Nickel determination in osteoblast-like cell culture medium by adsorptive cathodic stripping voltammetry with a mercury microelectrode

The purpose of this study is to investigate the influence of nickel, which is an alloying element in commonly used metallic biomaterials, on the biomaterials mineralization process. An electrochemical method was developed to quantify this metal ion in osteoblast-like cell culture medium (OST) by performing adsorptive cathodic stripping voltammetry (CSV) with dimethylglyoxime (DMG) at a mercury film microelectrode (MFM). The optimized analytical conditions and the square-wave CSV parameters for the analysis are: DMG concentration: 5.00 × 10⁻⁴ mol L⁻¹; ammonium chloride buffer: 0.10 mol L⁻¹ (pH 9.2); frequency: 50 Hz, amplitude 20 mV; step: 2 mV; adsorption time: 10 s, deposition potential: −0.70 V and reduction potential: −1.20 V. The limit of detection was 7.70 × 10⁻⁹ mol L⁻¹ for an adsorption time of 10 s. The results achieved by CSV using the MFM were compared to those obtained by atomic absorption spectrometry (AAS) to ensure the reliability of the electrochemical method. The mineralization process was evaluated by biochemical and histochemical assays.     

Utilisation de la phenyl-2 dimethyl-4,5 phosphorine comme equivalent synthetique de h=cP. Application a la synthese de la dimethyl-3,4 phosphorine

3,4-Dimethylphosphorin is prepared in five steps from 2,3-dimethylbutadiene and 2-phenyl-4,5-dimethylphosphorin; this synthetic scheme is formally equivalent to a [4+2] cycloaddition between 2,3-dimethylbutadiene and HCP.     

Regioselectivite de la reaction des dialkyl cuprates de magnesium sur des aldehydes α,β-ethyleniques

Various magnesium organocuprates give conjugative addition products with α,β-ethylenic aldehydes, and even with acrolein. The enolates may be trapped with bromine or trimethylsilyl chloride.     

Probing the glycosidic linkage: UV and IR ion-dip spectroscopy of a lactoside

The beta(1-->4) glycosidic linkage found in lactose is a prevalent structural motif in many carbohydrates and glycoconjugates. Using UV and IR ion-dip spectroscopies to probe benzyl lactoside isolated in the gas phase, we find that the disaccharide unit adopts only a single, rigid structure. Its fully resolved infrared ion-dip spectrum is in excellent agreement with that of the global minimum structure computed ab initio. This has glycosidic torsion angles of phi(H) (H1-C1-O-C4') approximately 180 degrees and psi(H) (C1-O-C4'-H4') approximately 0 degrees which correspond to a rotation of approximately 150 degrees about the glycosidic bond compared to the accepted solution-phase conformation. We discuss the biological implications of this discovery and the generality of the strategies employed in making it.     

Conversion directe des phospholes en dihydro-6,7 phosphepines dans la sphere de coordination du tungstene

In the presence of AlCl₃, [1-β-chloroethyl-3,4-dimethylphosphole]pentacarbonyltungsten($\text{1}$) rearranges into [1-chloro-3,4-dimethyl-6,7-dihydrophosphepin]pentacarbonyltungsten ($\text{3}$).     

Reduction des oxydes de phosphines par le systeme Cp2TiCl2-Mg

Phosphine oxides with at least one aryl-P bond are reduced into the corresponding phosphines by stoechiometric amounts of Mg-Cp₂TiCl₂ in boiling THF.     

Volume and heat capacity of model non-aqueous self-assembly systems

Blends of immiscible polymers are often stabilized by block copolymers which can form non-aqueous micelles and microemulsions in the liquid polymers. The phase diagrans, apparent volumes and apparent heat capacities of model non-aqueous binary and ternary systems were studied in order to investigate the conditions under which such self-assembly systems could form. 1,2-Hexanediol, which can cosolubilize hexane and ethyleneglycol, forms inverse micelles in hexane and weak microaggregates in ethyleneglycol. Genapol X-060, a commercial alcoholic surfactant containing on the average an aliphatic chain of 13 carbons and 6 oxyethylenes (C₁₃E₆), forms microaggregates in poly(ethyleneglycol) 400. These self-assembly systems are strengthen in the presence of a third component which has an affinity for the inner phase.Presented at the Symposium, 76^th CSC Congress, Sherbrooke, Quebec, May 30–June 3, 1993, honoring Professor Donald Patterson on the occasion of his 65^th birthday.     

Thermodynamic properties of quinoxaline-1,4-dioxide derivatives: a combined experimental and computational study

The mean (N-O) bond dissociation enthalpies were derived for three 2-methyl-3-(R)-quinoxaline 1,4-dioxide (1) derivatives, with R = methyl (1a), ethoxycarbonyl (1b), and benzyl (1c). The standard molar enthalpies of formation in the gaseous state at T = 298.15 K for the three 1 derivatives were determined from the enthalpies of combustion of the crystalline solids and their enthalpies of sublimation. In parallel, accurate density functional theory-based calculations were carried out in order to estimate the gas-phase enthalpies of formation for the corresponding quinoxaline derivatives. Also, theoretical calculations were used to obtain the first and second N-O dissociation enthalpies. These dissociation enthalpies are in excellent agreement with the experimental results herewith reported.     

A New Method to Prepare Transition Metal Salts of Bulk and Supported Heteropolyacids. Application to the Catalysis of the Oxidative Dehydrogenation of Isobutyric Acid

Transition metal salts of heteropolyacids have been prepared taking into account the strong acidic and cation exchanging properties of the solid heteropolyacids. The exchange between protons and the transition metal cation is carried out by stirring a suspension of the hydrated heteropolyacid in a solution of the metal acetylacetonate complex in toluene. The exchange occurs on the surface of the solid particles and diffusion of protons and metal cations into the hydrated lattice leads to the substitution of all the protons. The method can be utilized in order to prepare supported vanadyl and copper molybdophosphates from supported heteropolyacids and they have been studied in the catalysis of the oxidative dehydrogenation of isobutyric acid. The effect of vanadyl counter-ions on the catalytic behavior is the same as observed with bulk catalysts but, on the contrary, copper supported molybdophosphate shows an acid catalytic activity not observed with bulk catalysts.     

Synthesis and complexing properties of a double-calix[4]arene crown ether

The template synthesis of copper(II) phthalocyanine by the condensation of dicyanobenzene within the supercages of Cu(II) exchanged X and Y type zeolites was studied using differential scanning calorimetry. The exotherms for intrazeolite and surface complexation have been resolved. These thermal events exhibit a dependence on the copper loading and hydration level which has been interpreted as a pressure effect.