Multiresidue determination of 11 new fungicides in grapes and wines by liquid–liquid extraction/clean-up and programmable temperature vaporization injection with analyte protectants/gas chromatography/ion trap mass spectrometry

A gas chromatographic ion trap mass spectrometry (GC-ITMS) method was developed for the determination of 11 new generation fungicides (benalaxyl, benalaxyl-M, boscalid, cyazofamid, famoxadone, fenamidone, fluquinconazole, iprovalicarb, pyraclostrobin, trifloxystrobin and zoxamide) in grapes and wines. Samples were extracted with ethyl acetate:hexane (1:1, v/v) and cleaned-up with graphitized carbon black/primary secondary amine (GCB/PSA) solid-phase extraction (SPE) cartridges using acetonitrile:toluene (3:1, v/v) as eluent. The addition of analyte protectants (3-ethoxy-1,2-propanediol, d-sorbitol and l-gulonic acid γ-lactone) in the final extracts allowed to avoid the matrix-induced response enhancement effect on quantitation process with absolute recoveries ca. 100%. Precision (expressed as relative standard deviation) was lower than 16% for all fungicides. Limits of detection and quantitation were lower than 0.01 mg/kg or mg/L, except for cyazofamid, much smaller in all cases than maximum residue levels (MRLs) established by European Union for grapes and by Switzerland and Italy for wines. The proposed method was applied to determine fungicide residues in three different white grapes for vinification produced in Ribeiro area in Galicia (NW Spain), as well as in their corresponding final wines.     

Optimization of matrix solid-phase dispersion extraction method for the analysis of isoflavones in Trifolium pratense

A method based on matrix solid-phase dispersion (MSPD) has been developed for the determination of 12 isoflavones in Trifolium pratense L. Dried leaf samples were blended with C₁₈, placed in small columns and isoflavones extracted with dichloromethane–methanol. Analyses were performed by high performance liquid chromatography with diode array detection (HPLC-DAD) with 2-methoxyflavone as internal standard. Several dispersants, eluents and clean-up steps were tested during the optimization of the process in order to obtain the best selectivity and yields. Mean recoveries ranged from 70% to 119%, with relative standard deviations <18%. The limits of detection were between 0.006 mg/l for biochanin A and 0.108 mg/l for daidzin. The performance of the optimized method in real samples was compared with a conventional method based in solid–liquid extraction (SLE).     

Preparation of porous methacrylate monoliths with oxidized single-walled carbon nanohorns for the extraction of nonsteroidal anti-inflammatory drugs from urine samples

Microchimica Acta - A copolymer was prepared from glycidyl methacrylate, ethylene glycol dimethacrylate and oxidized single-walled carbon nanohorns via photo-polymerization and used in spin columns...     

Green solid-phase peptide synthesis 4. γ-Valerolactone and N-formylmorpholine as green solvents for solid phase peptide synthesis

Herein, we report the use of γ-valerolactone (GVL) and N-formylmorpholine (NFM) as DMF substitutes in polystyrene based SPPS. The solubility of selected amino acids and coupling reagents were studied in GVL and NFM, followed by their use in the successful synthesis of Aib-enkephalin pentapeptide (H-Tyr-Aib-Aib-Phe-Leu-NH₂) and Aib-ACP decapeptide (H-Val-Gln-Aib-Aib-Ile-Asp-Tyr-Ile-Asn-Gly-NH₂).     

Isobaric vapor–liquid equilibria for binary and ternary mixtures with cyclohexane,cyclohexene, and morpholine at 100 kPa

Vapor–liquid equilibria (VLE) data at 100 kPa have been determinated for the ternary system cyclohexane + cyclohexene + morpholine and two constituent binary systems cyclohexane + morpholine and cyclohexene + morpholine. The thermodynamic consistency of experimental data has been verified. Both binary systems deviate moderately from ideality without the presence of an azeotrope. The VLE data have been well correlated using local composition models (Wilson, NRTL and UNIQUAC) and have been also predicted with the original UNIFAC.     

Determination of Hg and Pb in compact fluorescent lamp by slurry sampling inductively coupled plasma optical emission spectrometry

Mercury and lead were determined in an extraction solution applied to compact fluorescent lamps by axial view inductively coupled plasma optical emission spectrometry (ICP OES). The solution contained 50% v/v HNO₃ and 10% v/v H₂O₂. The compact fluorescent lamps were treated by removing the socket and breaking the rest of the lamp inside the solution, followed by placing the mixture in an ultrasonic bath for 1 h. The mixture was filtrated in a coarse paper filter and the resulting extraction slurry was analyzed. The determination of Pb in the slurry required calibration by the analyte addition technique, while for Hg, external calibration was adequate. The quantification limits (10 s, n = 7), for Hg (194.164 nm) and Pb (220.353 nm) were, respectively, 10 and 30 µg per lamp. Analysis of spiked samples demonstrated reasonable accuracy of the method, with recoveries in the range from 99 to 120% for Hg and from 91 to 107% for Pb. Fifteen analyzed samples showed Hg masses per lamp in the range from 1.6 to 27 mg, and six samples were above the limit allowed by the European Community that is 5 mg per compact lamp. The values for Pb were between 0.07 and 0.75 mg per lamp. By filtrating the slurry in a membrane filter, and analyzing the resulting solution, it was found that all Hg was extracted to the liquid phase of the slurry, while a fraction of about 40% m/v of Pb is retained in the solid particles. The lamp cover glass, after extraction of the phosphor layer, was also analyzed for Hg and Pb. The concentration of Hg in the glass is quite low; however, the Pb content is high.     

Iron,copper and zinc ammonium-1-hydroxyalkylidene-diphosphonates with zero-, one- and two-dimensional covalent metal–ligand structures extended into three-dimensional supramolecular networks by charge-assisted hydrogen-bonding

Hydrothermal synthesis with MCl₂ (M = Fe, Cu, and Zn) and disodium 5-ammonium-1-hydroxypentylidene-1,1-bisphosphonate, (Na⁺)₂[⁺H₃N(CH₂)₄C(OH)(PO₃²⁻)(PO₃H⁻)] (Na₂HAC₅OHP₂) or sodium 3-ammonium-1-hydroxypropylidene-1,1-bisphosphonate hydrate, Na⁺[⁺H₃N(CH₂)₂C(OH)(PO₃H^–)(PO₃H^–)]·H₂O (NaH₂PAM·H₂O) the sodium salt of pamidronic acid, H₃PAM) yielded the one-dimensional (1D) iron, molecular copper and two-dimensional (2D) zinc compounds 1D-{[Fe(μ₃-η⁵-HAC₅OHP₂)]·H₂O}, 1, [Cu(η²-H₂AC₅OHP₂)₂], 2, 2D-{[Zn₂(μ₅-η⁷-AC₅OHP₂)Cl], 3, and 2D-{[Zn(μ₂-η³-H₂PAM)₂], 4, respectively. The bisphosphonate ligand bridges (μ_n) between 2–5 metal atoms and uses 2–7 oxygen donor atoms towards metal coordination (ηⁿ). The zwitterionic nature of the now bis- or tetrakis-deprotonated ammonium–bisphosphonate is retained in the metal complexes. From the reaction of NiCl₂ and Na₂HAC₅OHP₂ the zwitterionic 5-ammonium-1-hydroxypentylidene-1-phosphonic acid, ⁺H₃N(CH₂)₄CH(OH)PO₃H⁻, 5 was obtained as a product of the ligand P–C bond hydrolysis. Adjacent strands, molecules or layers in 1–4, respectively are organized through the Coulomb attraction between the positive ammonium group and the negative phosphonate groups, supported by hydrogen-bonding. Each protic H atom on the C–OH, NH₃⁺ and –PO₃H⁻ group is involved in charge-assisted hydrogen-bonding. The ammonium-pentylidene groups act as hydrophobic separators between the hydrophilic units with the polar M{C(OH)(PO₃)₂} and {NH₃} units. Bond valence sum calculations support the Fe(II) oxidation state in 1, which was experimentally determined from a quantitative polarographic Fe(II)/Fe(III) speciation analysis as well as a temperature variable magnetic study.     

Continuous solid-phase extraction method for the determination of amines in human urine following on-line microwave-assisted acid hydrolysis

Humans are exposed to endogenous or exogenous formation of aromatic amines (AAs) and N-nitrosamines (NAms), which are considered to be potent carcinogens. The objective of this study was to monitor AAs and NAms in human urine to obtain a way to assess exposure. However, while NAms can be directly detected in urine samples, AAs require hydrolysis to convert their conjugates into free amines. A semiautomatic flow-base method is proposed for the simultaneous determination of aliphatic and aromatic NAms, anilines and chloroanilines in human urine in one analytical run. Conjugated AAs are released from urine by on-line microwave-assisted acid hydrolysis without degradation of NAms; all amines were then preconcentrated using solid-phase extraction. Separation/determinations are carried out by gas chromatography and mass spectrometry operating in selected ion monitoring mode. The method is fast (∼15 min for 25 mL of sample) and provides low limits of detection (from 2 to 26 ng/L) with good precision (relative standard deviation within and between days less than 7%). Finally, the proposed method was successfully applied to check AAs and NAms in the human urine of exposed and unexposed researchers. The kinetics of amine excretion in the urine of the researchers exposed is calculated after termination of the exposure and shows half-life times between 1.3 and 2.1 h, and that the dosage absorbed was eliminated within 6 h after exposure.