Overcoming matrix effects using the dilution approach in multiresidue methods for fruits and vegetables

During recent years matrix effects in liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) have quickly become a major concern in food analysis. The phenomenon of ion suppression can lead to errors in the quantification of the analytes of interest, as well as can affect detection capability, precision, and accuracy of the method. Sample dilution is an easy and effective method to reduce interfering compounds, and so, to diminish matrix effects. In this work, matrix effects of 53 pesticides in three different matrices (orange, tomato and leek) were evaluated. Several dilutions of the matrix were tested in order to study the evolution of signal suppression. Dilution of the extracts led to a reduction of the signal suppression in most of the cases. A dilution factor of 15 demonstrated to be enough to eliminate most of the matrix effects, opening the possibility to perform quantification with solvent based standards in the majority of the cases. In those cases where signal suppression could not be reduced, a possible solution would be to use stable isotope-labelled internal standards for quantification of the problematic pesticides.     

Conformational flexibility of a synthetic glycosylaminoglycan bound to a fibroblast growth factor. FGF-1 recognizes both the (1)C(4) and (2)S(O) conformations of a bioactive heparin-like hexasaccharide

The first direct NMR determination of the conformation of a conformationally flexible heparin-like hexasaccharide bound to a key receptor, FGF-1, is described. The determination has been based on the use of a 13C-labeled protein and a regular 12C sugar. FGF-1 recognizes several conformations of the iduronic moieties of the hexasaccharide. Therefore, this case is different than that described for the controversial recognition of heparin-like saccharides by AT-III, which seems to recognize just one conformation of the iduronic acid residues.     

Characterization of slate ornaments from Teotihuacan by nuclear and conventional techniques

Several ornaments named tezcacuitlapilli (coccyx-mirrors) are described and chemical analyses of raw materials (slate and pigments) were carried out by neutron activation, X-ray diffraction, scanning electron microscopy and radiography. Elemental and statistical analyses revealed that three different kinds of slate were used in their manufacture. The white pigment contains gypsum while ochre, yellow and red pigments contain iron oxide. These ornaments were identified as coming from the Cave of the Sun Pyramid of Teotihuacan. An attempt was undertaken to reconstruct the contexts of their manufacture and symbolic interpretation.     

Critical study of and improvements in chromatographic methods for the analysis of type B trichothecenes

Various analytical methods used in the analysis of type B trichothecenes (deoxynivalenol, nivalenol, 3- and 15-acetyldeoxynivalenol) in cereals were compared and optimised in this work. These methods use either GC-electron-capture detection (ECD) of trimethylsilyl, trifluoroacetyl and heptafluorobutyryl derivatives or HPLC with UV or photodiode array detection of analytes. A new HPLC procedure using fluorescence detection prior derivatisation with coumarin-3-carbonyl chloride has been also tested. Five extraction solvents and two solid-phase extraction cartridges (silica, Florisil) plus a especial clean-up column (MycoSep 225) were compared in order to obtain the best recovery of the mycotoxins with minimal presence of coextractives in the chromatograms. The chosen extraction solvent was a mixture of acetonitrile-water (84:16, v/v). The MycoSep 225 column was chosen as the best alternative for clean-up of grain samples. For GC-ECD analysis, derivatisation of analytes with heptafluorobutyric anhydride prior the final determination was chosen as the most suitable procedure. HPLC-photodiode array (at 221 nm) analysis was more suitable for determination of type B trichothecenes than HPLC of the fluorescent coumarin-3-carbonyl derivatives. Recoveries obtained in spiked corn, rice and wheat are reported. The utility of the proposed methodology was assayed in cereal cultures of various Fusarium strains.     

Unexpected reactivity of pyridinium salts toward alkynyl Fischer complexes to produce oxo‐heterocycles

The unprecedented reaction of ketone‐containing aromatic pyridinium salts 3a ‐ e and alkynyl Fischer complexes 1a ‐ f proceeds via a mild domino process to provide 4,6‐disubstituted pyran‐2‐ones 5a ‐ k and 2,3,5‐trisubstituted furans 6a ‐ h (45‐97%). According of the results of isotopic labeling experiments, a mechanism involving an initial Michael addition appears to be the key step, obtaining a mesomeric structure responsible for the formation of both products.     

Njaoamine I,a cytotoxic polycyclic alkaloid from the Haplosclerida sponge Haliclona (Reniera) sp.

A new cytotoxic polycyclic alkaloid containing a quinoline moiety, njaoamine I (1) has been isolated from the methanol extract of the sponge Haliclona (Reniera) sp. collected at Okuza Island, Tanzania. The structure of compound 1 was determined by 1D and 2D NMR and HRMS data analysis. Its relative configuration was elucidated by a NOESY experiment and confirmed by comparison of its NMR spectral data to those of njaoamines A–H. Moreover, njaoamine G (2) was also detected by LC/MS analysis of the methanol extract. Njaoamine I (1) displays cytotoxic activity against a panel of three human tumor cell lines in the micromolar range.     

Transition‐Metal π‐Ligation of a Tetrahalodiborane

The reaction of tetraiododiborane (B₂I₄) with trans‐[Pt(BI₂)I(PCy₃)₂] gives rise to the diplatinum(II) complex [{(Cy₃P)(I₂B)Pt}₂(μ₂:η³:η³‐B₂I₄)], which is supported by a bridging diboranyl dianion ligand [B₂I₄]^2?. This complex is the first transition‐metal complex of a diboranyl dianion, as well as the first example of intact coordination of a B₂X₄ (X=halide) unit of any type to a metal center.     

A two-step extraction method for differentiating chromium species in water

The hexavalent Cr species Cr(VI) in natural waters can be quantitatively extracted by diethyldithiocarbamate (DDTC) in the pH range 4.0–4.5 into chloroform, followed by back-extraction into a Hg(II) solution for graphite furnace atomic absorption spectrometry (GFAAS). The trivalent Cr(III) species can be oxidized to Cr(VI) by KMnO₄ and then extracted by the DDTC-Hg(II) procedure. The proposed two-step extraction method combined with GFAAS is suitable for Cr speciation studies in natural water systems.     

Phase transfer and its applications in nanotechnology

As nanoparticle syntheses in aqueous and organic systems have their own merits and drawbacks, specific applications may call for the transfer of newly formed nanoparticles from a polar to a non-polar environment (or vice versa) after synthesis. This critical review focuses on the application of phase transfer in nanoparticle synthesis, and features core-shell structures in bimetallic nanoparticles, replacement reactions in organic media, and catalytic properties of various nanostructures. It also describes the reversible organic and aqueous phase transfer of semiconductor and metallic nanoparticles for biological applications, and the use of phase transfer in depositing noble metals on semiconductor nanoparticles (258 references).