Development of new solid-phase microextraction fibers by sol-gel technology for the determination of organophosphorus pesticide multiresidues in food

Allyloxy bisbenzo 16-crown-5 trimethoxysilane was first used as precursor to prepare the sol-gel-derived bisbenzo crown ether/hydroxyl-terminated silicone oil (OH-TSO) SPME coating. The coating procedure involving sol solution composition and conditioning process was presented. Compared with commercial SPME stationary phases, the new coatings showed higher extraction efficiency and therefore could provide higher sensitivity for organphosphorous pesticides (OPs). Limits of detection (LODs) were in the range of 0.003-1.0 ng/g for these OPs in food samples (honey, juice, orange and pakchoi). The optimal extraction conditions of the new coatings to OPs in these samples were investigated by adjusting extraction time, salt addition, extraction temperature, and dilution ratios of samples with distilled water by using SPME coupled with gas chromatography (GC)-flame photometric detection (FPD). The method was applied to determine the concentrations of OPs in real samples.     

Hydrothermal Synthesis and Structural Characterization of a Tubular Arsenic-Vanadate: [CoII(2,2′-bpy)2]2[AsIII8VIV14O42(H2O)]·H2O

The hydrothermal reaction of VOSO₄, As₂O₃, CoC₂O₄·2H₂O and 2,2-bipy yields a novel arsenic-vanadate [Co^II(2,2-bpy)₂]₂[As^III₈V^IV ₁₄O₄₂(H₂O)]·H₂O (1), which is characterized by IR, elemental analysis, TGA, magnetic susceptibility and single crystal X-ray diffraction analysis. X-ray diffraction shows that compound 1 is the first example of tubular arsenic–vanadium cluster containing infinite {[Co(2,2-bpy)₂]₂[As₈V₁₄O₄₂(H₂O)]} chain constructed from [As₈V₁₄O₄₂(H₂O)] clusters interconnected through [Co(2,2-bpy)]²⁺ units. Crystal data: 1, orthorhombic, P 2₁2₁2₁, a=12.1401(2) Å, b=15.8722(1) Å, c=39.9533(5) Å, Z=4.Graphical Abstract: A novel polyoxoarsenicvanadate, [Co^II(2,2-bipy)₂]₂ [As^III₈V^IV ₁₄O₄₂(H₂O)]·H₂O, is depicted along with a tubular hybrid solid with a rhombic tube formed within the chain.     

Two-dimensional catena–polymer [[[bis (µ-aqua)(bis (µ-cpiap-K2O1:O2)sodium(I))] (µ-chlorido) bis(µ-cpiap-K5N1:O1:O2:O3,O3′)dicopper(II)]bis(µ-aqua)(aqua)bis(cpiap-K2O1,O2)copper(II)] hexa hydrate

The new title two-dimensional hetero-tetra nuclear Cu₃–Na coordination polymer {[NaCu₃Cl(cpiap)₂(H₂O)₃]_n·6nH₂O} (1) consists of crystallographically two-independent copper(II) centers, each bridged by a sodium cation through carboxylate-oxygen of the deprotonated H₃cpiap ligand (H₃cpiap = 2-(carboxyphenyl)iminoaceticpropanoic acid) to Cu^II (2) and Cu^II (2⁻) cations, and through water molecules to Cu^II (1) cation. Cu^II (2) and Cu^II (1) cations are bridged by carboxylate-oxygen atoms of the ligand in a syn-anti mode which, alternate regularly within the chain being bridged by a tetra coordinated sodium cation. Each Cu^II (2) and Cu^II (2⁻) cation in (1) is in an octahedral environment formed by four carboxylate-oxygens from two cpiap³⁻ ligands, one nitrogen atom and a bridging chloride atom. Cu^II (1) cation is in a square pyramidal environment formed by three water molecules and two carboxylate-oxygens from two cpiap³⁻ ligands. The ligand acts simultaneously as monodentate and tridentate toward Cu^II (1) and Cu^II (2) cations respectively. The lattice water molecules involved in OH···O hydrogen bonding are situated in the void spaces between layers. The zigzag chains, which run along the b-axes further construct three-dimensional metal-organic framework via hydrogen bonding and weak face-to-face π-π interactions. Weak CH···O interactions are also present.     

Oxidations by a H2O2-VO3 −-pyrazine-2-carboxylic acid reagent

Alkanes (cyclohexane, hexane, heptane isomers) are effectively oxidized in CH₃CN at 20–70°C by hydrogen peroxide when catalyzed by a Bu₄NVO₃-pyrazine-2-carboxylic acid system. Alkyl hydroperoxide is the main product; an alcohol and a ketone or an aldehyde are also formed. Under these conditions benzene is oxidized to give phenol, while alkyl benzenes yield oxygenation products both of the ring and the side chain. It has been assumed that the interaction of H₂O₂ with VO₃ ^– gives rise to generation of HO radicals and other radical-like vanadium containing species that abstract a hydrogen atom from an alkane, RH. The radical R^. formed reacts with O₂ to produce ROO^. which is then transformed to alkyl hydroperoxide.Presented at the VIII International Symposium on Homogeneous Catalysis (Amsterdam, 1992).Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 1, pp. 64–68, January, 1993.     

氧化藏红T褪色催化荧光法测定痕量钒

研究了在酸性介质中柠檬酸存在下，痕量钒（Ｖ）催化溴酸钾氧化藏红Ｔ的褪色反应及其动力学条件，建立了催化荧光测定痕量钒的新方法。催化反应在沸水浴中进行８ｍｉｎ，为假零级反应，反应的表观活化能力为９９．２１ｋＪ／ｍｏｌ，反应速度常数为０．１２／ｓ；该方法的检出限为２．２×１０＾－８ｇ／Ｌ；线性范围为０．２￣２．４μｇ／Ｌ研究了共存离子的影响，用于人发和煤灰中痕量钒的测定，结果令人满意。     

Profiling fatty acids in vegetable oils by reactive pyrolysis-gas chromatography with dimethyl carbonate and titanium silicate

A novel methodology in on-line pyrolysis-gas chromatography (Py-GC) for the fast analysis of fatty acids in vegetable oils with minimal sample treatment and the use of non-toxic reagents is described. Pyrolysis at 500 degrees C for 10 s of sub-microgram quantity of vegetable oil dissolved in dimethyl carbonate (DMC) and in the presence of nanopowder titanium silicon oxide resulted in the production of fatty acid methyl esters (FAMEs) as unique products. Pyrolysis performed by means of a resistively heated filament pyrolyser interfaced to a GC-MS apparatus enabled the direct analysis of evolved FAMEs. The DMC/Py-GC-MS analysis was tested on soybean, coconut, linseed, walnut and olive oil and the results compared to the classical BF(3)-methanol as reference methodology. The DMC method exhibited a lower precision and was biased towards lower levels of polyunsaturated fatty acids (PUFA) in comparison to the BF(3)-methanol method, but was more advantageous in terms of reduced sample treatment, waste generation and risk factors of employed chemicals.     

Liquid structure of vanadium tetrachloride from neutron diffraction study

Assuming the separation of the intermolecular scattering function into the radial and angular parts and using Egelstaffet al’s orientational model for tetrachlorides, the structure of liquid vanadium tetrachloride has been studied. It has been observed that such a separation is approximate for this liquid and the introduction of a third correction term is required to account for the molecular structure function. The chlorine-chlorine partial structure and effective angleaveraged intermolecular chlorine-chlorine potential in the liquid has been evaluated. Without taking the third correction term, introduced to generate theoretically the molecular structure function, the centre structure function has been obtained in an approximate way from the experimentally observed molecular structure function and from it the centre radial distribution function, centre direct correlation function and the angle-averaged vanadium-vanadium effective potential has been evaluated.     

Effect of the extent of reduction of V2O5 on the adsorption of propylene and the oxidative dehydrogenation of propane to give propylene on V2O5 and V2O5/TiO2-SiO2

An increase in the propylene output in the oxidative dehydration of propane on V₂O₅/TiO₂-SiO₂ was observed after prior reduction of V₂O₅ in the reaction mixture to V₂O₄, which reduces the destructive chemisorption of propylene. A low titanium dioxide content in TiO₂-SiO₂ hinders the deep reduction of V₂O₅ to V₂O₃, which reduces the conversion of propane. __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 43, No. 6, pp. 373–378, November–December, 2007.     

液膜法分离钒(Ⅳ)的研究

本文用P204-兰113A-煤油组成的滤膜体系处理钒(Ⅳ)的溶液,并考察了表面活性剂、载体、外相pH值、内相酸度、起始钒(Ⅳ)浓度以及乳水比等因素对分离的影响。