Analytical capabilities of inductively coupled plasma orthogonal acceleration time-of-flight mass spectrometry (ICP-oa-TOF-MS) for multi-element analysis of food and beverages

Analytical capabilities of ICP-oa-TOF-MS for rapid, simultaneous and reliable determination of more than 50 major, trace and ultra-trace elements in different food and beverages samples (milk and dairy based products, cereals, meat, offal, sugar and sugar products, potatoes, fats, baby food samples, fruit juices, alcoholic beverages), following microwave closed vessel digestion of samples, were described. Under optimum instrumental conditions, and by using Rh as an internal standard and an external calibration method, ICP-oa-TOF-MS enables an accurate analysis, taking about one minute per a sample for all elements and isotopes of interest even for some elements such Zn, Ni, Cu, As or Co whose assay is more difficult when using conventional quadrupole instruments. In order to verify the accuracy and precision of the proposed method, 8 commercially available reference materials representing 3 major groups of food (milk and dairy based products, meat, cereals) were analysed, yielding results in agreement with certified values and the precision bellow 15%. In addition, accuracy was confirmed by spiked analytical recoveries study and accurate isotopic ratio determinations with the precision typically better than 5% with 5 s data acquisition period, also for other elements of interest whose content was not certified and different sample matrices. Limits of detection (3σ) have varied from 0.04 ng g⁻¹ for Th to 1630 ng g⁻¹ for Ca.     

Catalytic decomposition of nitric oxide by perovskites

Catalytic decomposition of nitric oxide has been studied for nearly a century, using materials ranging from noble metals to alkaline earth metal oxides, without much success. Only since about last fifteen years some progress in finding promising materials has been made. Of the numerous catalyst systems studied, very few show tangible decomposition rates : copper substituted zeolites, silver-cobalt mixed oxides, some perovskites, and supported noble metals. Although at 773 K the rates of decomposition over zeolites are two to three orders higher than those over remaining systems, these materials have very low thermal stability, above 773 K. In this respect, perovskites have much higher potential, although so far no composition exhibiting practical decomposition rates has been found. Systematic study of the effect of composition on the performance should help to advance the complete understanding of this important reaction. In this paper a current state of art is outlined, and some latest preliminary results for new specially formulated perovskites are presented.     

Lucifensin, a novel insect defensin of medicinal maggots: synthesis and structural study

Recently, we identified a new insect defensin, named lucifensin that is secreted/excreted by the blowfly Lucilia sericata larvae into a wound as a disinfectant during the medicinal process known as maggot therapy. Here, we report the total chemical synthesis of this peptide of 40 amino acid residues and three intramolecular disulfide bridges by using three different protocols. Oxidative folding of linear peptide yielded a peptide with a pattern of disulfide bridges identical to that of native lucifensin. The synthetic lucifensin was active against Gram-positive bacteria and was not hemolytic. We synthesized three lucifensin analogues that are cyclized through one native disulfide bridge in different positions and having the remaining four cysteines substituted by alanine. Only the analogue cyclized through a Cys16-Cys36 disulfide bridge showed weak antimicrobial activity. Truncating lucifensin at the N-terminal by ten amino acid residues resulted in a drop in antimicrobial activity. Linear lucifensin having all six cysteine residues alkylated was inactive. Circular dichroism spectra measured in the presence of α-helix-promoting compounds showed different patterns for lucifensin and its analogues. Transmission electron microscopy revealed that Bacillus subtilis treatment with lucifensin induced significant changes in its envelope.     

Assay of Citrus Flavonoids, Troxerutin, and Ascorbic Acid in Food Supplements and Pharmaceuticals by Capillary Zone Electrophoresis

Capillary electrophoretic method suitable for the assay of citrus flavonoids (hesperidin, diosmin, and rutin), troxerutin, and ascorbic acid in food supplements and pharmaceutical formulations was devised and validated. The separation was carried out at 25 kV in uncoated fused-silica capillary (50 μm i.d.; total length, 32 cm (21 cm to detector); and spectrophotometric detection at 280 nm) maintained at 25 °C with 40 mM sodium tetraborate buffer of pH 9.5 containing 25 % (v/v) of methanol as the background electrolyte. The samples were injected hydrodynamically (50 mbar, 6 s). The calibration curves were linear (correlation coefficients r?=?0.9994–0.9998) for 0.05–0.50 mg/mL of hesperidin, diosmin, rutin, and troxerutin and 0.10–1.00 mg/mL of ascorbic acid when using cinnamic acid (0.05 mg/mL) as internal standard (IS). The LOQ values (S/N?=?10) ranged between 0.02 and 0.04 mg/mL of an analyte. The intra- and interday repeatability of migration times and corrected peak areas was characterized by RSD?≤?3.6 %. Single CE analysis of a standard mixture containing all five analytes and the IS took less than 11 min. Accuracy of the method was evaluated by the added/found analyte recovery experiments (recoveries, 95.5–99.8 %). The method was applied to the analysis of five commercially available food supplements and pharmaceuticals.     

Antioxidants and stabilizers

Summary The efficiency of polyolefine melt stabilizer 2, 2-thiobis-(4,6-di-tert.butylphenol) (I) as a hydroperoxide decomposing antioxidant was studied under model conditions.tert.Butylhydroperoxide was used to simulate the reaction with polypropylene hydroperoxide. The reaction was performed at 85°C in chlorobenzene solution. Decomposition of tert.butylhydroperoxide by I and formation of the sulphoxide II and the sulphone III from sulphide I were followed quantitatively. Formation of small amounts of effective peroxidolytic species from II or III, responsible for acceleration of hydroperoxide decomposition was considered.     

Uranyl prepared by the internal gelation. Part I. The determination of the gelation regions in uranyl nitrate systems

In the present paper preparation conditions for the formation of various types of uranyl gel, using the internal gelation route, are described. Various types of the gel can be prepared differing in their physico-mechanical properties. The research parameters were selected with respect to practical preparation conditions. The results of the paper represent an attempt to investigate systematically some of the basic chemistry problems of the gel process.     

Antioxidants and stabilizers, 116 Influence of the carbon black chezacarb EC on polyolefin thermooxidation: A model study with cyclohexene doped with chain-breaking antioxidants

The ageing of polyolefins is accelerated by carbon black Chezacarb EC used as a filler. Conditions for selection of suitable chain-breaking antioxidants protecting against degradation were simulated using cyclohexene doped with various amounts of carbon black and oxidized at 60°C. The results obtained reveal an acceleration of cyclohexene oxidation in the phase following the induction period (IP). The oxidation acceleration is similar to the effect caused by powdered copper(0) or copper(II) ions. Polynuclear phenolic antioxidants are able to stabilize cyclohexene for periods longer than 120 h only in the presence of low amounts of Chezacarb (up to 0.5 wt.-%). At higher Chezacarb concentrations, merely a prolongation of IP may be achieved. Arylene diamines are efficient stabilizers only if combined with a high concentration of Chezacarb (10 wt.-%). None of the chain-breaking antioxidants used was able to diminish the oxidation rate of cyclohexene in the phase after IP.     

Catalytic performance of La0.66Sr0.34Co0.2Fe0.8O3 perovskite in propane combustion: Effect of preparation and specific surface area

Several compositions in a system of La_1-x SrxCo_1-y FeyO_3-δ perovskites are known as very good electronic and ionic conductors, as well as excellent catalysts for hydrocarbon oxidation. In this study La_0.66Sr_0.34Co_0.2Fe_0.8O₃ was selected as possibly the optimum composition. To assess the effect of preparation and calcination conditions on the activity in propane combustion, a series of different samples was prepared by a method based on slurry of reactive component precursors processed by freeze-drying. Three different materials were used as source of iron and the samples were aged at successively higher temperatures (1,153–1,343 K). The specific surface areas varied between 5.9 and 1 m²/g, depending on iron precursor and/or aging. The activity was determined in an integral U-shape reactor, typically for 1 and 2 vol% propane in air, with 1 g catalyst and 200 or 100 ml/min flowrate. Kinetics determined on the basis of a wider range of concentrations (1–4.3 vol% propane; 10 vol%-pure oxygen) for a selected, the least aged sample indicated that the propane catalytic combustion is best represented by a Mars van Krevelen model with 0.5 order in oxygen and the two kinetic constants having E _app of 83 and 81 kJ/mol, respectively. For the aged samples, the pseudofirst order E _app varied from 85 to 98 kJ/mol.     

Flame retardancy afforded by polyaniline deposited on wood

Wood scantlings were coated with polyaniline (PANI) during the in situ polymerization of aniline with ammonium peroxydisulfate in an aqueous medium. The coating was made in hydrochloric or phosphoric acid solutions in both the absence and presence of stabilizers, poly(N‐vinylpyrrolidone) or colloidal silica. The PANI‐coated wood was placed in a flame or in a furnace operating at 400 or 600°C, and the decrease in the mass was determined. The wood coated with PANI was less reduced in its mass than uncoated samples and was converted to charcoal rather than to ashes. The deposition of related polymers, polypyrrole and poly(1,4‐phenylenediamine), provided similar protection against heat exposure. Fourier transform infrared and Raman spectra of the residues after the burning of PANI‐coated wood were compared. The soaking of wood in PANI colloids did not result in similar protection of wood against fire; the coating of the cellulose fibers with PANI during the polymerization was needed for the enhanced stability of wood at elevated temperatures. The concept of carbonization processes at the surface layer of PANI‐coated cellulose fibers leading to the formation of carbonaceous microtubes is offered to explain the improved stability of wood against flame and heat exposure. © 2006 Wiley Periodicals, Inc. J Appl PolymSci 103: 24–30, 2007     

Antioxidants and stabilizers, 117. Contribution to the transformation mechanism of 2,6-di-tert-butyl-4-methylphenol,a processing stabilizer for polyolefins

2,6-Di-tert-butyl-4-methylphenol (1) , a polyolefin processing stabilizer, is transformed during the stabilization process primarily into 2,6-di-tert-butyl-4-methyl-phenoxyl (2) . The important consecutive transformation pathway of 2 involves irreversible C? C coupling giving 4,4′-ethylenebis(2,6-di-tert-butylphenol) (8) and reversible C? C coupling accounting for formation of 2,6-di-tert-butyl-4-methyl-4-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,5-cyclohexadiene-1-one (9) . The stepwise transformation of 9 into the parent phenol 1 , the stable dimer 8 and a variety of other products was found in EPR and chromatographic studies of free radical and molecular products generated from 9 in oxidative environment. It follows that compounds 1, 8 and 9 are stepwise transformed into coloured quinoide and quinonemethinoide compounds in the ultimate phase, and the antioxidant chain-breaking character of 1 is thus lost. It is considered that most of the free radical species formed transiently during transformation of 1 and/or of derived phenolic coupling products disappear from the system via disproportionation and alkylperoxy radicals (RO₂) or oxygen trapping. Labile, cross-conjugated, peroxidic species generated by the latter process contribute to the fragmentation of coupling products.