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11.
Gianni Zotti Giuseppe Pilloni Mario Bressan Mario Martelli 《Journal of Electroanalytical Chemistry》1977,75(2):607-612
The electrochemical reduction of chlorodi-(1,3-bisdiphenylphosphinopropane)ruthenium(II)hexafluorophosphate, [RuCl(DPP)2](PF6), has been studied on the mercury electrode in 1,2-dimethoxyethane +0.1 M TBAP. The polarogram shows two reversible one-electron waves corresponding to the formation of [RuCl(DPP)2] and [RuCl(DPP)2]. Both products are unstable and decay through a disproportionation pathway and a fast internal metalation via Cl? elimination with formation of HRu(C6H4PPh·CH2CH2 CH2·PPh2)(DPP), respectively. The hypothesis is put forward that the geometry of a metal-complex can be one of the factors which allow us to obtain d7 monomeric complexes by electrochemical methods. 相似文献
12.
The relative permittivity of 1,2-dimethoxyethane and N,N-dimethylformamide mixtures from −10 to 40°C
Gianni Goldoni Luigi Marcheselli Andrea Marchetti Lorenzo Tassi Giuseppe Tosi 《Journal of solution chemistry》1992,21(9):953-962
Binary solutions of N,N-dimethylformamide and 1,2-dimethoxyethane have been investigated by means of dielectric measurements at temperatures ranging from –10 to +40°C, and for nine mixtures covering the whole miscibility field expressed by the mole fraction of one component (0X11). The experimental data were used to study the dependence of on T and X1, of the type = (T), = (X1), and = (T,X1). Further, the excess mixing function E has been evaluated in order to identify particular patterns of interaction between unlike molecules and any other factor that could modify such patterns. The minimum in the E vs. composition plots suggests the formation of an adduct of stoichiometric ratio DMFDME=11 at all the investigated temperatures. 相似文献
13.
Graziella Tocco Michela Begala Giovanna Delogu Carmen Picciau Gianni Podda 《Tetrahedron letters》2004,45(37):6909-6913
In the presence of catalytic amount of indium(III) chloride (10 mol %), 2,2′-dihydroxybiphenyl and bis(2-hydroxyphenyl)methane react quickly, without using any solvent, with ketones or β-keto esters possessing at least one hydrogen atom in α to the ketone-carbonyl group, to afford some new dibenzo(d,f)(1,3)dioxepines and some 12H-dibenzo(d,g)(1,3)dioxocin derivatives, respectively. 相似文献
14.
Luca Bernazzani Maria Rita Carosi Celia Duce Paolo Gianni Vincenzo Mollica 《Journal of solution chemistry》2006,35(11):1567-1585
Excess molar volumes, V
m
E, over the whole composition range for binary mixtures of 1-butanol, 2-butanol, and 2-methyl-2-propanol + 1-octanol, or 2-octanol, or di-n-butyl ether, or n-hexylacetate were determined at 298.15 K from density measurements carried out with a vibrating-tube densimeter. Small V
m
E values, both positive and negative, are displayed by mixtures containing 1- or 2-octanol, whereas positive and larger values are always found for mixtures containing dibutyl ether and hexylacetate. These results can be justified in terms of H-bonding interactions and/or steric hindrance due to the branched alkyl chains. Partial molar volumes at infinite dilution of the isomeric butanols in the C8 compounds were also calculated from the apparent molar volumes in dilute solution. The solute-solvent interactions and the effects of the local organisation of the solvent around the butanol molecules were discussed using the void and cavity volumes as different estimates of the intrinsic volume of the molecules. The volumetric behavior of butanols seems to be determined by the solute-solvent interactions rather than packaging effects. 相似文献
15.
Gianni Zotti Sandro Zecchin Giuseppe Pilloni 《Journal of organometallic chemistry》1979,181(2):375-386
The new iron compound, trans-[Fe(DPE)2(MeCN)2] (ClO4)2 (DPE=PPh2CH2CH2PPh2), has been prepared and investigated electrochemically. In acetonitrile the complex shows two reduction steps, consistent with the formation of the stable iron(I) species, [Fe(DPE)2(MeCN)]+ and the rather labile π-bonded acetonitrile adduct, Fe(DPE)2(π-MeCN), respectively. Acetonitrile substitution by carbon monoxide leads to formation of the carbonylated species, which have been characterized, and examined by electrochemical techniques. A significant feature is that trans-[Fe(CO)2(DPE)2]2+, unlike trans-[Fe(DPE)2(MeCN)2]2+, takes up two electrons in a single process, the unstable d7 intermediate undergoing a fast disproportionation. A tentative interpretation of this behaviour is suggested. 相似文献
16.
In this paper we propose a recursive quadratic programming algorithm for nonlinear programming problems with inequality constraints that uses as merit function a differentiable exact penalty function. The algorithm incorporates an automatic adjustment rule for the selection of the penalty parameter and makes use of an Armijo-type line search procedure that avoids the need to evaluate second order derivatives of the problem functions. We prove that the algorithm possesses global and superlinear convergence properties. Numerical results are reported. 相似文献
17.
Galaverna G Sforza S Tedeschi T Corradini R Dossena A Marchelli R 《Electrophoresis》2003,24(15):2698-2703
Direct chiral separation of chiral peptide nucleic acid (PNA) monomers has been achieved for the first time by capillary electrophoresis (CE) with charged cyclodextrins as chiral selectors added to the electrophoretic buffer. Selectively modified 6-deoxy-6-N-histamino-beta-cyclodextrin and sulfobutyl ether-beta-CD were successfully used as chiral selectors for the enantiomeric separation of chiral monomers based on different aminoethylamino acids bearing thymine or adenine as nucleobases. Chiral separations were obtained at low selector concentrations (1-3 mM) with good enantioselectivity and resolution factors. Separations were optimized as a function of pH in order to exploit the effect of the electrostatic interactions between the oppositely charged selector and selectand. The method has been applied to the analysis of the enantiomeric excess of chiral monomers used for the solid phase synthesis of chiral PNA oligomers. CE chiral analysis showed that a very high enantiomeric purity was generally achieved in the synthesis of all monomers, except for histidine and aspartic acid based monomers in which ca. 10% of the "wrong" enantiomer was always present. 相似文献
18.
Stańczak P Valensin D Juszczyk P Grzonka Z Valensin G Bernardi F Molteni E Gaggelli E Kozłowski H 《Chemical communications (Cambridge, England)》2005,(26):3298-3300
The interaction between the single hexarepeat unit of chicken prion protein [ChPrP(54-59)] and Cu(II) was investigated by NMR, finding different coordination modes for the trans/trans and cis/trans isomers. 相似文献
19.
Valensin D Luczkowski M Mancini FM Legowska A Gaggelli E Valensin G Rolka K Kozlowski H 《Dalton transactions (Cambridge, England : 2003)》2004,(9):1284-1293
Potentiometric and spectroscopic data have shown that octarepeat dimer and tetramer are much more effective ligands for Cu(II) ions than simple octapeptide. Thus, the whole N-terminal segment of prion protein due to cooperative effects, could be more effective in binding of Cu(II) than simple peptides containing a His residue. The gain of the Cu(II) binding by longer octarepeat peptides derives from the involvement of up to four imidazoles in the coordination of the first Cu(II) ion. This type of binding increases the order of the peptide structure, which allows successive metal ions for easier coordination. 相似文献
20.
Vladimir Dolgovskiy Stéphane Schilt Nikola Bucalovic Gianni Di Domenico Serge Grop Benoît Dubois Vincent Giordano Thomas Südmeyer 《Applied physics. B, Lasers and optics》2014,116(3):593-601
We demonstrate the first ultra-stable microwave generation based on a 1.5-μm diode-pumped solid-state laser (DPSSL) frequency comb. Our system relies on optical-to-microwave frequency division from a planar-waveguide external cavity laser referenced to an ultra-stable Fabry–Perot cavity. The evaluation of the microwave signal at ~10 GHz uses the transportable ultra-low-instability signal source ULISS®, which employs a cryo-cooled sapphire oscillator. With the DPSSL comb, we measured ?125 dBc/Hz phase noise at 1 kHz offset frequency, likely limited by the photo-detection shot-noise or by the noise floor of the reference cryo-cooled sapphire oscillator. For comparison, we also generated low-noise microwave using a commercial Er:fiber comb stabilized in similar conditions and observed >20 dB lower phase noise in the microwave generated from the DPSSL comb. Our results confirm the high potential of the DPSSL technology for low-noise comb applications. 相似文献