Ozonolysis of tetramethylethylene: characterization of cyclic and open-chain oligoperoxidic products

The ozonolysis of tetramethylethylene (TME) in solution to high conversion in nonparticipating solvents at -60 degrees C yields predominantly oligoperoxides. For the first time, these products have been characterized using electrospray ionization mass spectrometry (ESI-MS) under soft ionization conditions. The predominant structure formed in reactions carried out in pentane (up to 2.0 M TME) is shown to be the cyclic hexamer of acetone carbonyl oxide (oligocarbonyl oxide with degree of polymerization, n = 6), but cyclic structures with n up to 19 are observed. A small proportion of the oligoperoxides formed are open-chain compounds with end groups that suggest that chain termination of oligocarbonyl oxides can occur through reaction with either water or hydrogen peroxide. Ozonolysis in dried butyl acetate similarly produces mainly cyclic oligoperoxides. However, ozonolyses carried out in undried butyl acetate yield mainly open-chain oligoperoxides, confirming that propagating carbonyl oxide chains are readily terminated by water. Relative amounts of the open-chain oligomers so-formed suggest that undried butyl acetate contains ca. 0.1% w/w water. The ozonolysis of TME in the participating solvent, methanol, at -60 degrees C yields 2-methoxyprop-2-yl hydroperoxide via reaction of acetone carbonyl oxide with methanol; no oligoperoxidic products are formed in this case.     

The Effect of Preparation Method and Calcination Temperature on the Crystallite Size and Surface Area of Perovskite-Type SrFeO x

We have investigated the synthesis of perovskite-type SrFeO_x (2.5 x 3.0) using three preparative methods: sol-gel, mechanochemical processing and solid state reactions at high temperature of the corresponding oxides. The sample obtained after calcination of the gel from sol-gel method, contained the least amount of strontium carbonate impurity. The amount of strontium carbonate impurity decreased with the increase in calcination temperature. Perovskites obtained have been characterized by X-ray diffraction (XRD) and nitrogen adsorption isotherms. Samples obtained from three methods have been compared with respect to calcination temperature, crystallite size and specific surface area.Issued as NRCC No. 46479.     

Intermolecular coupling of alkenes to heterocycles via C-H bond activation

The intermolecular coupling of unactivated alkenes to a range of heterocycles using a Rh(I) catalyst was investigated. A variety of functional groups were incorporated into the alkene, including esters, nitriles, acetals, and phthalimide. Furthermore, the heterocycle tolerated substitution with both electron-rich and electron-deficient groups. The intermolecular coupling became possible after it was discovered that weak acids dramatically increase the rate of both the inter- and intramolecular reactions. An extensive optimization of additives was performed, and HCl.PCy(3) (Cy = cyclohexyl) and HCl.P-t-Bu(2)Et were in general found to be the best additives for the reaction.     

A high performance liquid chromatography – inductively coupled plasma-mass spectrometry interface employing desolvation for speciation studies of platinum in chemotherapy drugs

A novel interface between high performance liquid chromatography (HPLC) and inductively coupled plasma-mass spectrometry (ICP-MS) is described. The eluent from the HPLC is nebulised into a heated cyclone spray-chamber and the solvent removed using a Nafion membrane drier, held at 75 degrees C, and a cryogenic condenser. The condenser consists of 6 Peltier heat pumps connected to liquid cooled aluminium blocks. At a nebuliser gas flow rate of 0.6 l min(-1), the membrane drier removes 58% of the vapour and the Peltier condenser 75% of the remaining vapour, i.e. a total desolvation efficiency of 89%. This enables the use of HPLC solvents which otherwise would destabilise the ICP, e.g. 100% acetonitrile or methanol, and permits the use of solvent gradients with minimal baseline drift. The system has been applied to the determination of platinum species in an organoplatinum drug used for chemotherapy in human plasma ultrafiltrate of patients treated with this new drug (JM-216). The limit of detection for platinum species has been 0.6 ng nl(-1) (i.e. 120 pg of Pt) and several species have been separated with good resolution.     

Fluorescence recovery after photobleaching measurements of polymers in a surface forces apparatus

The surface forces apparatus has been combined with fluorescence recovery after photobleaching to measure translational diffusion of polymer confined between mica sheets. This article presents findings using polydimethylsiloxane with number‐average molecular weight M_n = 2200 g mol^?1, the chains end‐labeled with soluble fluorescent dye. Melts with thickness 10 nm display a translational diffusion coefficient (D) with a bulk component and a slower component assigned to surface diffusion. Reduction of thickness to 1.8 nm causes mobility to split into two populations—an immobile fraction (immobile on the time scale of 30–60 min) and a mobile fraction who's D slow only weakly with diminishing film thickness. However, when load causes the confining mica sheets to flatten, D of the mobile fraction drops by up to an additional order of magnitude, depending on the local pressure that squeezes on the polymer. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2010     

Generation of Nucleophilic Chromium Acetylides from gem-Trichloroalkanes and Chromium Chloride: Synthesis of Propargyl Alcohols

Nucleophilic mixed chromium(II) and chromium(III) acetylides are generated from the smooth reduction of primary 1,1,1-trichloroalkanes with chromium(II) chloride in the presence of an excess amount of triethylamine at room temperature. These species arise from chromium(III) vinylidene carbenoids. It has been demonstrated that uncommon low-valent Cr(II) acetylides are formed by C-H insertion of Cr(II)Cl(2) into terminal alkynes, formed in situ through the Fritsch- Buttenberg-Wiechell (FBW) rearrangement, whereas Cr(III) acetylides are concomitantly generated by HCl elimination from the chromium(III) vinylidene carbenoid. Both divergent pathways result, overall, in the formation of nucleophilic acetylides. In situ trapping with electrophilic aldehydes afforded propargyl alcohols. Furthermore, deuteration experiments and the use of deuterium labeled 1,1,1-trichloroalkane substrates demonstrated the prevalence of low-valent Cr(II) acetylides, potentially useful, yet highly elusive synthetic intermediates.     

Simplified method for concentration of mitochondrial membrane protein complexes

Extracting and concentrating mitochondrial protein complexes from gel strips after blue native PAGE (BN‐PAGE) can be daunting tasks using the traditional methods, such as electroelution, passive diffusion and centrifugal concentration. We present a simplified gel electrophoresis method to concentrate mitochondrial protein complexes with excellent recovery rate. Mitochondrial complex I present in a long gel strip from BN‐PAGE can be easily concentrated into a 0.8 cm gel strip when a second BN‐PAGE is performed with a Y‐shaped gel and the addition of 0.01% n‐dodecyl β‐D ‐maltoside and 0.001% SDS in the cathode buffer. Once completed, the concentrated protein complex in the gel strip is ready for SDS‐PAGE or proteomic studies.     

Improvement of the traceability of reference materials certified for purity: evaluation of a semi-preparative high-performance liquid chromatography approach

A semi-preparative high-performance liquid chromatography process was evaluated as a tool to quantitatively determine the purity or percentage mass fraction content (% m/m) of organic compounds. The method is simple and does not require the identification and subsequent quantitation of organic-related structure impurities. A protocol was developed and tested on four reference materials certified for purity from 95% m/m to 99.3% m/m. Comparing the purity results of each certified reference material using the new approach with their respective certified values showed no significant analytical bias. Semi-preparative high-performance liquid chromatography has proved the potential to be a primary method directly traceable to mass with an uncertainty statement written down also in terms of mass with expanding uncertainty ranging from 0.8% to 1.3% m/m compared to 0.3 to 2.0% m/m for the certified purity values at the 95% confidence interval.