Selective extraction of triazine herbicides from food samples based on a combination of a liquid membrane and molecularly imprinted polymers

A selective extraction technique based on the combination of liquid membrane (microporous membrane liquid–liquid extraction) and molecularly imprinted polymers (MIP) was applied to triazines herbicides in food samples. Simazine, atrazine and propazine were extracted from aqueous food samples through the hydrophobic porous membrane that was impregnated with toluene, which also formed part of the acceptor phase. In the acceptor phase, the compounds were re-extracted onto MIP particles. The extraction technique was optimised for the amount of molecularly imprinted polymers particles in the organic acceptor phase, extraction time, and type of organic acceptor solvent and desorption solvent. An extraction time of 90 min and 50 mg of MIP were found to be optimum parameters. Toluene as the acceptor phase was found to give higher triazines binding onto MIP particles compared to hexane and combinations of diethyl ether and hexane. 90% methanol in water was found to be the best desorption solvent compared to acetonitrile, methanol and water. The selectivity of the technique was demonstrated by extracting spiked lettuce and apple extracts where clean chromatograms were obtained compared to liquid membrane extraction alone or to the microporous membrane liquid–liquid extraction – non-imprinted polymer combination. The MIP showed a certain degree of group specificity and the extraction efficiency in lettuce extract was 79% (0.72) for simazine, 98% (1.55) for atrazine and 86% (3.08) for propazine.     

Miniaturized module with biosensors for potentiometric determination of urea

We describe the construction of a miniaturized module which allows carrying out potentiometric urea determination with the usage of biosensors. The module was fabricated using new hybrid technologies developed in our group which combine ceramic and polymeric materials. Its simplicity and easy way of preparation makes the system very useful for analytical measurements in a flow mode. Application of urease-modified polymer membranes deposited on silver screen-printed electrodes in the module allows to determine urea concentration in clinical range. Moreover, it is a very promising construction for other applications in that other enzymes can be immobilized and various bioanalytes can be determined using this module.     

Stereoselective syntheses of heptaprenylphosphoryl β-d-arabino-and β-d-ribo-furanoses

The stereoselective syntheses of heptaprenylphosphoryl β-d-arabinofuranose and heptaprenylphosphoryl β-d-ribofuranose are described. In the synthesis of the d-arabino product, the stereoselectivity was achieved by the coupling of a suitably protected β-d-arabinofuranosyl phosphate intermediate with an activated form of heptaprenol and subsequent deprotection. In the case of the ribo-analog, the desired β-anomer could be obtained by the more convenient phosphoramidite method. The products were successfully employed in the mycobacterial epimerase assay.     

N‐Fusion Approach in Construction of Contracted Carbaporphyrinoids: Formation of N‐Fused Telluraporphyrin

Insertion of PCl₃ into 5,10,15,20‐tetraaryl‐21‐telluraporphyrin leads to a phosphorus complex of N‐fused dihydrotelluraporphyrin with an inverted tellurophene ring. Its CNN coordination core places the macrocycle in the family of contracted carbaporphyrinoids. A cycle of direct transformations affords an elegant triangle of three mutually convertible N‐fused porphyrinoids, with distinct spectroscopic features: antiaromatic, nonaromatic and aromatic. The nonaromatic species has a dome shaped skeleton which forms in the solid state a ball and socket structure with C₆₀.     

Influence of temperature on mass transfer in an incomplete trapping supported liquid membrane extraction of triazole fungicides

The influence of temperature in a supported liquid membrane (SLM) extraction of triazole fungicides was investigated. The mass transfer parameters such as diffusion coefficient, flux and apparent viscosity were determined at temperatures ranging from 5 to 40°C. Increase in temperature led to an increase in diffusion coefficient and flux with a flowing acceptor solution. The apparent viscosity also decreased with an increase in temperature. However, the increase in mass transfer parameters did not result in an overall increase in extraction efficiency with a stagnant or circulation acceptor phase. Stripping of the analytes from the membrane into the acceptor phase as well as the configuration of the extraction unit could have limited the influence of temperature on mass transfer. The partition coefficient of analytes from the acceptor solution to the membrane, K_A, was found to be much higher than that from the donor solution to the membrane K_D, thus triazole compounds preferred to remain in the membrane even with an increased extraction temperature.     

Prototropy and π‐electron delocalization for purine and its radical ions – DFT studies

Complete tautomeric equilibria and π‐electron delocalization were studied at the B3LYP/6‐311+G** level for neutral purine ( P ) and its charged radicals ( P ^+? and P ^??). All possible nine tautomers (four NH and five CH forms) and all possible 36 tautomeric equilibria (six NⁱH → N^kH, twenty NH → CH, and ten CⁱH → C^kH conversions) were considered. The greatest variations of the tautomeric equilibrium constants (as pK_T) were observed for the NH → CH conversions when proceeding from neutral to reduced purine ( P + e → P ^??). These variations completely change the tautomeric preferences. One‐electron oxidation ( P ? e → P ^+?) has considerably smaller effect on the pK_T values and does not change the tautomeric preferences. π‐Electron delocalization depends on the position of the moving proton and on the type of the electron transfer. For individual tautomers, some linear relations between the relative stabilities and the HOMA (harmonic oscillator model of aromaticity) indices occur for neutral and oxidized purine. For reduced purine, a scatter plot is found. Copyright © 2010 John Wiley & Sons, Ltd.     

p-Chlorophenol adsorption on activated carbons with basic surface properties

The adsorption of p-chlorophenol (PCP) from aqueous solution on activated carbons (ACs) with basic surface properties has been studied. The ACs were prepared by two methods. The first method was based on the modification of a commercial CWZ AC by high temperature treatment in an atmosphere of ammonia, nitrogen and hydrogen. The second approach comprised the carbonization followed by activation of N-enriched polymers and coal tar pitch using CO₂ and steam as activation agent. The resultant ACs were characterized in terms of porous structure, elemental composition and surface chemistry (pH_PZC, acid/base titration, XPS). The adsorption of PCP was carried out from an aqueous solution in static conditions. Equilibrium adsorption isotherm was of L2 type for polymer-based ACs, whereas L3-type isotherm was observed for CWZ ACs series. The Langmuir monolayer adsorption capacity was related to the porous structure and the amount of basic sites. A good correlation was found between the adsorption capacity and the volume of micropores with a width < 1.4 nm for polymer-based ACs. Higher nitrogen content, including that in basic form, did not correspond to the enhanced adsorption of PCP from aqueous solution. The competitive effect of water molecule adsorption on the PCP uptake is discussed.     

Amplitude variations in coarticulated vowels

This paper seeks to characterize the nature, size, and range of acoustic amplitude variation in naturally produced coarticulated vowels in order to determine its potential contribution and relevance to vowel perception. The study is a partial replication and extension of the pioneering work by House and Fairbanks [J. Acoust. Soc. Am. 22, 105-113 (1953)], who reported large variation in vowel amplitude as a function of consonantal context. Eight American English vowels spoken by men and women were recorded in ten symmetrical CVC consonantal contexts. Acoustic amplitude measures included overall rms amplitude, amplitude of the rms peak along with its relative location in the CVC-word, and the amplitudes of individual formants F1-F4 along with their frequencies. House and Fairbanks' amplitude results were not replicated: Neither the overall rms nor the rms peak varied appreciably as a function of consonantal context. However, consonantal context was shown to affect significantly and systematically the amplitudes of individual formants at the vowel nucleus. These effects persisted in the auditory representation of the vowel signal. Auditory spectra showed that the pattern of spectral amplitude variation as a function of contextual effects may still be encoded and represented at early stages of processing by the peripheral auditory system.     

Convergence to stable laws for a class of multidimensional stochastic recursions

We consider a Markov chain ${\{X_n\}_{n=0}^\infty}$ on ${\mathbb R^d}$ defined by the stochastic recursion X _n  = M _n X _n-1 + Q _n , where (Q _n , M _n ) are i.i.d. random variables taking values in the affine group ${A(\mathbb R^d)=\mathbb R^d\rtimes {\rm GL}(\mathbb R^d)}$ . Assume that M _n takes values in the group of similarities of ${\mathbb R^d}$ , and the Markov chain has a unique stationary measure ν, which has unbounded support. We denote by |M _n | the expansion coefficient of M _n and we assume ${\mathbb E [|M|^\alpha]=1}$ for some positive α. We show that the partial sums ${S_n=\sum_{k=0}^n X_k}$ , properly normalized, converge to a normal law (α ≥ 2) or to an infinitely divisible law, which is stable in a natural sense (α < 2). These laws are fully nondegenerate, if ν is not supported on an affine hyperplane. Under an aperiodicity hypothesis, we prove also a local limit theorem for the sums S _n . If α ≤ 2, proofs are based on the homogeneity at infinity of ν and on a detailed spectral analysis of a family of Fourier operators P _v considered as perturbations of the transition operator P of the chain {X _n }. The characteristic function of the limit law has a simple expression in terms of moments of ν (α > 2) or of the tails of ν and of stationary measure for an associated Markov operator (α ≤ 2). We extend the results to the situation where M _n is a random generalized similarity.     

Inflationary predictions at small γ

This Letter explores single field inflation models with a constant, but arbitrary speed of sound cs$c_s$, obtained by deforming the kinetic energy terms to a Dirac–Born–Infeld form. Allowing cs<1$c_s<1$ provides a simple parametrization of non-Gaussianity. The dependence of inflationary observables on the parameter cs$c_s$ is considered in the leading order slow roll approximation. The results show that in most cases the dependence is actually rather weak for the range of cs$c_s$ allowed by existing bounds on non-Gaussianity.