Stereoselective syntheses of polyhydroxylated azepane derivatives from sugar-based epoxyamides. Part 1: synthesis from d-mannose

An approach to the synthesis of polyhydroxyazepane derivatives from sugar-based epoxyamides or epoxyalcohols, in which the total regioselective epoxide opening by nitrogen nucleophiles is the key step, is described. Thus, novel polyhydroxyazepane carboxamides and aminomethyl polyhydroxyazepanes, with potential pharmacological interest, are synthesized from diacetone d-mannose. Configurational assignments of the obtained products were determined.     

Thermal behavior study of biodiesel standard reference materials

Quality control of fuel-related properties of biodiesel, such as thermal stability, is needed to obtain consistent engine performance by fuel users, since biodiesel is susceptible to auto-oxidation when exposed to air, light, and temperature during storage. In this work two pure standard reference materials of biodiesels produced from soy oil and animal feedstocks were studied. Differential scanning calorimetry and thermogravimetry measurements were performed and the analysis of the results revealed small temperature variations in the thermal events among the two standards, these differences are due mainly to their chemical composition, been highly influenced by the amounts of unsaturated esters.     

��-convergence of energies for nematic elastomers in the small strain limit

We study two variational models recently proposed in the literature to describe the mechanical behaviour of nematic elastomers either in the fully nonlinear regime or in the framework of a geometrically linear theory. We show that, in the small strain limit, the energy functional of the first one Γ-converges to the relaxation of the second one, a functional for which an explicit representation formula is available.     

Direct amperometric determination of tert-butylhydroquinone in biodiesel

The direct amperometric determination of tert-butylhydroquinone (TBHQ) in biodiesel at an unmodified glassy carbon electrode is reported. A biodiesel aliquot was added into an electrochemical cell containing a 75% (v/v) ethanol-water solution under stirring (with final concentration of 50 mmol L⁻¹ HClO₄). The amperometric method involved the continuous application of three sequential potential pulses to the working electrode (700 mV for 300 ms, 0 mV for 100 ms and −50 mV for 1 s). TBHQ was continuously monitored at the first (direct oxidation) and optionally at the second (reduction) potential pulse while the third potential pulse was applied for cleaning of the electrode surface. For comparison, the samples were also analyzed by high-performance liquid-chromatography and a good agreement between the results was verified. Recovery values for spiked samples were between 90% and 95% and the reproducibility of the proposed method was around 5% (n = 5). The proposed method can be easily adapted for on-site analysis.     

Experimental and theoretical analysis of bias ionization by?α-particles in a nitrogen laser

Nitrogen laser performance with TE configuration and wedge electrodes is analyzed with background ionization in the laser discharge channel by α particles at a low exposition rate. With the bias ionization, the laser power presents two peaks as a function of gas pressure, with one at the normal low pressure, without bias ionization, and the other at high pressure generated by bias ionization. A simple theoretical model has been developed in a trial to understand this behavior. This model was first tested in later results for a TE configuration nitrogen laser, with flat electrodes, without and with bias ionization. It has been observed that due to the competition between electrode shielding by positively charged α particles and bulk ionization by impact, the laser energy is suppressed with pressure below 50 Torr and enhanced above it.     

Production of metakaolin from industrial cellulose waste

Research focused on the transformation and utilization of industrial wastes into products of commercial interest plays an increasingly important role. Residual pulp can become useful in the manufacture of different materials, providing high value to this waste and reducing its environmental impact when disposed of improperly in the environment. The main constituents of this waste are kaolin and calcium carbonate (CaCO₃). Starting from kaolin, metakaolin can be produced by calcination of the residue at 630?°C for 2?h in a rotary reactor with air flow, followed by solubilization with hydrochloric acid to remove the CaCO₃. The development of technological alternatives aimed at the reuse of certain wastes can result in applications of real economic interest to the chemical industry and ceramics and glass, which is the case in this study. The raw material and metakaolin obtained were analyzed by thermogravimetric analysis and derivative thermogravimetric analysis, X-ray diffraction, and X-ray fluorescence spectroscopy with promising results. This is because metakaolin was obtained free of contamination by other materials.     

Advances on the Determination of the Astatine Pourbaix Diagram: Predomination of AtO(OH)2− over At− in Basic Conditions

It is generally assumed that astatide (At^?) is the predominant astatine species in basic aqueous media. This assumption is questioned in non‐complexing and non‐reductive aqueous solutions by means of high‐pressure anion‐exchange chromatography. Contrary to what is usually believed, astatide is found to be a minor species at pH=11. A different species, which also bears a single negative charge, becomes predominant when the pH is increased beyond 7. Using competition experiments, an equilibrium constant value of 10^?6.9 has been determined for the formation of this species from AtO(OH) with the exchange of one proton. The identification of this species, AtO(OH)₂^?, is achieved through relativistic quantum mechanical calculations, which rule out the significant formation of the AtO₂^? species, while leading to a hydrolysis constant of AtO(OH) in excellent agreement with experiment when the AtO(OH)₂^? species is considered. Beyond the completion of the Pourbaix diagram of astatine, this new information is of interest for the development of ²¹¹At radiolabeling protocols.