全文获取类型
收费全文 | 409篇 |
免费 | 19篇 |
国内免费 | 3篇 |
专业分类
化学 | 259篇 |
晶体学 | 3篇 |
力学 | 15篇 |
数学 | 80篇 |
物理学 | 74篇 |
出版年
2023年 | 2篇 |
2022年 | 3篇 |
2021年 | 5篇 |
2020年 | 9篇 |
2019年 | 3篇 |
2018年 | 1篇 |
2017年 | 8篇 |
2016年 | 17篇 |
2015年 | 15篇 |
2014年 | 16篇 |
2013年 | 23篇 |
2012年 | 50篇 |
2011年 | 36篇 |
2010年 | 19篇 |
2009年 | 14篇 |
2008年 | 25篇 |
2007年 | 22篇 |
2006年 | 23篇 |
2005年 | 22篇 |
2004年 | 19篇 |
2003年 | 20篇 |
2002年 | 13篇 |
2001年 | 3篇 |
2000年 | 2篇 |
1999年 | 6篇 |
1997年 | 3篇 |
1996年 | 5篇 |
1995年 | 1篇 |
1994年 | 2篇 |
1993年 | 4篇 |
1992年 | 2篇 |
1991年 | 1篇 |
1990年 | 1篇 |
1989年 | 1篇 |
1988年 | 1篇 |
1987年 | 2篇 |
1986年 | 2篇 |
1985年 | 8篇 |
1984年 | 5篇 |
1983年 | 4篇 |
1981年 | 1篇 |
1980年 | 4篇 |
1979年 | 2篇 |
1977年 | 1篇 |
1975年 | 1篇 |
1974年 | 2篇 |
1973年 | 2篇 |
排序方式: 共有431条查询结果,搜索用时 15 毫秒
321.
322.
Thomas Straub Matti Haukka Ari M.P. Koskinen 《Journal of organometallic chemistry》2005,690(3):674-677
The metathesis reaction of Cp*(CO)3MoBr and NaW(CO)3Cp produced Cp*(CO)3Mo-W(CO)3Cp (1), featuring an unsupported Mo-W bond. Exposure of solutions of 1 to light leads to the quantitative formation of the corresponding homometallic dimers. In the solid state, the title complex exhibits an anti-arrangement of the η5-cyclopentadienyl and the η5-pentamethyl-cyclopentadienyl ligands and six terminal carbonyls. Comparison to corresponding complexes of molybdenum and tungsten reveals that the Mo-W distance is dictated by the presence of a Cp and a Cp* ligand. This is the first time that an unsupported Mo-W single bond distance is reported. 相似文献
323.
Lehtovuori V Myllyperkiö P Linnanto J Manzoni C Polli D Cerullo G Haukka M Korppi-Tommola J 《The journal of physical chemistry. B》2005,109(37):17538-17544
Mechanisms of the light-induced ligand exchange reaction of (trans-I) Ru(dcbpy)(CO)2I2 (dcbpy = 4,4'-dicarboxylic acid-2,2'-bipyridine) in ethanol have been studied by transient absorption spectroscopy. Ultraviolet 20 fs excitation pulses centered at 325 nm were used to populate a vibrationally hot excited pi bipyridyl state of the reactant that quickly relaxes to a dissociative Ru-I state resulting in the release of one of the carbonyl groups. Quantum yield measurements have indicated that about 40% of the initially exited reactant molecules form the final photoproduct. A 62 fs rise component in the transient absorption (TA) signal was observed at all probe wavelengths in the visible region for the ongoing reaction, while the rise for the photoproduct was pulse limited (20 fs). We assign the observed 62 fs time component to the depopulation of the repulsive CO dissociative state. Vibrational coherences of the TA signals were observed at a wavenumber of 90 cm(-1). The resolved frequency, typical of I-Ru-I vibrational modes, is assigned to trans-cis isomerization of the iodines of the five-coordinated intermediate and damping of this oscillation in 500 fs to simultaneous solvent coordination. Cooling of the hot reactant and the product molecules occurs on a much slower time scale from 4 to 270 ps (Lehtovuori, V.; Aumanen, J.; Myllyperki?, P.; Rini, M.; Nibbering, E. T. J.; Korppi-Tommola, J. J. Phys. Chem. A 2004, 108, 1644). 相似文献
324.
A home-made temperature control unit has been developed for a commercial capillary electrophoresis apparatus, the Waters Quanta 4000. The effect of the unit on the absolute migration times and peak areas of nine β-blockers is described. It was found that this homemade temperature control unit considerably (≥ 100 %) improved the repeatability of the separation. 相似文献
325.
Vuorinen PS Jussila M Sirén H Palonen S Riekkola ML 《Journal of chromatography. A》2003,990(1-2):45-52
A contactless conductivity detector integrated into the capillary cassette of Agilent 3DCE equipment is described. The detector is user-friendly, compact and easily modified. The UV detector of the 3DCE equipment is available parallel with the contactless conductivity detector increasing the detection power. Two electrolyte solutions, 2-(N-morpholino)ethanesulfonic acid–histidine solution (20 mM, pH 6.0) and ammonium acetate (10 mM, pH 4.0), were used as the separation media for inorganic cations and organic catecholamines, respectively. The detection limit for all metal cations except barium was under 0.5 mg/l, and that for four catecholamines was ca. 10 mg/l. This last value was the same order of magnitude as achieved with parallel UV detection. 相似文献
326.
Yohannes G Shan J Jussila M Nuopponen M Tenhu H Riekkola ML 《Journal of separation science》2005,28(5):435-442
Asymmetrical flow field-flow fractionation (AsFIFFF) was used to determine the hydrodynamic particle sizes, molar masses, and phase transition behaviour of various poly(N-isopropylacrylamide) (PNIPAM) samples synthesised by reversible addition--fragmentation chain transfer (RAFT) and conventional free radical polymerisation processes. The results were compared with corresponding data obtained by dynamic light scattering (DLS) and size exclusion chromatography (SEC). Agreement between the three methods was good except at higher molar masses, where the molar mass averages obtained by SEC were much lower than those obtained by AsFIFFF and light scattering. The aggregation of the polymers, which are thermally sensitive, was studied by DLS and AsFIFFF at various temperatures. In deionised water there was an abrupt change in the particle size due to phase separation at approximately equal to 32-35 degrees C. The critical temperatures determined by AsFIFFF were 3-5 degrees C higher than those obtained by DLS. 相似文献
327.
The SKβ X-ray emission spectra of the SO2?3 and SO3F? ions are studied in detail and the observed fine structures are interpreted with the aid of existing molecular orbital (MO) calculations. The different MO methods are compared with regard to success and the effect of d-orbitals is discussed. The spectrometer is a double-crystal type with an instrument fwhm resolution of 0.25 eV for SKβ X-rays. 相似文献
328.
In an attempt to prepare structural and functional models for the active site of the hydrolytic enzyme zinc phosphotriesterase, five new zinc complexes of the ligands 2,6-bis[N-(N-(carboxylmethyl)-N-((1-methylimidazol)methyl)amine)methyl]-4-methylphenolate (BCIMP) and the corresponding asymmetric ligand 2-(N-isopropyl-N-((1-methylimidazolyl)methyl)aminomethyl)-6-(N-carboxylmethyl-N-((1-methylimidazolyl)methyl)aminomethyl)-4-methylphenol (ICIMP) have been synthesized, viz. Na[Zn(2)(BCIMP)Ac(2)] (1), [Zn(2)(BCIMP)(Ph(2)Ac)] (2), [Zn(2)(ICIMP)Ac(2)] (3), [Zn(4)(ICIMP)(2)(Me(3)Ac)(2)][ClO(4)](2) (4), and [Zn(4)(ICIMP)(2)(Ph(2)Ac)(2)][ClO(4)](2) (5). The X-ray structure of complex 5 has been determined and reveals that the complex is a dimer of dimers in the solid state, which in solution dissociates to potent structural models. Studies using NMR show that only one carboxylate coligand bridges the dizinc units in the case of diphenyl acetate and pivalate, while the steric bulk of acetate is sufficiently small to permit the coordination of two acetates/dizinc unit. Functional studies involving the hydrolysis/transesterification of 2-hydroxypropyl p-nitrophenyl phosphate (HPNP) show that the complex with ICIMP (compound 5) has a significantly higher rate of catalysis than the BCIMP complex (compound 2). This is attributed to the vacant/labile coordination site that is available in the ICIMP complex but not the BCIMP complex. 相似文献
329.
Two-dimensional thermal field-flow fractionation (2D-ThFFF) is a new instrumental technique devised for continuous fractionation of soluble macromolecules and particles. The sample mixture is introduced into a disc-shaped channel and the separated sample components are collected continuously from the channel outlets. The method is based on a two-dimensional fractionation mechanism with radial and tangential flow components in the channel. The effects of flow components and thermal gradient on the fractionation were studied in the separation of polystyrene samples of different molecular masses using cyclohexane or a binary solvent consisting of 25% ethylbenzene and 75% cyclohexane as carrier. The continuous separation of polystyrene samples was improved with increasing thermal gradient and with the use of slow radial and tangential flow rates. The technique can be applied to preparative continuous separation of macromolecules. 相似文献
330.
Luzyanin KV Kukushkin VY Haukka M Frausto da Silva JJ Pombeiro AJ 《Dalton transactions (Cambridge, England : 2003)》2004,(17):2728-2732
The nitrile ligands in the platinum(IV) complexes trans-[PtCl4(RCN)2] (R=Me, Et, CH2Ph) and cis/trans-[PtCl4(MeCN)(Me2SO)] are involved in a metalla-Pinner reaction with N-methylbenzohydroxamic acid (N-alkylated form of hydroxamic acid, hydroxamic form; F1), PhC(=O)N(Me)OH, to achieve the imino species [PtCl4[NH=C(R)ON(Me)C(=O)Ph]2 (1-3) and [PtCl4[NH=C(Me)ON(Me)C(=O)Ph](Me2SO)] (7), respectively. Treatment of trans-[PtCl4(RCN)2] (R=Me, Et) and cis/trans-[PtCl4(MeCN)(Me2SO)] with the O-alkylated form of a hydroxamic acid (hydroximic form), i.e. methyl 2,4,6-trimethylbenzohydroximate, 2,4,6-(Me3C6H2)C(OMe)=NOH (F2A), allows the isolation of [PtCl4[NH=C(R)ON=C(OMe)(2,4,6-Me3C6H2)]2] (5, 6) and [PtCl4[NH=C(Me)ON=C(OMe)(2,4,6-Me3C6H2)](Me2SO)] (8), correspondingly. In accord with the latter reaction, the coupling of nitriles in trans-[PtCl4(EtCN)2] with methyl benzohydroximate, PhC(OMe)=NOH (F2B), gives [PtCl4[NH=C(Et)ON=C(OMe)Ph]2] (4). The addition proceeds faster with the hydroximic F2, rather than with the hydroxamic form F1. The complexes 1-8 were characterized by C, H, N elemental analyses, FAB+ mass-spectrometry, IR, 1H and 13C[1H] NMR spectroscopies. The X-ray structure determinations have been performed for both hydroxamic and hydroximic complexes, i.e. 2 and 6, indicating that the imino ligands are mutually trans and they are in the E-configuration. 相似文献