Evaluation by HPLC-UV of Polar Pesticides in Rice Fields

Analysis of carbamate pesticides and their metabolites in water by solid phase extraction and liquid chromatography: A review

Carbamates are an important, broad class of pesticides that are used extensively as insecticides, fungicides, and herbicides. Sensitive, economical, fast, and environmental friendly procedures are constantly developed to investigate their residues in water samples. The state of the art in methods based on solid phase extraction (SPE) and liquid chromatographic determination are examined here. SPE is presently the most extended method for preconcentration of carbamate pesticide residues and their transformation products from water samples. Advantages and limitations of alkyl bonded-silica, and polymeric sorbents, carbon, and mixed-phases in off-line and on-line procedures are discussed. Beca…

Serum metabolome analysis by 1H-NMR reveals differences between chronic lymphocytic leukaemia molecular subgroups.

Chronic lymphocytic leukaemia (CLL) is a heterogeneous disease exhibiting variable clinical course and survival rates. Mutational status of the immunoglobulin heavy chain variable regions (IGHVs) of CLL cells offers useful prognostic information for high-risk patients, but time and economical costs originally prevented it from being routinely used in a clinical setting. Instead, alternative markers of IGHV status, such as zeta-associated protein (ZAP70) or messenger RNA levels are often used. We report a (1)H-NMR-based metabolomics approach to examine serum metabolic profiles of early stage, untreated CLL patients (Binet stage A) classified on the basis of IGHV mutational status or ZAP70. M…

Monitoring the Early Steps of Unfolding of Dicalcium and Mono-Ce3+-Substituted Forms of P43M Calbindin D9k

Early steps of unfolding of P43M Calbindin D9k have been evaluated by NMR spectroscopy on the native dicalcium and on the paramagnetic monocerium-substituted derivative. Although at 2 M GdmHCl the ...

Electronic characterisation of the oxidized state of the blue copper protein Rusticyanin by 1 H NMR: Is the axial methionine the dominant influence for the high redox potential

The oxidized state of rusticyanin, the blue copper protein with the highest redox potential in its class, has been investigated through (1)H nuclear magnetic resonance applied to its cobalt(II) derivative. The assignment of the protons belonging to the coordinated residues has been performed. Many other amino acids situated in the vicinity of the metal ion, including six hydrophobic residues (isoleucine140 and five phenylalanines) have also been identified. The orientation of the main axes of the magnetic susceptibility tensor for the cobalt(II)-rusticyanin as well as its axial, Deltachi(ax), and rhombic, Deltachi(rh), magnetic susceptibility anisotropy components have been determined. A co…

BEHAVIOUR OF GRAPHITIZED CARBON BLACK IN THE EXTRACTION OF POLAR NON-IONIC NITROGEN-CONTAINING PESTICIDES. A CHECKING OF HYPOTHESES

Graphitized Carbon Black (GCB) extractive cartridges are evaluated for on-line coupling with a C8 analytical column to determine eleven carbamates and one carboximide pesticide from spiked deionized water at the 1.2 μg/L level. Several experiments were carried out to ascertain whether GCB saturation, pesticide degradation on the surface, existence of by-pass channels, mobility among the bulk cartridge, or strong retention on the surface interfere with the determination of pesticides. Problems in on-line CGB elution are partially solved by modifying the acetonitrile/water gradient to contain a front of 100% acetonitrile for a few seconds. Eluting the same GCB cartridges off-line with dichlor…

Backbone dynamics of rusticyanin: the high hydrophobicity and rigidity of this blue copper protein is responsible for its thermodynamic properties.

Local dynamics and solute-solvent exchange properties of rusticyanin (Rc) from Thiobacillus ferrooxidans have been studied by applying heteronuclear ((1)H, (15)N) NMR spectroscopy. (15)N relaxation parameters have been determined for the reduced protein, and a model-free analysis has been applied. The high average value of the generalized order parameter, S(2) (0.93), indicates that Rc is very rigid. The analysis of cross correlation rates recorded in both the reduced and the oxidized forms conclusively proves that Rc possesses the same dynamic features in both oxidation states. The accessibility of backbone amide protons to the solvent at different time scales has also been studied by appl…

Comparison of different sorbents for on-line liquid-solid extraction followed by high-performance liquid chromatographic determination of nitrogen-containing pesticides

Abstract LiChrolut EN [poly(styrene-divinylbenzene), PSDVB], Carbograph (graphitized carbon black, GCB), Isolute CN (cyanopropylsilica), Isolute C 2 (ethylsilica), and LiChrospher RP18 (octadecylsilica) were studied for on-line solid-phase extraction of twelve nitrogen containing pesticides from water. Determination (UV 210 nm) was performed with a Spherisorb C 8 analytical column and an acetonitrile-water gradient. The mean recoveries from 50 ml ranged from 83% for RP18 to 44% for GCB, and decreased in the following order: RP18, CN, LiChrolut EN, C 2 , and GCB. GCB showed poor recoveries due to incomplete desorption with the acetonitrile-water gradient used, and memory effects were detecte…

An NMR view of the unfolding process of rusticyanin: Structural elements that maintain the architecture of a β-barrel metalloprotein

The unfolding process of the blue copper protein rusticyanin (Rc) as well as its dynamic and D(2)O/H(2)O exchange properties in an incipient unfolded state have been studied by heteronuclear NMR spectroscopy. Titrations of apo, Cu(I), and Cu(II)Rc with guanidinium chloride (GdmCl) show that the copper ion stabilizes the folded species and remains bound in the completely unfolded state. The oxidized state of the copper ion is more efficient than the reduced form in this respect. The long loop of Rc (where the first ligand of the copper ion is located) is one of the most mobile domains of the protein. This region has no defined secondary structure elements and is prone to exchange its amide p…

Influence of dissolved humic material and ionic strength on C8 extraction of pesticides from water

A mixture of twelve intermediate polarity pesticides, mostly carbamate-type, have been chromatographied on an octadecyl-silica bonded-phase column using acetonitrile-water gradient mobile phase and UV detection. Pesticides were extracted from aqueous matrix by solid-phase extraction. The extraction system consisted of a glass microcolumn containing octyl-silica solidphase conditioned with methanol and water. The elution was by acetonitrile-dichloromethane (50:50). Studies of extraction factors like volume of sample, addition of 10% sodium chloride and presence of dissolved humic material are investigated.