Migration of Ethylene Terephthalate Oligomers from Roasting Bags into Olive Oil

Summary A high-performance liquid-chromatographic method with UV detection (HPLC–UV) has been developed for quantification of ethylene terephthalate oligomers in olive oil, from which they were extracted with acetonitrile. Oligomers, from monomers (M₁) to pentamers (M₅), were jointly and/or individually identified by liquid chromatography with mass spectrometry (electron-impact mass spectrometry (EIMS) low- and high-resolution) and were quantified by HPLC–UV using an acetonitrile solution of the major oligomer (the trimer M₃) as standard. For M₃ recovery was 98.9%, the detection limit was 60 g L^–2, and method precision was 2.03% (RSD). Migration of oligomers M₁–M₅ into 50 mL olive oil sealed in each of two brands of 10 cm × 10 cm poly(ethylene terephthalate) roasting bag was evaluated under two sets of conditions that approached but remained below the limit at which the bag material became physically deformed – heating for 7 min at 850 W in a microwave oven, or for 60 min at 200 °C in a conventional oven. Total migration was approximately 2.7 mg dm^–2 under the former conditions and 3.5–4.1 mg dm^–2 under the latter.Presented at the International Symposium on Separation and Characteristics of Natural and Synthetic Macromolecules, Amsterdam, The Netherlands, February 5–7, 2003     

On the structure formation of hydrophobed particles in the boundary layer of water and octane phases

Two-dimensional aggregation of the surface modified glass beads was carried out in the boundary layer of water and octane phases. The effect of particles' hydrophobicity was investigated on the structure of forming aggregates and the growth process. The structure of the aggregates and their growth were characterized by a density function which demonstrates the change of mean particle density as a function of aggregate size. The growth yielded fractal or nonfractal structures in the investigated systems. The fractal structure of the aggregates was observed to be dependent on restructuring processes controlled by the surface properties of the beads.The experimental results are compared with earlier findings for aggregation of hydrophobic beads in the boundary layer of water and air phases.On leave from Loránd Eötvös University, Budapest, Hungary     

Isolation and characterization of 3,5,6-trihydroxy-carotenoids from petals ofLilium tigrinum

Summary Reinvestigation by HPLC of the petals ofLilium tigrinum and the isolation of some minor compounds is reported. Using HPLC-controlled, preparative-column chromatography, 5,6-diakarpoxanthin (6), 6-epikarpoxanthin (2), 5,6-diacapsokarpoxanthin (8), and 9Z-antheraxanthin (9Z-13) were isolated and characterized. Based on spectroscopic data the absolute configurations of6 and8 were identical with those originating from paprika, thus the 5,6-diakarpoxanthin (6) and 5,6-diacapsokarpoxanthin (8) have the 3S, 5S, 6S configuration and 6-epikarpoxanthin (2) has the 3S, 5R, 6S configuration. Presented at: Balaton Symposium on High-Performance Separation Methods, Siófok, Hungary, September 3–5, 1997.     

High-performance liquid chromatographic determination of glycogen in sea urchin gonads with refractive index detection

A high-performance liquid chromatographic method using refractive index detection for the determination of glycogen in sea urchin (Paracentrotus lividus) gonads is developed. After alkaline digestion with sodium carbonate, samples are adjusted to pH 4.6 with citric acid and incubated with amyloglucosidase to hydrolyze the glycogen. The resulting glucose is determined using a Spherisorb NH2 column as the stationary phase and an acetonitrile-water mixture (80:20, v/v) as the mobile phase. The relative standard deviation (%) was 3.57, the limit of detection was 40.1 microg/mL, and the recovery percentage was 97.2%.     

A ferrocene-based heteroditopic ligand for electrochemical sensing of cations and anions

A ferrocene-based heteroditopic receptor containing urea and crown ether units shows electrochemical responses to dihydrogenphosphate and fluoride anions. K+ cations can only be detected in the presence of dihydrogenphosphate.     

Determination of azolic fungicides in wine by solid-phase extraction and high-performance liquid chromatography-atmospheric pressure chemical ionization-mass spectrometry

A method for simultaneous analysis of eight azolic fungicides: cyproconazole, diniconazole, tetraconazole, thiabendazole, flusilazole, triadimenol, triadimefon, carbendazim and the degradation product 2-aminobenzimidazole in wine samples is described. The compounds are isolated from the samples and concentrated by solid-phase extraction on polymeric cartridges. The determination is carried out by liquid chromatography with mass spectrometric detection in positive ionization and selected ion monitoring modes. The influence of parameters such as the mobile phase composition, column temperature, corona current and fragmentor voltage is studied and the proposed method is validated. Recoveries of the nine compounds added to wine samples range from 83 to 109%, with relative standard deviations below 10%. The quantitation limits are between 9 and 31 microg/L. Real wine samples are analyzed by the proposed method, also.     

Thermal characterization of benzylcellulose derivatives prepared from bleached pinus kraft pulp

The thermal characterization (DSC and TG) of benzylcellulose derivatives prepared from the benzylation of bleached Pinus Kraft pulp is described in this paper. The objective of this study was to examine the changes in glass transition temperature (T _g) and the thermal stability of the benzylated product as a function of the benzylation extent (degree of substitution). The DSC analysis showed that the benzylcelluloses can display glass transition temperature at two different regions and that thermal stability is slightly higher than that of the parent cellulose. This revised version was published online in August 2006 with corrections to the Cover Date.     

As, Bi, Sb and Sn determination in atmospheric particulate matter by direct solid sampling-hydride generation-electrothermal atomic absorption spectrometry

A novel, rapid and simple method by hydride generation-electrothermal atomic absorption spectrometry (HG-ETAAS) after direct As, Bi, Sb and Sn hydrides generation from untreated filters of atmospheric particulate matter (PM₁₀ and PM_2.5) was optimised. PM₁₀ and PM_2.5 were not subjected to any pre-treatment: circular portions between 0.28 and 6.28 cm² were directly placed into the reaction vessel of a batch mode generation system. A 2⁸ × 3/64 Plackett–Burman design was used as a multivariate strategy for the evaluation of the effects of several variables affecting the hydride generation, trapping and atomisation efficiencies. Trapping temperature was the most statistically significant variable for As, Bi and Sn. Atomisation temperature was also statistically significant for Sb determination. Optimum values of significant variables were selected by using univariate optimisation approaches. An aqueous calibration method was used throughout. The developed method has been found to be precise with relative standard deviations of 6.2, 5.3, 9.1 and 7.5% for 11 determinations in a filter sample containing 0.7, 1.0, 1.4 and 1.7 μg l⁻¹ for As, Bi, Sb and Sn, respectively. Results obtained by direct solid sampling-HG-ETAAS have been found statistically comparable with those obtained after conventional method based on an acid digestion followed to ICP-MS. Absolute detection limits were 37, 15, 30, and 41 ng l⁻¹ for As, Bi, Sb and Sn, respectively. Detection limits referred to the air volume sampled (in the range of 0.020–0.050 ng m⁻³) were low enough for the determination of several hydride-forming elements from PM₁₀ and PM_2.5 samples collected in a non-polluted suburban area of A Coruña (NW Spain).     

Symmetry numbers and chemical reaction rates

This article shows how to evaluate rotational symmetry numbers for different molecular configurations and how to apply them to transition state theory. In general, the symmetry number is given by the ratio of the reactant and transition state rotational symmetry numbers. However, special care is advised in the evaluation of symmetry numbers in the following situations: (i) if the reaction is symmetric, (ii) if reactants and/or transition states are chiral, (iii) if the reaction has multiple conformers for reactants and/or transition states and, (iv) if there is an internal rotation of part of the molecular system. All these four situations are treated systematically and analyzed in detail in the present article. We also include a large number of examples to clarify some complicated situations, and in the last section we discuss an example involving an achiral diasteroisomer.     

A new selective cleavage of n,n-dicarbamoyl-protected amines using lithium bromide

A mild and new procedure for the selective cleavage of an alkoxycarbonyl group (Boc, CBz) in N,N-dicarbamoyl-protected amino compounds is described. The method is based on the use of lithium bromide in acetonitrile and is compatible with a large range of other functionalities present in the substrates. Compared with other reported methodologies, the procedure is particularly useful for the Cbz-selective cleavage in N,N-Ts,Cbz-diprotected amines. A rationalization of the selectivity supported by ab initio calculations is also presented.