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排序方式: 共有321条查询结果,搜索用时 31 毫秒
31.
McKeown BA Gonzalez HE Friedfeld MR Gunnoe TB Cundari TR Sabat M 《Journal of the American Chemical Society》2011,133(47):19131-19152
Cationic platinum(II) complexes [((t)bpy)Pt(Ph)(L)](+) [(t)bpy =4,4'-di-tert-butyl-2,2'-bipyridyl; L = THF, NC(5)F(5), or NCMe] catalyze the hydrophenylation of ethylene to generate ethylbenzene and isomers of diethylbenzene. Using ethylene as the limiting reagent, an 89% yield of alkyl arene products is achieved after 4 h at 120 °C. Catalyst efficiency for ethylene hydrophenylation is diminished only slightly under aerobic conditions. Mechanistic studies support a reaction pathway that involves ethylene coordination to Pt(II), insertion of ethylene into the Pt-phenyl bond, and subsequent metal-mediated benzene C-H activation. Studies of stoichiometric benzene (C(6)H(6) or C(6)D(6)) C-H/C-D activation by [((t)bpy)Pt(Ph-d(n))(THF)](+) (n = 0 or 5) indicate a k(H)/k(D) = 1.4(1), while comparative rates of ethylene hydrophenylation using C(6)H(6) and C(6)D(6) reveal k(H)/k(D) = 1.8(4) for the overall catalytic reaction. DFT calculations suggest that the transition state for benzene C-H activation is the highest energy species along the catalytic cycle. In CD(2)Cl(2), [((t)bpy)Pt(Ph)(THF)][BAr'(4)] [Ar' = 3,5-bis(trifluoromethyl)phenyl] reacts with ethylene to generate [((t)bpy)Pt(CH(2)CH(2)Ph)(η(2)-C(2)H(4))][BAr'(4)] with k(obs) = 1.05(4) × 10(-3) s(-1) (23 °C, [C(2)H(4)] = 0.10(1) M). In the catalytic hydrophenylation of ethylene, substantial amounts of diethylbenzenes are produced, and experimental studies suggest that the selectivity for the monoalkylated arene is diminished due to a second aromatic C-H activation competing with ethylbenzene dissociation. 相似文献
32.
Frazier BA Bartholomew ER Wolczanski PT DeBeer S Santiago-Berrios M Abruña HD Lobkovsky EB Bart SC Mossin S Meyer K Cundari TR 《Inorganic chemistry》2011,50(24):12414-12436
A series of Werner complexes featuring the tridentate ligand smif, that is, 1,3-di-(2-pyridyl)-2-azaallyl, have been prepared. Syntheses of (smif)(2)M (1-M; M = Cr, Fe) were accomplished via treatment of M(NSiMe(3))(2)(THF)(n) (M = Cr, n = 2; Fe, n = 1) with 2 equiv of (smif)H (1,3-di-(2-pyridyl)-2-azapropene); ortho-methylated ((o)Mesmif)(2)Fe (2-Fe) and ((o)Me(2)smif)(2)Fe (3-Fe) were similarly prepared. Metatheses of MX(2) variants with 2 equiv of Li(smif) or Na(smif) generated 1-M (M = Cr, Mn, Fe, Co, Ni, Zn, Ru). Metathesis of VCl(3)(THF)(3) with 2 Li(smif) with a reducing equiv of Na/Hg present afforded 1-V, while 2 Na(smif) and IrCl(3)(THF)(3) in the presence of NaBPh(4) gave [(smif)(2)Ir]BPh(4) (1(+)-Ir). Electrochemical experiments led to the oxidation of 1-M (M = Cr, Mn, Co) by AgOTf to produce [(smif)(2)M]OTf (1(+)-M), and treatment of Rh(2)(O(2)CCF(3))(4) with 4 equiv Na(smif) and 2 AgOTf gave 1(+)-Rh. Characterizations by NMR, EPR, and UV-vis spectroscopies, SQUID magnetometry, X-ray crystallography, and DFT calculations are presented. Intraligand (IL) transitions derived from promotion of electrons from the unique CNC(nb) (nonbonding) orbitals of the smif backbone to ligand π*-type orbitals are intense (ε ≈ 10,000-60,000 M(-1)cm(-1)), dominate the UV-visible spectra, and give crystals a metallic-looking appearance. High energy K-edge spectroscopy was used to show that the smif in 1-Cr is redox noninnocent, and its electron configuration is best described as (smif(-))(smif(2-))Cr(III); an unusual S = 1 EPR spectrum (X-band) was obtained for 1-Cr. 相似文献
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34.
Manuel Caetano Leonardo Padrino T Hector Gutiérrez Alberto J. Fernández Jimmy Castillo 《Mikrochimica acta》1998,128(3-4):169-175
Trace level vanadium determination is reported using a dual beam thermal lens spectrometer. The thermal lens was generated using an argon ion beam laser (pump beam) which was focused into a sample cuvette. The thermal lens signal (TLs) was monitored with a He-Ne laser beam and a photodiode detector. Multichannel averager software was developed for processing the transient TLs. The optimal set up, ensuring maximum sensitivity and linear calibration graphs was obtained using experimental design techniques. Under optimized conditions, the detection limits for aqueous and ethanol-water (2+3 v/v) and (4+1 v/v) vanadium complex solutions were, respectively, 0.0071 mg/l, 0.0065 and 0.0039 mg/l. 相似文献
35.
Cairó Laurent Giacomini Hector Llibre Jaume 《Rendiconti del Circolo Matematico di Palermo》2003,52(3):389-418
We complete the classication of all Lotka-Volterra systemsx=x(ax+by+c),y=y(Ax+By+C), having a Liouvillian first integral. In our classification we take into account the first integrals coming from the existence
of exponential factors. 相似文献
36.
In this work we study the centers of planar analytic vector fields which are limit of linear type centers. It is proved that all the nilpotent centers are limit of linear type centers and consequently the Poincaré-Liapunov method to find linear type centers can be also used to find the nilpotent centers. Moreover, we show that the degenerate centers which are limit of linear type centers are also detectable with the Poincaré-Liapunov method. 相似文献
37.
Hector Freytes 《Archive for Mathematical Logic》2008,47(1):15-23
An algebraic setting for the validity of Pavelka style completeness for some natural expansions of Łukasiewicz logic by new
connectives and rational constants is given. This algebraic approach is based on the fact that the standard MV-algebra on
the real segment [0, 1] is an injective MV-algebra. In particular the logics associated with MV-algebras with product and
with divisible MV-algebras are considered.
The author express his gratitude to Roberto Cignoli, for his advice during the preparation of this paper. 相似文献
38.
39.
Sans résumé 相似文献
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