Assessment of pesticide contamination in soil samples from an intensive horticulture area, using ultrasonic extraction and gas chromatography-mass spectrometry

In order to reduce the amount of sample to be collected and the time consumed in the analytical process, a broad range of analytes should be preferably considered in the same analytical procedure. A suitable methodology for pesticide residue analysis in soil samples was developed based on ultrasonic extraction (USE) and gas chromatography–mass spectrometry (GC–MS). For this study, different classes of pesticides were selected, both recent and old persistent molecules: parent compounds and degradation products, namely organochlorine, organophosphorous and pyrethroid insecticides, triazine and acetanilide herbicides and other miscellaneous pesticides. Pesticide residues could be detected in the low- to sub-ppb range (0.05–7.0 μg kg⁻¹) with good precision (7.5–20.5%, average 13.7% R.S.D.) and extraction efficiency (69–118%, average 88%) for the great majority of analytes. This methodology has been applied in a monitoring program of soil samples from an intensive horticulture area in Póvoa de Varzim, North of Portugal. The pesticides detected in four sampling programs (2001/2002) were the following: lindane, dieldrin, endosulfan, endosulfan sulfate, 4,4′-DDE, 4,4′-DDD, atrazine, desethylatrazine, alachlor, dimethoate, chlorpyrifos, pendimethalin, procymidone and chlorfenvinphos. Pesticide contamination was investigated at three depths and in different soil and crop types to assess the influence of soil characteristics and trends over time.     

Acetate- and thiol-capped monodisperse ruthenium nanoparticles: XPS, XAS, and HRTEM studies

Monodisperse ruthenium nanoparticles were prepared by reduction of RuCl3 in 1,2-propanediol. The mean particle size was controlled by appropriate choice of the reduction temperature and the acetate ion concentration. Colloidal solutions in toluene were obtained by coating the metal particles with dodecanethiol. High-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), and X-ray absorption spectroscopy (XANES and EXAFS for the Ru K-absorption edge) were performed on particles of two different diameters, 2 and 4 nm, and in different environments, polyol/acetate or thiol. For particles stored in polyol/acetate XPS studies revealed superficial oxidation limited to one monolayer and a surface coating containing mostly acetate ions. Analysis of the EXAFS spectra showed both oxygen and ruthenium atoms around the ruthenium atoms with a Ru-Ru coordination number N smaller than the bulk value, as expected for fine particles. In the case of 2 nm acetate-capped particles N is consistent with particles made up of a metallic core and an oxidized monolayer. For 2 nm thiol-coated particles, a Ru-S bond was evidenced by XPS and XAS. For the 4 nm particles XANES and XPS studies showed that most of the ruthenium atoms are in the zerovalent state. Nevertheless, in both cases, when capped with thiol, the Ru-Ru coordination number inferred from EXAFS is much smaller than for particles of the same size stored in polyol. This is attributed to a structural disorganization of the particles by thiol chemisorption. HRTEM studies confirm the marked dependence of the structural properties of the ruthenium particles on their chemical environment; they show the acetate-coated particles to be single crystals, whereas the thiol-coated particles appear to be polycrystalline.     

Comprehensive examination of mesophases formed by DMPC and DHPC mixtures

Mixtures of long- and short-chain phospholipids, specifically 14:0 and 6:0 phosphatidylcholines (DMPC and DHPC), have been used successfully in NMR studies as magnetically alignable substrates for membrane-associated proteins. However, recent publications have shown that the phase behavior of these mixtures is much more complex than originally thought. Using polarized light microscopy and small-angle neutron scattering, phase diagrams of DMPC/DHPC mixtures at molar ratios of 2, 3.2, and 5 have been determined. Generally, at temperatures below the main-chain melting transition of DMPC (T(M) = 23 degrees C), an isotropic phase of disk-like micelles is found. At high temperatures (T > 50 degrees C), a lamellar phase consisting of either multilamellar vesicles (MLV) or extended lamellae is formed, which at low lipid concentrations (e.g., MLV) coexists with an excess of water. At intermediate temperatures and lipid concentrations, a chiral nematic phase made up of worm-like micelles was observed.     

A heteronuclear bidentate Lewis acid as a phosphorescent fluoride sensor

Reaction of dimesityl-1,8-naphthalenediylborate (1) with C6F5HgCl results in the formation of a B/Hg heteronuclear bidentate Lewis acid (2), which complexes fluoride to afford [2-mu2-F]-. Structural and photophysical studies carried out in solution and in the solid state indicate that 2 is a highly selective and sensitive phosphorescent fluoride sensor. The proximity of the two Lewis acidic sites enforced by the 1,8-naphthalenediyl backbone promotes fluoride anion chelation and is, therefore, responsible for the high binding constant. The interplay of conjugative and spin-orbit coupling effects mediated by the boron and mercury atoms, respectively, results in the phosphorescent signaling of fluoride binding. Remarkably, fluoride binding occurs in partially aqueous solutions and results in a drastic change of the phosphorescence observed when the solutions are frozen.     

NMR and structural investigations of a nonplanar iron corrolate: modified patterns of spin delocalization and coupling in a slightly saddled chloroiron(III) corrolate radical

An undecasubstituted chloroiron corrolate, octamethyltriphenylcorrolatoiron chloride, (OMTPCorr)FeCl, has been synthesized and studied by X-ray crystallography and (1)H and (13)C NMR spectroscopy. It is found that, although the structure is slightly saddled, the average methyl out-of-plane distance is only 0.63 Angstroms, while it is much greater for the dodecasubstituted porphyrinate analogue (OMTPP)FeCl (1.19 Angstroms) (Cheng, R.-J.; Chen, P.-Y.; Gau, P.-R.; Chen, C.-C.; Peng, S.-M. J. Am. Chem. Soc. 1997, 119, 2563-2569). In addition, the distance of iron from the mean plane of the four macrocycle nitrogens is also smaller for (OMTPCorr)FeCl (0.387 Angstroms) than for (OMTPP)FeCl (0.46 Angstroms). The (1)H and (13)C NMR spectra of (OMTPCorr)FeCl, as well as the chloroiron complexes of triphenylcorrolate, (TPCorr)FeCl; 7,13-dimethyl-2,3,8,12,17,18-hexaethylcorrolate, (DMHECorr)FeCl; 7,8,12,13-tetramethyl-2,3,17,18-tetraethylcorrolate, (TMTECorr)FeCl; and the phenyliron complex of 7,13-dimethyl-2,3,8,12,17,18-hexaethylcorrolate, (DMHECorr)FePh, have been assigned, and the spin densities at the carbons that are part of the aromatic ring of the corrole macrocycle have been divided into the part due to spin delocalization by corrole --> Fe pi donation and the part due to the unpaired electron present on the corrole ring. It is found that although the spin density at the beta-pyrrole positions is fairly similar to that of (TPCorr)FeCl, the meso-phenyl-carbon shift differences delta(m) - delta(p) are opposite in sign of those of (TPCorr)FeCl. This finding suggests that the radical electron is ferromagnetically coupled to the unpaired electrons on iron, rather than antiferromagnetically coupled, as in all of the other chloroiron corrolates. The solution magnetic moment was measured for (OMTPCorr)FeCl and found to be mu(eff) = 4.7 +/- 0.5 micro(B), consistent with S = 2 and ferromagnetic coupling. From this study, two conclusions may be reached about iron corrolates: (1) the spin states of chloroiron corrolates are extremely sensitive to the out-of-plane distance of iron, and (2) pyrrole-H or -C shifts are not useful in delineating the spin state and electron configuration of (anion)iron corrolates.     

Synthesis, characterization, and x-ray crystal structures of cyclam derivatives. 8. Thermodynamic and kinetic appraisal of lead(II) chelation by octadentate carbamoyl-armed macrocycles

En route toward the development of hybrid organic-inorganic extracting materials incorporating lead-selective chelators and their implementation in water purification processes, the lead(II) binding properties of three N-carbamoylmethyl-substituted 1,4,8,11-tetraazacyclotetradecanes (cyclams) have been fully investigated by spectroscopic (IR, UV-vis, MALDI-TOF MS, (1)H and (13)C NMR), X-ray crystallographic, potentiometric, and kinetic methods. Solution NMR studies revealed that the Pb(2+) ion is entrapped in a molecular cage constituted by the four macrocyclic nitrogen and four amidic oxygen atoms. Protonation and lead binding constants determined in aqueous solution were shown to be linearly dependent, so that all three derivatives possess a similar affinity at any pH value. Thermodynamic and kinetic parameters revealed the crucial role played by the intramolecular hydrogen bonds also evidenced in the crystal structure of the tetraacetamide derivative L(1), which involve the lone pair of each macrocyclic tertiary amine and one amidic hydrogen atom belonging to the appended arm. In contrast to L(1), the absence of such intramolecular interactions for N-(dimethyl)carbamoylmethyl- and N-(diethyl)carbamoylmethyl-substituted cyclams (L(2) and L(3), respectively) accounts for the 2-3 orders of magnitude enhancement of their proton and lead binding affinities. Stopped-flow kinetic measurements enabled unraveling the formation process of the three lead(II) complexes that proceeds in a single rate-limiting step according to the Eigen-Winkler mechanism, while the apparent rate constants were found to increase in the order L(3) < L(2) < L(1) as a consequence of the more acidic character of L(1). A common proton-assisted dissociation mechanism has been found for the three lead(II) complexes, which involves the rapid formation of a protonated, six-coordinate intermediate followed by either a unimolecular decomposition or a bimolecular attack of a second hydronium ion.     

Separation of water-soluble vitamins by reversed-phase high performance liquid chromatography with ultra-violet detection: application to polyvitaminated premixes

Nine water-soluble vitamins: [thiamine (B1), ascorbic acid (C), nicotinamide (PP), pyridoxine (B6), calcium pantothenate (B5), folic acid (B9), cyanocobalamin (B12), riboflavin (B2) and biotin (B8)] were separated on a YMC-Pack Pro C18 column (250 mm x 4.6 mm, 5 microm particle size) in a single run with a gradient elution of mobile phase consisting of 0.025% trifluoroacetic acid pH 2.6 (solvent A) and acetonitrile (solvent B). The separation was achieved within 17 min with a flow rate of 0.8 ml min(-1) and the detection was performed at two wavelengths (210 and 275 nm). The calibration graphs plotted with six concentrations of each vitamin were linear with a regression coefficient R2 > 0.995. The method was applied for the quantification of vitamins B1, C, PP, B6, B5, B9 B2 and B8 in polyvitaminated premixes (premixes) used for the fortification of infant nutrition products. The sample preparation involves an aqueous extraction of vitamins and two different samples dilution were used prior the LC-analysis. The specificity of the method was demonstrated by the retention characteristics, UV spectra and by comparing the peak purity with the standard of each vitamin. The repeatability of the method was evaluated at different level of concentrations on 12 premixes and the coefficients of variation (CVr) were below 6.5%. The values of the intermediate precision (CV1) were below 9.6% (n = 6). The concentrations of vitamins found in premixes with our method were comparable to the declared values, since no bias was found between the two sets of results at 95% confidence. The simplicity of the procedure should make it highly desirable for quality control of premixes in the food industry.     

Analysis of complex samples by solvating gas chromatography (supercritical fluid to gas transition)

The various forms of chromatography are primarily determined by differences in the physical state of the mobile phases. The main chromatographic categories include gas chromatography (GC), liquid chromatography, and supercritical fluid chromatography. Adjusting a temperature and pressure will change the mobile phase from liquid to supercritical fluid to gas, with concomitant changes in their physical properties. In this paper, the technique transition-phase chromatography (TPC) is described. In TPC, different mobile phase conditions exist inside the column. This phase transformation within the column results in huge differences in density, solvating power, viscosity, diffusivity, and, as a consequence, in the chromatographic properties of the mobile phase. TPC experiments using capillary columns packed in our laboratory have shown that when the mobile phase is transformed from supercritical fluid to gas, high column efficiencies can be achieved. The transition from supercritical fluid to gas (also called solvating GC), a particular case of the TPC, is evaluated for the separation of complex real samples (environmental, food, and fuels).     

Mixed effect of the supporting electrolyte and the zinc anode in the electrochemical homocoupling of 2-bromopyridines catalyzed by nickel complexes in an undivided cell

[reactions: see text] Nickel-catalyzed electroreductive homocoupling of 2-bromomethylpyridines and 2-bromopyridine has been investigated in an undivided cell in the presence of a zinc sacrificial anode. A series of reactions were performed with various types and concentrations of supporting electrolyte. It was observed that a key step in this process is the formation of an arylzinc through a nickel-zinc transmetalation. This intermediate can be transformed back to the reactive arylnickel species to afford the homocoupling as the final product. The back process from the arylzinc intermediate is, however, suppressed in the presence of high concentration (0.2 M) of tetraalkylammonium salts. On the contrary, with NaI, the formation of the dimer is not prevented, whatever the NaI concentration.     

Charge-transfer complexation as a general phenomenon in the copigmentation of anthocyanins

Color intensification of anthocyanin solutions in the presence of natural polyphenols (copigmentation) is re-interpreted in terms of charge transfer from the copigment to the anthocyanin. Flavylium cations are shown to be excellent electron acceptors (E(red) approximately -0.3 V vs SCE). It is also demonstrated, for a large series of anthocyanin-copigment pairs, that the standard Gibbs free energy of complex formation decreases linearly with EA(Anthoc) - IP(Cop), the difference between the electron affinity of the anthocyanin, EA(Anthoc), and the ionization potential of the copigment, IP(Cop). Based on this correlation, copigmentation strengths of potential candidates for copigments can be predicted.