.
Maspoch D Domingo N Ruiz-Molina D Wurst K Hernández JM Vaughan G Rovira C Lloret F Tejada J Veciana J 《Chemical communications (Cambridge, England)》2005,(40):5035-5037
A metal-organic open-framework with an unprecedented (6,3)-helical topology, large channels and mixed ferro- and antiferromagnetic interactions has been synthesized using a three-connecting tricarboxylic polychlorotriphenylmethyl radical and Co(ii) ions. 相似文献
23.
24.
Roques N Maspoch D Imaz I Datcu A Sutter JP Rovira C Veciana J 《Chemical communications (Cambridge, England)》2008,(27):3160-3162
The reaction of a 3-connecting PTMTC radical with Tb(III) ions forms a three-dimensional open-framework with the formula [Tb(PTMTC)(DMF)(3)] (1), which associates a lattice complex T topology with large channels, guest-induced reversible crystal to amorphous transformations and ferromagnetic metal-radical interactions. 相似文献
25.
26.
Alfonso-Prieto M Borovik A Carpena X Murshudov G Melik-Adamyan W Fita I Rovira C Loewen PC 《Journal of the American Chemical Society》2007,129(14):4193-4205
The structures of Helicobacter pylori (HPC) and Penicillium vitale (PVC) catalases, each with two subunits in the crystal asymmetric unit, oxidized with peroxoacetic acid are reported at 1.8 and 1.7 A resolution, respectively. Despite the similar oxidation conditions employed, the iron-oxygen coordination length is 1.72 A for PVC, close to what is expected for a Fe=O double bond, and 1.80 and 1.85 A for HPC, suggestive of a Fe-O single bond. The structure and electronic configuration of the oxoferryl heme and immediate protein environment is investigated further by QM/MM density functional theory calculations. Four different active site electronic configurations are considered, Por*+-FeIV=O, Por*+-FeIV=O...HisH+, Por*+-FeIV-OH+ and Por-FeIV-OH (a protein radical is assumed in the latter configuration). The electronic structure of the primary oxidized species, Por*+-FeIV=O, differs qualitatively between HPC and PVC with an A2u-like porphyrin radical delocalized on the porphyrin in HPC and a mixed A1u-like "fluctuating" radical partially delocalized over the essential distal histidine, the porphyrin, and, to a lesser extent, the proximal tyrosine residue. This difference is rationalized in terms of HPC containing heme b and PVC containing heme d. It is concluded that compound I of PVC contains an oxoferryl Por*+-FeIV=O species with partial protonation of the distal histidine and compound I of HPC contains a hydroxoferryl Por-FeIV-OH with the second oxidation equivalent delocalized as a protein radical. The findings support the idea that there is a relation between radical migration to the protein and protonation of the oxoferryl bond in catalase. 相似文献
27.
Nunes JP Figueira MJ Belo D Santos IC Ribeiro B Lopes EB Henriques RT Vidal-Gancedo J Veciana J Rovira C Almeida M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(35):9841-9849
The gold and nickel bisdithiolene complexes based on new highly extended ligands incorporating fused tetrathiafulvalene and thiophene moieties (alpha-tdt=thiophenetetrathiafulvalenedithiolate and dtdt=dihydro- thiophenetetrathiafulvalenedithiolate), were prepared and characterised by using cyclic voltammetry, single crystal X-ray diffraction, EPR, magnetic susceptibility and electrical transport measurements. These complexes, initially obtained under anaerobic conditions as diamagnetic gold monoanic [nBu(4)N][Au(alpha-tdt)(2)] (4), [nBu(4)N][Au(dtdt)(2)] (3) and nickel dianionic species [(nBu(4)N)(2)][Ni(alpha-tdt)(2)] (8), [(nBu(4)N)(2)][Ni(dtdt)(2)] (7), can be easily oxidised to the stable neutral state just by air or iodine exposure. The monoanionic complexes crystallise in at least two polymorphs, all of which have good cation and anion segregation in alternated layers, the anion layers making a dense 2D network of short SS contacts. All of the neutral complexes, obtained as microcrystalline or quasi amorphous fine powder, present relatively large magnetic susceptibilities that correspond to effective magnetic moments in the range 1-3 mu(B) indicative of high spin states and very high electrical conductivity that in case of the Ni compound can reach sigma(RT) approximately 250 S cm(-1) with a clear metallic behaviour. These compounds are new examples of the still rare single-component molecular metals. 相似文献
28.
Caballero A Lloveras V Curiel D Tárraga A Espinosa A García R Vidal-Gancedo J Rovira C Wurst K Molina P Veciana J 《Inorganic chemistry》2007,46(3):825-838
The synthesis, optical and electrochemical properties, and X-ray characterization of two thiazole derivatives capped by ferrocenyl groups (5 and 7) and their model compounds with one ferrocenyl, either at 2 or 5 position of the mono- or bis-thiazolyl rings (3, 9, 11, and 14), are presented. Bisferrocenyl thiazole 5 forms the mixed-valence species 5*+ by partial oxidation which, interestingly, shows an intramolecular electron-transfer phenomenon. Moreover, the reported heteroaromatic compounds show selective ion-sensing properties. Thus, ferrocenylthiazoles linked across the 5 position of the heteroaromatic ring are selective chemosensors for Hg2+ and Pb2+ metal ions; 5-ferrocenylthiazole 3 operates through two channels, optical and redox, for Hg2+ and only optical for Pb2+, whereas 1,1'-bis(thiazolyl)ferrocene 14 is only an optical sensor for both metal ions. Moreover, complex 3 behaves as an electrochemically induced switchable chemosensor because of the low metal-ion affinity of the oxidized 3*+ species. On the other hand, ferrocenylthiazole 9, in which the heterocyclic ring and the ferrocene group are linked across the 2 position, is a selective redox sensor for Hg2+ metal ions, and it responds optically, as does bis(thiazolyl)ferrocene 11, to a narrow range of cations (Zn2+, Cd2+, Hg2+, Ni2+, and Pb2+). Finally, bis(ferrocenyl)thiazole 5 is a dual optical and redox sensor for Zn2+, Cd2+, Hg2+, Ni2+, and Pb2+, whereas bis(ferrocenyl) compound 7, bearing a bis(thiazole) unit as a bridge, is only a chromogenic sensor for Zn2+, Cd2+, Hg2+, Ni2+, and Pb2+. The experimental data and conclusions about both the electronic and ion-sensing properties are supported by DFT calculations which show, in addition, an unprecedented intramolecular electron-transfer reorganization after the first one-electron oxidation of compound 5. 相似文献
29.
30.
Amriou S Wang C Batsanov AS Bryce MR Perepichka DF Ortí E Viruela R Vidal-Gancedo J Rovira C 《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(12):3389-3400
Derivatives of 9-(1,3-dithiol-2-ylidene)fluorene (9) and 9-(1,3-dithiol-2-ylidene)thioxanthene (10) have been synthesised using Horner-Wadsworth-Emmons reactions of (1,3-dithiol-2-yl)phosphonate reagents with fluorenone and thioxanthen-9-one. X-ray crystallography, solution electrochemistry, optical spectroscopy, spectroelectrochemistry and simultaneous electrochemistry and electron paramagnetic resonance (SEEPR), combined with theoretical calculations performed at the B3P86/6-31G** level, elucidate the interplay of the electronic and structural properties in these molecules. These compounds are strong two-electron donors, and the oxidation potentials depend on the electronic structure of the oxidised state. Two, single-electron oxidations (E(1)ox < E(1)ox) were observed for 9-(1,3-dithiol-2-ylidene)fluorene systems (9). In contrast, derivatives of 9-(1,3-dithiol-2-ylidene)thioxanthene (10) display the unusual phenomenon of inverted potentials (E(1)ox > E(1)ox) resulting in a single, two-electron oxidation process. The latter is due to the aromatic structure of the thioxanthenium cation (formed on the loss of a second electron), which stabilises the dication state (10(2+)) compared with the radical cation. This contrasts with the nonaromatic structure of the fluorenium cation of system 9. The two-electron oxidation wave in the thioxanthene derivatives is split into two separate one-electron waves in the corresponding sulfoxide and sulfone derivatives 27-29 owing to destabilisation of the dication state. 相似文献