全文获取类型
收费全文 | 367篇 |
免费 | 7篇 |
国内免费 | 2篇 |
专业分类
化学 | 234篇 |
力学 | 15篇 |
数学 | 72篇 |
物理学 | 55篇 |
出版年
2023年 | 1篇 |
2022年 | 2篇 |
2021年 | 7篇 |
2020年 | 3篇 |
2019年 | 5篇 |
2018年 | 12篇 |
2017年 | 4篇 |
2016年 | 9篇 |
2015年 | 9篇 |
2014年 | 7篇 |
2013年 | 16篇 |
2012年 | 18篇 |
2011年 | 21篇 |
2010年 | 14篇 |
2009年 | 20篇 |
2008年 | 27篇 |
2007年 | 23篇 |
2006年 | 22篇 |
2005年 | 18篇 |
2004年 | 23篇 |
2003年 | 18篇 |
2002年 | 11篇 |
2001年 | 6篇 |
2000年 | 2篇 |
1999年 | 4篇 |
1998年 | 8篇 |
1997年 | 5篇 |
1996年 | 9篇 |
1995年 | 5篇 |
1994年 | 3篇 |
1993年 | 2篇 |
1992年 | 4篇 |
1991年 | 1篇 |
1990年 | 1篇 |
1989年 | 4篇 |
1988年 | 2篇 |
1987年 | 5篇 |
1986年 | 1篇 |
1985年 | 3篇 |
1984年 | 2篇 |
1983年 | 2篇 |
1982年 | 3篇 |
1981年 | 1篇 |
1979年 | 2篇 |
1978年 | 3篇 |
1977年 | 3篇 |
1973年 | 1篇 |
1971年 | 1篇 |
1966年 | 1篇 |
1963年 | 2篇 |
排序方式: 共有376条查询结果,搜索用时 23 毫秒
71.
Baratta W Ballico M Del Zotto A Zangrando E Rigo P 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(23):6701-6709
The Vaska-type iridium(I) complex [IrCl(CO){PPh(2)(2-MeC(6)H(4))}(2)] (1), characterized by an X-ray diffraction study, was obtained from iridium(III) chloride hydrate and PPh(2)(2,6-MeRC(6)H(3)) with R=H in DMF, whereas for R=Me, activation of two ortho-methyl groups resulted in the biscyclometalated iridium(III) compound [IrCl(CO){PPh(2)(2,6-CH(2)MeC(6)H(3))}(2)] (2). Conversely, for R=Me the iridium(I) compound [IrCl(CO){PPh(2)(2,6-Me(2)C(6)H(3))}(2)] (3) can be obtained by treatment of [IrCl(COE)(2)](2) (COE=cyclooctene) with carbon monoxide and the phosphane in acetonitrile. Compound 3 in CH(2)Cl(2) undergoes intramolecular C-H oxidative addition, affording the cyclometalated hydride iridium(III) species [IrHCl(CO){PPh(2)(2,6-CH(2)MeC(6)H(3))}{PPh(2)(2,6-Me(2)C(6)H(3))}] (4). Treatment of 2 with Na[BAr(f) (4)] (Ar(f)=3,5-C(6)H(3)(CF(3))(2)) gives the fluxional cationic 16-electron complex [Ir(CO){PPh(2)(2,6-CH(2)MeC(6)H(3))}(2)][BAr(f) (4)] (5), which reversibly reacts with dihydrogen to afford the delta-agostic complex [IrH(CO){PPh(2)(2,6-CH(2)MeC(6)H(3))}{PPh(2)(2,6-Me(2)C(6)H(3))}][BAr(f)(4)] (6), through cleavage of an Ir-C bond. This species can also be formed by treatment of 4 with Na[BAr(f)(4)] or of 2 with Na[BAr(f)(4)] through C-H oxidative addition of one ortho-methyl group, via a transient 14-electron iridium(I) complex. Heating of the coordinatively unsaturated biscyclometalated species 5 in toluene gives the trans-dihydride iridium(III) complex [IrH(2)(CO){PPh(2)(2,6-MeC(6)H(3)CH=CHC(6)H(3)Me-2,6)PPh(2)}][BAr(f) (4)] (7), containing a trans-stilbene-type terdentate ligand, as result of a dehydrogenative carbon-carbon double bond coupling reaction, possibly through an iridium carbene species. 相似文献
72.
Teolato P Rampazzo E Arduini M Mancin F Tecilla P Tonellato U 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(8):2238-2245
Silica nanoparticles (about 15 nm diameters), which contain a derivative of 6-methoxy-8-(p-toluensulfonamido)-quinoline (TSQ) as a Zn(II) fluorescent probe covalently linked to the silica network, were prepared and studied as Zn(II) fluorescent chemosensors. The systems selectively detect Zn(II) ions in water rich solutions with a submicromolar sensitivity: 0.13 microM concentrations of Zn(II) can be measured with the only interference of Cu(II) and Cd(II) ions. Compared with free TSQ, the nanoparticles based systems have the advantage that they can be employed in aqueous solutions without aggregation problems while at the same time, they maintain a similar Zn(II) affinity and sensing ability. Addition of a second, substrate insensitive, fluorophore to the particles leads to the realization of a ratiometric sensor. 相似文献
73.
Claudio Bianchini Pierluigi Barbaro Michela Macchi Andrea Meli Francesco Vizza 《Helvetica chimica acta》2001,84(10):2895-2923
As part of our modelling studies of the hydrodenitrogenation of N‐heterocycles contained in raw oil materials, we investigated the selective hydrogenation of quinoline to 1,2,3,4‐tetrahydroquinoline by rhodium catalysts modified with the tripodal polyphosphane ligand MeC(CH2PPh2)3. Experiments in standard autoclaves and in high‐pressure sapphire NMR tubes, kinetic and isotope labelling studies, and independent reactions with isolated compounds have contributed to the elucidation of the catalytic mechanism as well as identification of the electronic requisites of the metal catalyst for selective and efficient hydrogenation. 相似文献
74.
Mirka Bergamo Tiziana Beringhelli Giuseppe D'Alfonso Pierluigi Mercandelli Massimo Moret Angelo Sironi 《Angewandte Chemie (International ed. in English)》1998,37(15):2128-2131
The first five-membered rings of metal atoms connected by M–M or M-H-M bonds only have been obtained by a Re2+Re3 condensation in which a polyhydride acts as a bridging bidentate ligand toward a coordinatively unsaturated fragment (see scheme below). In spite of the octahedral coordination of the Re centers, the Re5 rings display conformations (twisted and envelope) comparable with those observed for organic five-membered rings of tetrahedral carbon atoms. 相似文献
75.
76.
Barbara Roda Andrea Zattoni Pierluigi Reschiglian Myeong Hee Moon Elisa Michelini Aldo Roda 《Analytica chimica acta》2009,635(2):132-143
Field-flow fractionation (FFF) is a mature technique in bioanalysis, and the number of applications to proteins and protein complexes, viruses, derivatized nano- and micronsized beads, sub-cellular units, and whole cell separation is constantly increasing. This can be ascribed to the non-invasivity of FFF when directly applied to biosamples. FFF is carried out in an open-channel structure by a flow stream of a mobile phase of any composition, and it is solely based on the interaction of the analytes with a perpendicularly applied field. For these reasons, fractionation is developed without surface interaction of the analyte with packing or gel media and without using degrading mobile phases. The fractionation device can be also easily sterilized, and analytes can be maintained under a bio-friendly environment. This allows to maintain native conditions of the sample in solution.In this review, FFF principles are briefly described, and some pioneering developments and applications in the bioanalytical field are tabled before detailed report of most recent FFF applications obtained also with the hyphenation of FFF with highly specific, sensitive characterization methods. Special focus is finally given to the emerging use of FFF as a pre-analytical step for mass-based identification and characterization of proteins and protein complexes in proteomics. 相似文献
77.
We prove an existence result for forced oscillations of delay differential equations on compact manifolds with nonzero Euler-Poincaré characteristic. When the period is smaller than the delay we need the asymptotic fixed point index theory for C1 maps due to Eells and Fournier, and Nussbaum. 相似文献
78.
Sanchez-Escribano V Arrighi L Riani P Marazza R Busca G 《Langmuir : the ACS journal of surfaces and colloids》2006,22(22):9214-9219
Cu-Pd/Al2O3 bimetallic catalysts have been characterized by XRD, TEM, and EDX techniques. The surface structure has been investigated by FT-IR spectroscopy of low-temperature adsorbed CO in the reduced and in the oxidized state. Evidence has been provided of the formation of Cu-Pd alloy nanoparticles, both of the alpha-phase (disordered fcc) and of the beta-phase (ordered CsCl-type). IR spectra suggest that Cu likely decorates the edges while Pd mostly stays at the main faces. Part of copper disperses as Cu+ on the support even after reduction. The presence of copper seems to modify strongly the sate of oxidized Pd centers in oxidized high-Pd content materials. The redox chemistry of the system, where Pd is reduced more easily than Cu, appears to be very complex. 相似文献
79.
Reschiglian P Zattoni A Roda B Roda A Parisi D Moon MH Min BR 《Annali di chimica》2006,96(5-6):253-257
Low-impact ionization sources like electrospray ionization (ESI) and matrix-assisted, laser desorption/ionization (MALDI) equipped with time-of-flight (TOF) mass analyzers provide intact protein analysis over a very wide molar mass range. ESI/TOFMS provides also indications on the higher-order structure of intact proteins and non-covalent protein complexes. However, direct analysis of intact proteins mixtures in real samples shows limited success, mainly because spectra become very complex to interpret. This is also due to sample contaminants, and to the mechanism of competitive ionization in ESI or MALDI. Rapid and efficient sample clean-up and separation methods can significantly enhance the power of TOFMS for intact protein analysis. However, if protein native conditions want to be maintained, the methods should affect neither the three-dimensional structure nor the non-covalent chemistry of the proteins. Reversed-phase (RP) HPLC, size-exclusion chromatography (SEC), and capillary zone electrophoresis (CZE) are on-line or off-line coupled to ESI/TOFMS or MALDI/TOFMS. In fact, these separation methods often show limitations when applied to the analysis of native proteins. Organic modifiers and saline buffers are required in the case of RP HPLC or CZE. They can induce protein degradation or affect ionization when MS is performed after separation. High voltages used in CZE can contribute to alter proteins from their native form. In the case of high molar mass proteins, SEC is scarcely selective, and barely able to detect protein aggregates. Sample entanglement/adsorption on the stationary phase can also occur. 相似文献
80.
Four analogues of ochratoxin A (OTA) differing for the aminoacidic moiety were synthesised using ochratoxin α (OTα) as the starting material. The condensation reaction between protected amino acids and OTα, carried out in the presence of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC???HCl) and N-hydroxybenzotriazole (HOBt) as coupling agents, followed by deprotection and PTLC purification afforded OTA alanine, leucine, serine and tryptophane analogues in satisfactory yields (33-47%, based on OTα). 相似文献