MSPD procedure for determining buprofezin,tetradifon, vinclozolin,and bifenthrin residues in propolis by gas chromatography–mass spectrometry

A simple and effective extraction method based on matrix solid-phase dispersion (MSPD) was developed to determine bifenthrin, buprofezin, tetradifon, and vinclozolin in propolis using gas chromatography–mass spectrometry in selected ion monitoring mode (GC–MS, SIM). Different method conditions were evaluated, for example type of solid phase (C₁₈, alumina, silica, and Florisil), the amount of solid phase and eluent (n-hexane, dichloromethane, dichloromethane–n-hexane (8:2 and 1:1, v/v) and dichloromethane–ethyl acetate (9:1, 8:2 and 7:3, v/v)). The best results were obtained using 0.5 g propolis, 1.0 g silica as dispersant sorbent, 1.0 g Florisil as clean-up sorbent, and dichloromethane–ethyl acetate (9:1, v/v) as eluting solvent. The method was validated by analysis of propolis samples fortified at different concentration levels (0.25 to 1.0 mg kg⁻¹). Average recoveries (four replicates) ranged from 67% to 175% with relative standard deviation between 5.6% and 12.1%. Detection and quantification limits ranged from 0.05 to 0.10 mg kg⁻¹ and 0.15 to 0.25 mg kg⁻¹ propolis, respectively.     

Multivariate optimization of a solid phase microextraction-headspace procedure for the determination of benzene, toluene, ethylbenzene and xylenes in effluent samples from a waste treatment plant

A method based on solid-phase microextraction (SPME) and gas chromatography with flame ionization detection (GC-FID) has been optimized for the determination of benzene, toluene, ethylbenzene and xylenes (BTEX) in water released from a waste treatment plant. The extraction step was optimized using fractional factorial and central composite designs including the following experimental factors: saline concentration; extraction time; desorption time; agitation velocity; headspace volume. A multiple function was used to describe the experimental conditions for simultaneous extraction of the compounds. The procedure, based on direct SPME at 50 degrees C, using a polydimethylsiloxane fiber, showed good linearity (r>0.997 over a concentration range 2-200 microg L(-1)) and repeatability (relative standard deviation (RSD)<4.23%) for all compounds, with limits of detection ranging from 0.05 to 0.28 microg L(-1), and limits of quantification ranging from 0.14 to 0.84 microg L(-1). Concentrations of the target compounds in these samples were between 145.8 and 1891 microg L(-1).     

Lempel–Ziv Factorization Using Less Time & Space

For 30 years the Lempel–Ziv factorization LZ _x of a string x = x[1..n] has been a fundamental data structure of string processing, especially valuable for string compression and for computing all the repetitions (runs) in x. Traditionally the standard method for computing LZ _x was based on Θ(n)-time (or, depending on the measure used, O(n log n)-time) processing of the suffix tree ST _x of x. Recently Abouelhoda et al. proposed an efficient Lempel–Ziv factorization algorithm based on an “enhanced” suffix array – that is, a suffix array SA _x together with supporting data structures, principally an “interval tree”. In this paper we introduce a collection of fast space-efficient algorithms for LZ factorization, also based on suffix arrays, that in theory as well as in many practical circumstances are superior to those previously proposed; one family out of this collection achieves true Θ(n)-time alphabet-independent processing in the worst case by avoiding tree structures altogether. The work of the first and third authors was supported in part by grants from the Natural Sciences & Engineering Research Council of Canada.     

Track overlap regime in ion-irradiated PMMA

Chemical and physical effects induced by bombardment of nearly monodisperse Poly(methyl methacrylate) (PMMA) with energetic ions (He⁺) at 200 keV have been studied. Bond scission is the main results of low fluence ion irradiation but, at high fluence there is a regime transition of PMMA from positive tone resist behavior to negative tone. The ion-induced chemical reactions in the macromolecular film give rise to gas evolution and chemical changes in the solid residue. The gas formed during the bombardment has been studied by means of a mass spectrometer, while the solid polymer has been characterized by measuring the molecular weight distribution (MWD) and the absorption coefficient in the Near Infrared (NIR), visible, and ultraviolet regions. X-ray Photoelectron Spectroscopy (XPS) has been performed to learn what happens at the surface of the polymer after bombardment. The main result of these studies is that at fluence higher than 10¹³ cm⁻² both chemical and physical effects follow a nonlinear behavior due to the transition from a single-track regime to a track overlap regime. This transition is explained in terms of progressive chemical change of the irradiated polymer from the pristine chemical structure to a new one depleted of the ester pendent groups. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 655–664, 1998     

Coulomb Friction Driving Brownian Motors

We review a family of models recently introduced to describe Brownian motors under the influence of Coulomb friction, or more general non-linear friction laws. It is known that, if the heat bath is modeled as the usual Langevin equation (linear viscosity plus white noise), additional non-linear friction forces are not sufficient to break detailed balance, i.e. cannot produce a motor effect. We discuss two possibile mechanisms to elude this problem. A first possibility, exploited in several models inspired to recent experiments, is to replace the heat bath's white noise by a "collisional noise", that is the effect of random collisions with an external equilibrium gas of particles. A second possibility is enlarging the phase space, e.g. by adding an external potential which couples velocity to position, as in a Klein-Kramers equation. In both cases, non-linear friction becomes sufficient to achieve a non-equilibrium steady state and, in the presence of an even small spatial asymmetry, a motor effect is produced.     

Synthesis, physicochemical properties and antioxidant activity of deferiprone-cyclodextrin conjugates and their iron(III) complexes

3-Hydroxy-1,2-dimethylpyridin-4(1H)-one (deferiprone) is a successful iron chelator, which has been widely investigated for its activity in mitigating iron overload and in protecting against oxidative stress due to Reactive Oxygen Species (ROS). Herein, we present the synthesis, characterisation, physicochemical properties and antioxidant activity of two novel bioconjugates of β-cyclodextrin bearing the deferiprone moiety either on the upper rim (1) or on the lower rim (2) of the cyclodextrin and their iron(III) complexes. Protonation and iron stability constants were measured by spectrophotometric titration for the two systems and antioxidant activity studied for both the ligands and the iron(III) complexes.     

Structural effects of lipophilic methotrexate conjugates on model phospholipid biomembranes

Lipophilic conjugates of the antitumor drug methotrexate (MTX) with lipoamino acids (LAAs) have been previously described as a tool to enhance MTX passive entrance into cells, overcoming a form of transport resistance which makes tumour cells insensitive to the antimetabolite. A knowledge of the mechanisms of interaction of such lipophilic derivatives with cell membranes could be useful for planning further lipophilic MTX derivatives with an optimal antitumour activity. To this aim, a calorimetric study was undertaken using a biomembrane model made from synthetic 1,2-dipalmitoyl-glycero-3-phosphocholine (DPPC) multilamellar liposomes. The effects of MTX and conjugates on the phase transition of liposomes were investigated using differential scanning calorimetry.

The interaction of pure MTX with the liposomes was limited to the outer part of the phospholipid bilayers, due to the polar nature of the drug. Conversely, its lipophilic conjugates showed a hydrophobic kind of interaction, perturbing the packing order of DPPC bilayers. In particular, a reduction of the enthalpy of transition from the gel to the liquid crystal phase of DPPC membranes was observed. Such an effect was related to the structure and mole fraction of the conjugates in the liposomes.

The antitumour activity of MTX conjugates was evaluated against cultures of a CCRF–CEM human leukemic T-cell line and a related MTX resistant sub-line. The in vitro cell growth inhibitory activity was higher for bis(tetradecyl) conjugates than for both the other shorter- and longer-chain derivatives. The biological effectiveness of the various MTX derivatives correlated very well with the thermotropic effects observed on the phase transition of DPPC biomembranes.     

Synthesis of AB and ABA block copolymers as compatibilizers in nylon 6/polycarbonate blends

Nylon 6 (Ny6) and Bisphenol A polycarbonate (PC) are immiscible and form biphasic blends. To improve the compatibility of Ny6 and PC several ABA and AB Ny6/PC block copolymers were synthesized, and their compatibilizing behavior on the blends were tested. Block copolymers were prepared by reacting monoamino- or diamino-terminated Ny6 homopolymers with high molecular weight PC at 130°C in anhydrous DMSO. The reaction of diamino- and monoamino-terminated Ny6 with polycarbonate produces block copolymers of the type PC-Ny6-PC (ABA) and PC-Ny6 (AB), respectively, plus a certain amount of unconverted PC degradated to lower molecular weights. To separate the block copolymer from the unconverted PC, a selective fractionation with tetrahydrofuran (THF) and trifluoroethanol (TFE) was carried out. Three different fractions were obtained: THF-soluble fraction, TFE-soluble fraction, and the TFE-insoluble fraction. The scanning electron microscopy (SEM) analysis of a 75/25 (wt/wt) Ny6/PC blend added with 2% of ABA or AB block copolymers, showed the presence of smaller PC particles more adherent to the polyamide matrix, with respect to the same blend nonadded, which is clearly biphasic. The size of the PC particles decreases from ABA to AB compatibilized blends and the adhesion with the matrix is increases in the same way. © 1996 John Wiley & Sons, Inc.     

An iron–organic polymeric smoke suppressant for poly(vinyl chloride)

The incorporation of a poly[ferrocene-1, 2 (1, 3: 1, 1′)diylmethylene] fraction with M?_n=2100 as a smoke suppressant additive into both unplasticized and di(2-ethylhexyl)phthalate-plasticized, calcium carbonate-filled poly(vinyl chloride) (PVC) compositions entails appreciable reductions in smoke evolution during combustion tests relative to unmodified formulations. Best results, with smoke density reductions in the range 25-80%, are obtained at the 3% loading level, with higher additive concentrations causing no further improvements. The findings of this study may have implications on the design of other polymeric engineering materials exposed to potential fire hazards.     

Sylow subgroups of finitary linear groups

In this paper we describe the structure and the conjugacy classes of Sylow p-subgroups of FGL(V, ), the group of finitary -automorphisms of the -vector space V.The Author is member of the GNSAGA.