Osmium catalyzed asymmetric dihydroxylation of methyl trans-cinnamate in ionic liquids, followed by supercritical CO2 product recovery

In this work, osmium-catalyzed asymmetric dihydroxylation (AD) of methyl trans-cinnamate was studied. Osmium and chiral ligand catalysts were immobilized in ionic liquid only, without any other reaction solvents, while the recovery of the product was performed by extraction with supercritical CO₂, and compared with results obtained by extractions with organic solvents such as hexane and diethyl ether. In supercritical CO₂ extraction experiments, optimal extraction pressure was found and ionic liquid chosen, so that the highest reaction yields coupled with lowest osmium content in the crude product can be achieved. Finally, recycle experiments of the same (ionic liquid + catalytic system) mixture were successfully conducted. Application of ionic liquids and supercritical CO₂ in osmium catalyzed AD allows for the isolation of the diol basically without contamination with osmium, in high yield and enantiomeric excess, and it makes possible the efficient reuse of ionic liquid solvent and the catalytic system.     

Alkaloid production by callous tissue cultures of Cereus peruvianus (Cactaceae)

The morphologically undifferentiated cells of nonregenerant callous tissue of Cereus peruvianus cultured in the original medium and in medium supplemented with tyrosine were used as an alkaloid source. Comparison of alkaloid production by C. peruvianus plants and by callous tissues indicated that alkaloid levels were almost twice as high in callous tissues as in shoots of C. peruvianus plants. The ratio of alkaloid concentration between mature plant and morphologically und ifferentiated cells of callous tissue was 1∶1.7. A relationship between culture medium containing tyrosine and alkaloid production was also observed in the callous tissues of C. peruvianus. Since increased alkaloid production may be induced by additional factors such as tyrosine, increasing levels of tyrosine or other conditions of the culture medium may be considered factors for inducing higher alkaloid production by C. peruvianus callous tissues.     

New aspects of gold nanorod formation via seed-mediated method

Gold nanorods (AuNRs) were obtained via a wet chemistry technique, in aqueous medium, employing crystallisation seeds. The kinetics of formation, the aspect ratio, and the selectivity of the particles were evaluated according to the parameters of synthesis: the growth-driving agent, seed, and gold precursor concentrations. In 2–4 h, the rod particles attained the expected size and shape under kinetic control, and were stable for at least 2 days. In order to obtain good quality AuNRs in good yields, without enrichment, we suggest keeping the growth-driving agent/gold molar ratio, the Au^I/seed ratio, and the concentration of the reagents in the final solution within specific ranges. For example, even if good molar ratios between the reagents are maintained, relatively highly concentrated reaction solutions lead to AuNRs with lower aspect ratios. The main properties of the prepared colloidal systems and the nanoparticles were evaluated by UV–vis spectroscopy and transmission electron microscopy, respectively.     

Ultra‐high pressure LC for astaxanthin determination in shrimp by‐products and active food packaging

Nowadays, there is increasing interest in natural antioxidants from food by‐products. Astaxanthin is a potent antioxidant and one of the major carotenoids in crustaceans and salmonids. An ultra‐high pressure liquid chromatographic method was developed and validated for the determination of astaxanthin in shrimp by‐products, and its migration from new packaging materials to food simulants was also studied. The method uses an UPLC® BEH guard‐column (2.1 × 5 mm, 1.7 µm particle size) and an UPLC® BEH analytical column (2.1 × 50 mm, 1.7 µm particle size). Chromatographic separation was achieved using a programmed gradient mobile phase consisting of (A) acetonitrile–methanol (containing 0.05 m ammonium acetate)–dichloromethane (75:20:5, v/v/v) and (B) ultrapure water. This method was evaluated with respect to validation parameters such as linearity, precision, limit of detection, limit of quantification and recovery. Low‐density polyethylene films were prepared with different amounts of the lipid fraction of fermented shrimp waste by extrusion, and migration was evaluated into food simulants (isooctane and ethanol 95%, v/v). Migration was not detected under the tested conditions. Copyright © 2012 John Wiley & Sons, Ltd.     

Tetragonal to monoclinic phase transition observed during Zr anodisation

Plasma electrolytic oxidation (PEO) is a coating procedure that utilises anodic oxidation in aqueous electrolytes above the dielectric breakdown voltage to produce oxide coatings that have specific properties. These conditions facilitate oxide formation under localised high temperatures and pressures that originate from short-lived microdischarges at sites over the metal surface and have fast oxide volume expansion. Anodic ZrO₂ films were prepared by subjecting metallic zirconium to PEO in acid solutions (H₂C₂O₄ and H₃PO₄) using a galvanostatic DC regime. The ZrO₂ microstructure was investigated in films that were prepared at different charge densities. During the anodic breakdown, an important change in the amplitude of the voltage oscillations at a specific charge density was observed (i.e., the transition charge density (Q ^T)). We verified that this transition charge is a monotonic function of both the current density and temperature applied during the anodisation, which indicated that Q ^T is an intrinsic response of this system. The oxide morphology and microstructure were characterised using SEM and X-ray diffraction experiments (XRD) techniques. X-ray diffraction analysis revealed that the change in voltage oscillation was correlated with oxide microstructure changes during the breakdown process.     

Electrochemical Behaviour and Square Wave Voltammetry of the Rice Herbicides Molinate,Bensulfuron-Methyl,Mefenacet and Thiobencarb

Abstract

Cyclic, differential pulse and square wave voltammetry were applied to develop an electroanalytical procedure for the determination of a group of herbicides used to treat rice crops: molinate, bensul-ruron-methyl, mefenacet and thiobencarb. The oxidation mechanism causes adsorption problems and consequent poisoning of the electrode surface by the products of the electrochemical reaction. Parameters such as pH, frequency and electrochemical electrode surface treatment were optimized. The analytical methodology developed using square wave voltammetry was applied to the determination of molinate and bensulfuron-methyl in simple or mixed commercial products.     

Optimized Synthesis of Silver Nanoparticles by Factorial Design with Application for the Determination of Melamine in Milk

A colorimetric method based on silver nanoparticles was developed for the determination of melamine in milk. Silver nanoparticles were synthesized without any stabilizer, using sodium borohydride as the reducing agent. Optimization of the variables for the formation of the nanoparticles was performed by factorial design, resulting in stable colloidal silver nanoparticles with a mean diameter of 14.0?±?2.7?nm. Spectrophotometric measurements performed at 475?nm showed a linear range from 0.033 to 1.50?mg?L^?1 of melamine with limits of detection and quantification of 0.009 and 0.031?mg?L^?1, respectively. The method provided highly sensitive determination of melamine in milk.     

Kinetic study of template removal of Al-MCM-41 synthesized at room temperature

The Al-MCM-41 molecular sieve with Si/Al = 20 molar ratio was synthesized at room temperature and characterized by X-ray diffractometry, surface area, thermogravimetry, and infrared spectroscopy. The kinetic study was conducted by Vyazovkin and Ozawa method, in order to verify the activation energy during the Hofmann degradation between 130 and 370 °C, in which most of surfactant removal occurs. The results suggest that the activation energy for template removal is close to 80 kJ mol^?1 lower in Al-MCM-41 synthesized at room temperature, when compared to results obtained for mesopores Al-MCM-41 and MCM-41 synthesized by hydrothermal method. This lower activation energy may be understood as consequence of textural properties, such as higher pore size.