Synthesis of α-Metoylene-γ-Lactones in Furanosidic Systems

Abstract

Synthesis of stereoisomeric α-methylene-γ-lactones in furanose-and furanuronoamide derivatives was easily accomplished by Reformatsky Reaction with ethyl bromcmethylacrylic ester and zinc. Pyridinium chlorochromate/3Å molecular sieve powder showed to be an excellent reagent for the oxidation of secondary hydroxyl groups of a furanose system and of α-hydroxy amides.     

Validation and quality control of methylmercury determinations by means of capillary electrophoresis

Methyl-Hg is one of the most dangerous pollutants in the environment. It is highly toxic and accumulates through the food chain. Tuna fish especially tends to concentrate Hg in the form of methyl-Hg. Quality assurance is a well established routine in analytical laboratories to control the variability of analytical results and to maintain adequate stability, detection power and reproducibility. Capillary electrophoresis (CE) has shown in recent years powerful capabilities for the resolution and analysis of very complex samples. The high resolution and peak capacity characteristics of this technique could be used favourably in speciation studies of organo-Hg compounds. Since the time needed for separation is usually very short in this technique, it lends itself to routine analysis. The application of quality control approaches in the analysis of methyl-Hg in tuna freeze-dried materials using CE is reported.     

Thermogravimetric analysis of polycarbonates and polythiocarbonates with chlorinated aromatic side-rings

The thermal stability and kinetics parameters of polycarbonates and polythiocarbonates derived from diphenols with chlorinated aromatic side-rings were studied. The polycarbonates exhibited a higher thermal stability than the polythiocarbonates, except for polythiocarbonate Ib, which displayed similar behaviour to that of the analogous polycarbonate. The kinetic parameters of the thermal decomposition were determined by using the Arrhenius relationship and a computer program. In the considered temperature range, all the polymers degraded in a single stage with first-order kinetics.

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Zusammenfassung Es wurde die thermische Stabilität und die kinetischen Parameter von aus Diphenolen mit chlorierten aromatischen Nebenringen abgeleiteten Polycarbonate und Polythiocarbonate untersucht. Polycarbonate zeigen eine höhere thermische Stabilität als Polythiocarbonate. Eine Ausnahme bildet das Polythiocarbonat Ib, das in seinem Verhalten den Polycarbonaten gleicht. Mittels der Arrheniusschen Gleichung und einem Rechnerprogramm wurden die kinetischen Parameter der thermischen Zersetzung ermittelt. Im untersuchten Temperaturbereich zersetzen sich alle Polymere in einer einstufigen Reaktion erster Ordnung.

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The authors acknowledge financial support from the Dirección de Investigación of the Pontificia Universidad Católica de Chile.     

Determination of Aristocularine Enantiomers by Dispersive Liquid–Liquid Microextraction and Chiral High-performance Liquid Chromatography

Here is reported a novel analytical approach for the extractive separation and determination of enantiomeric ratios of aristocularine in bovine serum albumin. The results demonstrate suitable analytical performances. The separation was performed by chiral high-performance liquid chromatography with a 5-µm column using a mobile phase of 1:1 n-hexane:ethanol at a flow rate of 0.7?mL?min^?1 with ultraviolet–visible absorption, circular dichroism, and polarimetric detection. The enantiomers were eluted at 13.2 and 15.6?min for (+) and (?)-aristocularine, with a resolution of 1.58 and a separation factor of 1.27. The analytical parameters for the dispersive liquid–liquid microextraction were optimized; under these conditions, the extraction recoveries were from 88.6% to 93.9% for a two-step extraction. The precision, reported as the percent relative standard deviation, had values from 2.9% to 3.2% for 0.5?µg?mL^?1 of analyte for five replicate measurements using ultraviolet–visible absorption and circular dichroism detection. The limits of detection were between 0.05 and 0.08?µg?mL^?1 with enrichment ratios up to a value of 12.     

Complexes of osmium (III) obtained from OsO4 and ethylenethioureas. A kinetic study of the reduction in HClO4 solutions

Summary OsO₄ reacts with imidazolidine-2-thione and itsN-methyl andN-ethyl derivatives in acidified 11 vol. H₂O:EtOH to give [OsL₆]³⁺. Complexes obtained in the presence of HClO₄ or HBF₄ have been isolated as crystals and characterized by elemental analysis, i.r. spectroscopy and magnetic measurements.All the ligands bind the metal through the sulphur atom and the magnetic measurements are consistent with low spin osmium(III). The kinetics of [OsL₆]³⁺ formation has been followed spectrophotometrically. Thepseudo-first order rate constants are linear both with respect to the acid and the ligand concentrations, indicating that the kinetically significant process involves one proton and one molecule of the ligand. A comparison of these results with those obtained for the analogous reaction with thiourea is reported.     

Creating a Model of Acceptance: Preservice Teachers Interact With Non‐English‐Speaking Latino Parents Using Culturally Relevant Mathematics and Science Activities at Family Learning Events

The following describes a culturally relevant mathematics and science content program implemented by preservice teachers (PSTs) at Family Math/Science Learning Events (FM/SLEs) conducted through two different university programs in south Texas. These experiences are required course activities designed to inform PSTs of the importance of interacting with Latino families' culture and language in after school settings. Data were collected from elementary PSTs attending FMLEs and include interactions recorded during the FMLE and interviews with Latino non‐English‐speaking parents after the event. Anecdotal data were also included from parents' interviews collected during culturally relevant Family Science Learning Events. Researchers investigated the following questions: (1) what did Latino parents and PSTs report learning from the FMLE and, (2) how do perceptions toward Latino parents change when PSTs are given the opportunity to interact with and interview Latino parents? Results show that PSTs perceptions of Latino parents can be changed through these events. Implications for teacher preparation programs include providing PSTs with opportunities for participation in FM/SLEs that incorporate planning and teaching culturally relevant math and science activities. The following model of acceptance requires PSTs to identify and reconstruct misconceptions and perceptions of parents, especially non‐English‐speaking Latino parents.     

Small generators of the ideal class group

Assuming the Generalized Riemann Hypothesis, Bach has shown that the ideal class group of a number field can be generated by the prime ideals of having norm smaller than . This result is essential for the computation of the class group and units of by Buchmann's algorithm, currently the fastest known. However, once has been computed, one notices that this bound could have been replaced by a much smaller value, and so much work could have been saved. We introduce here a short algorithm which allows us to reduce Bach's bound substantially, usually by a factor 20 or so. The bound produced by the algorithm is asymptotically worse than Bach's, but favorable constants make it useful in practice.

     

Design of an Optimal Grid for Finite Element Methods

ABSTRACT Finite element solutions of improved quality are obtained by optimizing the location of nodes of the finite element grid, while keeping the number of degrees of freedom fixed. The formulation of the grid optimization problem is based on the reduction of error associated with interpolation of the exact solution, using functions from the finite element space. Element sizes are selected as design variables: length in R1 and area in R2. Analytically derived optimality conditions are presented and an approximation to these conditions is introduced to obtain a set of operationally useful equations that can be used as guidelines for construction of improved grids. Example problems are given for illustration.     

Neutron scattering study of the magnetoelectric compound GaFeO 3

We present a neutron scattering study carried out on single-crystals of the magnetoelectric compound GaFeO₃, prepared by the floating-zone (FZ) method. The refinement of the crystal structure indicates the existence of a large amount of iron on the gallium site, corresponding to a strong internal substitution disorder. We show that the Ga/Fe disorder and the magnetic transition temperature are weakly dependent on the growth conditions. The disorder also affects the magnetic excitations; our measurements evidence damped spin waves, well defined only close to the Brillouin zone centre.     

Observation of defect clustering in Gd-doped calcium fluoride

Abstract

Solid solutions Ca_1-xGd_xF_2+x for 3 × 10^?7≤ x ≤10^?1 have been studied by electron paramagnetic resonance (EPR) and ionic thermal currents (ITC). The EPR experiments show the presence of two single-ion sites a cubic and a tetragonal Gd³⁺ center which co-exist with comparable abundances for intermediate impurity concentrations. The cubic center predominates at very low and high concentrations. Seven different relaxation processes have been identified from the ITC spectra and the variation of their intensity vs. x was measured. The absolute concentrations of the cubic and nn Gd³⁺ dipoles were calculated. The scavenging of interstitial fluorines by the neutral clusters explains both the abundance of cubic sites at high concentration and the variety of orientable clusters detected by ITC.