Development and validation of an analytical methodology for the determination of p,p′-DDT, p,p′-DDE and p,p′-DDD in fish oil pills

An analytical methodology was proposed and validated to be applied to the determination of p,p′-DDT and its metabolites p,p′-DDE and p,p′-DDD in fish oil. The analytical procedure presented in this paper involves a single-step clean up process prior to the analysis. A solution of 1,2,3,4-tetrachloronaphtalene was used as internal standard.The analytical technique used was gas chromatography coupled to an electron capture detector. Details on the validation process are provided.The limits of detection ranged from 2.6 to 4.7 pg μL^− 1. The BCR 598 standard reference material (cod liver oil) was used to evaluate the performance of the methodology with satisfactory recoveries for all the compounds.The analytes were determined in three different fish oil pills sold in Spain as a supplementary vitamin support. The sum of p,p′-DDT and metabolites was from 13.2 to 51.3 ng g^− 1, the dominant compound being p,p′-DDE.     

Characterization of three agave species by gas chromatography and solid-phase microextraction-gas chromatography-mass spectrometry

Steam distillation (SD) extraction-solid-phase microextraction coupled to GC-MS was developed for the determination of terpenes and Bligh-Dyer extraction-derivatization coupled with GC for the determination of fatty acids such as ethyl esters were used. It was found that the three different Agave species have the same profile of fatty acids; the quantity of these compounds is different in each Agave variety. On the other hand, different terpenes were identified in the three Agave plants studied: nine in A. salmiana, eight in A. angustifolia and 32 in A. tequilana Weber var. azul.     

Synthesis, characterization, and tautomerism of four novel copper(I) complexes from 3-hydroxy-3-(p-R-phenyl)-2-propenedithioic acids

The paper describes the synthesis and structural characterization of four novel copper(I) complexes [CuL(PPh(3))(2)] (L = 3-hydroxy-3-(p-R-phenyl)-2-propenedithioate). In addition, a tautomeric equilibrium in solution was found and Hammett correlations with (13)C NMR parameters were studied. The structure of one complex was fully established by X-ray diffraction analysis.     

Chemistry and Biology of Cylindrols: Novel Inhibitors of Ras Farnesyl-Protein Transferase from Cylindrocarpon lucidum

Farnesyl-protein transferase (FPTase) is an enzyme responsible for the farnesylation of Ras protein. Farnesylation is required for cell-transforming activity in several tumor-types, and therefore, inhibition of FPTase activity may be a potential target for anticancer drugs. Our continued search for novel inhibitors led to the isolation of a number of bicyclic resorcinaldehyde cyclohexanone derivatives named here cylindrols A(1) to A(4), cylindrols B and B(1), and a number of known compounds, from Cylindrocarpon lucidum. The compounds were isolated by bioassay-guided separation using Sephadex LH-20, silica gel, and reverse phase HPLC. Structures were elucidated by extensive application of 2D NMR and X-ray crystallography. The determination of absolute stereochemistry was accomplished by CD measurements. Chemical transformations of the most abundant compound resulted in a number of key derivatives which were critical for the evaluation of structure activity relationship. These compounds are members of ascochlorin family and showed a wide range of inhibitory activity (0.7 &mgr;M to >140 &mgr;M) against FPTase. The FPTase activity was noncompetitive with respect to both substrates. Isolation, structures, chemical transformations, and FPTase activity are discussed in detail.     

Remote Regiocontrol by a Thioether Group in Diels-Alder Reactions of Naphthazarin: Regioselective Access to Tetracyclic Polyhydroxyquinones

The synthesis of tetracyclic polyhydroxyquinones 5a and 5b was achieved through a sequence involving two Diels-Alder reactions with 1-methoxy-1,3-cyclohexadiene: the first with 2-(p-tolylthio)naphthazarin and the second on the resulting tricyclic derivative previously transformed into a (p-tolylsulfinyl)naphthazarin. The success of this strategy stemmed from the efficient remote regiocontrol exerted by the thioether substituent in the first step.     

Fragmentation of carbohydrate anomeric alkoxyl radicals. Synthesis of highly functionalized chiral vinyl sulfones

The reaction of derivatives of 3-acetyl-d-glucal, 3-acetyl-l-rhamnal, 3-acetyl-d-galactal, and 3-acetyl-d-lactal with sodium benzenesulfinate in acid medium catalyzed by HgSO₄ afforded diastereoisomeric mixtures of the corresponding 2,3-dideoxy-3-(phenylsulfonyl)-hexopyranoses through a Ferrier rearrangement. The anomeric alkoxyl radical fragmentation of these γ-hydroxy sulfones using the system (diacetoxyiodo)benzene and iodine gave vinyl sulfones with structures of 1,2-dideoxy-4-O-formyl-2-(phenylsulfonyl)-pent-1-enitol and configurations d-erythro, l-erythro, and d-threo at the two stereogenic centers.     

Determination of fungicide residues in fruits by coupled-column liquid chromatography

Coupled-column liquid chromatography with fluorescence detection was applied to the determination of o-phenylphenol and bitertanol residues in orange and banana fruits. After extraction with a mixture of acetone, dichloromethane-petroleum ether, and ethyl acetate, an extract aliquot of 100 microL was injected directly without any additional clean-up into the chromatographic system using two reversed phase C18 coupled columns. The LC-LC approach allowed automated sample clean up of the vegetal extracts, leading to a simple and rapid analytical procedure, with limits of quantification between 0.01 and 0.05 mg kg(-1). Recovery experiments performed on orange and banana samples fortified at different concentrations (0.01 - 4 mg kg(-1)) gave average recoveries between 70 and 113% with relative standard deviations lower than 15%. The procedure developed was finally applied to orange and banana samples from different geographical locations and the results were confirmed by GC-MS.     

alpha-(2,6)-Sialyltransferase-catalyzed sialylations of conformationally constrained oligosaccharides

It is demonstrated that conformationally restricted oligosaccharides can act as acceptors for glycosyltransferases. Correlation of the conformational properties of N-acetyl lactosamine (Galbeta(1-4)GlcNAc, LacNAc) and several preorganized derivatives with the corresponding apparent kinetic parameters of rat liver alpha-(2,6)-sialyltransferase-catalyzed sialylations revealed that this enzyme recognizes LacNAc in a low energy conformation. Furthermore, small variations in the conformational properties of the acceptors resulted in large differences in catalytic efficiency. Collectively, our data suggest that preorganization of acceptors in conformations that are favorable for recognition by a transferase may improve catalytic efficiencies.     

Design of ordered bimetallic complexes,Part 2:Trans-1,2-cyclohexanediaminetetraacetate bimetallates

Summary Knowledge of the kinetic and thermodynamic behaviour of aqueous solutions containing two divalent cations andtrans-1,2-cyclohexanediaminetetraacetate has been used to design synthetic pathways to ordered bimetallic complexesPart 1: E. Escriva, A. Fuertes and D. Beltran,Transition Met. Chem.,9, 184 (1984).