An evaluation of analytical techniques for determination of lead, cadmium, chromium, and mercury in food-packaging materials

Closed microwave digestion and a high-pressure asher have been evaluated for wet-oxidation and extraction of lead, cadmium, chromium, and mercury from a range of typical packaging materials used for food products. For the high-pressure asher a combination of nitric and sulfuric acids was efficient for destruction of a range of packaging materials; for polystyrene, however, nitric acid alone was more efficient. For microwave digestion, a reagent containing nitric acid, sulfuric acid, and hydrogen peroxide was used for all materials except polystyrene. Use of the high-pressure asher resulted in the highest recoveries of spiked lead (median 92%), cadmium (median 92%), chromium (median 97%), and mercury (median 83%). All samples were spiked before digestion with 40 microg L(-1) Cd, Cr, and Pb and 8 microg L(-1) Hg in solution. The use of indium as internal standard improved the accuracy of results from both ICP-MS and ICP-AES. Average recovery of the four elements from spiked packaging materials was 92 +/- 14% by ICP-MS and 87 +/- 15% (except for mercury) by ICP-AES. For mercury analysis by CVAAS, use of tin(II) chloride as reducing agent resulted in considerably better accuracy than use of sodium borohydride reagent.     

Synthesis of ynones by palladium-catalyzed acylation of terminal alkynes with acid chlorides

Phosphane-free oxime-derived palladacycle 2 is an efficient precatalyst for the copper-free acylation of terminal alkynes with different carboxylic acid chlorides in toluene in the presence of 3 equiv of TEA as base, giving the corresponding ynones in good yields. The coupling reaction can normally be performed under air or under inert atmosphere when very low catalyst loadings (10(-3) mol % Pd) (turnover numbers (TONs) up to 23,000, turnover frequencies (TOFs) up to 958 h(-1)) or sensitive carboxylic acid chlorides are used. In addition, Pd(OAc)(2) has been shown as an efficient catalyst for the ligandless process, although usually working under higher loading conditions. This new protocol allows one to perform the synthesis of ynones at 110 degrees C, at room temperature, or under microwave irradiation conditions.     

Analysis of polar hydrophilic aromatic sulfonates in waste water treatment plants by CE/MS and LC/MS

The present work describes the development and optimization of a capillary (zone) electrophoresis/mass spectrometric (CE/MS) analysis method for polar hydrophilic aromatic sulfonates (ASs). The compounds were detected by negative ion electrospray ionization (NIESI) and selected ion monitoring (SIM). In comparison with CE/UV, for CE/MS a lower-concentration volatile ammonium acetate buffer (5 mM) without organic modifier and a higher separation voltage were better suited for separation. Sensitivity of CE/MS was slightly better than for CF/UV, with the limit of detection (LOD) ranging between 0.1 and 0.4 mg l(-1). For verification of the CE/MS results, ASs were also analysed by ion-pair liquid chromatography/diode array UV detection coupled in series with electrospray mass spectrometry (IPC/DAD/ESI-MS). Real water samples of different waste water treatment plants (WWTPs) in Catalonia (NE Spain) were extracted by solid-phase extraction (SPE) with LiChrolut EN and analysed with CE/MS and LC/MS. ASs were found in influent and effluent water samples of the WWTPs in the microg l(-1) concentration range. LC/MS offered a higher separation efficiency and sensitivity than CE/MS. Therefore with LC/MS more compounds could be identified in the WWTPs. The persistency of the ASs was distinct: some compounds were well degraded during the water treatment process, while others were quite persistent.     

Preparation of RCM substrates for azepinoindole synthesis: reductive amination versus tetrahydro-γ-carboline formation

Treatment of N-(phenylsulfonyl)-2-vinyl-3-indolecarbaldehydes with primary aliphatic amines under mild reductive amination conditions leads to tetrahydro-γ-carbolines in high yield. The process can be suppressed by changing the protecting group at the indole nitrogen for a methoxymethyl group, thus allowing the preparation of RCM substrates for azepinoindole synthesis.     

Photoabsorption cross sections of sodium clusters: electronic and geometrical effects

We study the origin of the discrepancy between the photoabsorption cross sections of small jellium spheres calculated by the time dependent local density approximation (TDLDA) and experiments for small metallic clusters. We have specifically studied Na ₂₁ ⁺ . We conclude that both non-local exchange-correlation effects beyond the LDA and geometrical effects beyond the jellium approximation should be taken in the same calculation. We also present local and non-local calculations for Na _n ^? (n=19, 91 and 197) within the framework of the jellium model. The large anions show a fragmentation of the plasmon due to its interference with the ionization threshold. This feature is absent in the TDLDA results.     

Determination of amino acids in apple extracts by high performance liquid chromatography

Summary A rapid and sensitive method for the simultaneous determination of primary amino acids in apple is described. After sample preparation, amino acids were derivatized with o-phthaldialdehyde/2-mercaptoethanol and separated on a reversed phase column with a gradient of phosphate buffer-tetrahydrofuran-methanol as the mobile phase. Detection was carried out with a fluorescence detector at excitation and emission wavelengths of 340 nm and 425 nm respectively. Recovery studies showed good results for all substances (91–109%) (with coefficients of variation ranging, from 0.1 to 9.0%). This method was applied to the monitoring of amino acids during the ripening of apples.     

Palladium-catalyzed cascade reaction of alpha,beta-unsaturated sulfones with aryl iodides

Unlike traditionally used acyclic 1,2-disubstituted alkenes, the reaction of alpha,beta-unsaturated phenyl sulfones with aryl iodides under Heck reaction conditions (Pd(OAc)(2) as catalyst, Ag(2)CO(3) as base in DMF at 120 (0)C) takes place mainly by a cascade process, involving one unit of the alkene and three units of the aryl iodide, to afford a substituted 9-phenylsulfonyl-9,10-dihydrophenanthrene. The dominant formation of this 3:1 coupling product, instead of the Heck trisubstituted olefin, shows that aromatic C-H bond activation processes can compete with the usually fast syn beta-hydrogen elimination step in the Heck arylation of an acyclic olefin. The structural scope of this palladium-catalyzed cascade arylation of alpha,beta-unsaturated sulfones has proved to be wide with regard to substitution at the beta-position (alkyl, aryl, or alkenyl substitution), substitution at the sulfone unit (alkyl or phenyl sulfones), and configuration at the CdoublebondC bond (trans or cis). Moreover, although less favored than in the case of the arylation of alpha,beta-unsaturated sulfones, similarly substituted 9,10-dihydrophenanthrenes have also been obtained in the case of alpha,beta-unsaturated phosphine oxides and alpha,beta-unsaturated phosphonate esters. A Pd(0)-Pd(II)-Pd(IV) mechanistic pathway involving the successive formation of highly electrophilic sigma-alkylpalladium intermediates and palladacycles is proposed for this multicomponent arylation.