Determination of organophosphate and carbamate pesticides based on enzyme inhibition using a pH-sensitive fluorescence probe

A flow injection system for the determination of organophosphate and carbamate pesticides is described. A sensitive fluorescence probe was synthesized and used as the pH indicator to detect the inhibition of the enzyme acetylcholinesterase (ACNE). The percentage inhibition of enzyme activity is correlated to the pesticide concentration. Several parameters influencing the performance of the system are discussed. The detection limits of 3.5, 50, 12 and 25 mug/l for carbofuran, carbaryl, paraoxon and dichlorvos, in pure water, respectively were achieved with an incubation time of 10 min. A complete cycle of analysis, including incubation time, took 14 min. The detection system has been applied to the determination of carbofuran in spiked vegetable juices (Chinese cabbage and cole), achieving recovery values between 93.2 and 107% for Chinese cabbage juice and 108 and 118% for cole juice at the different concentration levels assayed. (C) 2004 Elsevier B.V. All rights reserved.

Separation of acidic and basic compounds in capillary electrochromatography with polymethacrylate-based monolithic columns

Methacrylate-based monolithic columns with electroosmotic flow (EOF) or very weak EOF are prepared by in situ copolymerization in the presence of a porogen in fused-silica capillaries pretreated with a bifunctional reagent. Satisfactory separations of acidic and basic compounds on the column with EOF at either low or high pH are achieved, respectively. With sulfonic groups as dissociation functionalities, sufficient EOF mobility still remains as high as 1.74 x 10(-4) cm(2) s(-1) V-1 at low pH. Under this condition, seven acidic compounds are readily separated within 5.7 min. Moreover, at high pH, the peak shape of basic compounds is satisfactory without addition of any masking amines into running mobile phase since the secondary interaction between the basic compounds and the monolithic stationary phase are minimized at high pH. Reversed-phase mechanism for both acidic and basic compounds is observed under investigated separation conditions. In addition, possibilities of acidic and basic compound separations on a monolithic column with extremely low EOF are discussed. (C) 2004 Elsevier B.V. All rights reserved.

Short columns with molecularly imprinted monolithic stationary phases for rapid separation of diastereomers and enantiomers

Three molecularly imprinted monolithic columns with different length but almost identical column volume had been prepared. It was observed that the separation factors of diastereomers and enantiomers were almost unaffected by column length. However, the short column with dimension of 38 mm x 8 mm W. showed much lower resistance to flow rate so that it could be operated at much higher flow rates. By combining stepwise gradient elution with elevated flow rate, the diastereomers of cinchonine and cinchonidine and the enantiomers of Cbz-DL-Trp and Fmoc-DL-Trp were successfully separated within 3 min on the short column with dimension of 38 mm. x 8 mm i.d.. Based on the above results, a cinchonine imprinted monolithic disk with dimension of 10 mm x 16 mm W. was further developed. The SEM image and the pore size distribution profile showed that large flow-through pores are present on the prepared monolith, which allowed mobile phase to flow through the disk with very low resistance. Chromatographic performances on the monolithic disk were almost unchanged compared with the long columns. A rapid separation of cinchonine and cinchonidine was achieved in 2.5 min at the flow rate of 9.0 ml/min. Furthermore, it was observed that there was almost no effect of the flow rate on the dynamic binding capacity at high flow rates. In addition, the effect of the loading concentration of analytes on the dynamic binding capacity, namely adsorption isotherm, was also investigated. A non-linear adsorption isotherm of cinchonine was observed on the molecularly imprinted monolith with cinchonine as template, which might be a main reason to result in the peak tailing of template molecule. (C) 2004 Elsevier B.V. All rights reserved.

Molecularly imprinted monolithic stationary phases for liquid chromatographic separation of enantiomers and diastereomers

The method for preparation of molecularly imprinted monolithic stationary phase has been improved to achieve liquid chromatographic separation of enantiomers and diastereomers. By adopting low polar porogenic solvents of toluene and dodecanol and optimal polymerization conditions, the molecularly imprinted monolithic stationary phases with good flow-through properties and high resolution were prepared. Enantiomers of amino acid derivatives and diastereomers of cinchona alkaloids were completely resolved using the monolithic stationary phases. The influence of porogenic composition, monomer-template ratio and polymerization conditions on the chromatographic performance was investigated. Some chromatographic conditions such as the composition of the mobile phase and the temperature were characterized. Scanning electron microscopy showed that the molecularly imprinted monolithic stationary phase has a large through-pore structure to allow the mobile phase to flow through the column at very low backpressure. Accelerated separations of enantiomers and diastereomers were therefore achieved at elevated flow rates. Finally, the chiral recognition performance of the prepared stationary phase in aqueous media was investigated. Hydrophobic interaction, and ionic and/or hydrogen bonding interactions were proposed to be responsible for the recognition mechanism. (C) 2002 Elsevier Science B.V. All rights reserved.

Determination of peptides and amino acids from wool and beer with sensitive fluorescent reagent 2-(9-carbazole)-ethyl chloroformate by reverse phase high-performance liquid chromotography and liquid chromotography mass spectrometry

A new method for the sensitive determination of amino acids and peptides using the tagging reagent 2-(9-carbazole)-ethyl chloroformate (CEOC) with fluorescence (FL) detection has been developed. Identification of derivatives was carried out by liquid chromotography mass spectrometry. The chromophore in the 2-(9-fluorenyl)-ethyl chloroformate (FMOC) reagent was replaced by carbazole, which resulted in a sensitive fluorescence lerivatizing agent CEOC. CEOC can easily and quickly label peptides and amino acids. Derivatives are stable enough to be efficiently analyzed by high-performance liquid chromatography. Studies on derivatization demonstrate excellent derivative yields over the pH range 8.8-10.0. Maximal yields close to 100% are observed with three- to fourfold molar reagent excess. Derivatives exhibit strong fluorescence and allow direct injection of the reaction mixture with no significant disturbance from the major fluorescent reagent degradation by-products, such as 2(9-carbazole)-ethanol and bis-(2-(9-carbazole)-ethyl) carbonate. In addition, the detection responses for CEOC derivatives are compared to those obtained with FMOC. The ratios AC(CEOC)/AC(FMOC) = 1.00-1.82 for fluorescence (FL) response and AC'(CEOC)/AC'(FMOC) = 1.00-1.21 for ultraviolet (UV) response are observed (here, AC and AC' are, respectively, FL and UV F response). Separation of the derivatized peptides and amino acids has been optimized on a Hypersil BDS C18 column. Excellent linear responses are observed. This method was used successfully to analyze protein hydrolysates from wool and from direct-derivatized beer. (C) 2003 Elsevier Science (USA). All rights reserved.

Artificial neural network classification based on high-performance liquid chromatography of urinary and serum nucleosides for the clinical diagnosis of cancer

Nucleosides in human urine and serum have frequently been studied as a possible biomedical marker for cancer, acquired immune deficiency syndrome (AIDS) and the whole-body turnover of RNAs. Fifteen normal and modified nucleosides were determined in 69 urine and 42 serum samples using high-performance liquid chromatography (HPLC). Artificial neural networks have been used as a powerful pattern recognition tool to distinguish cancer patients from healthy persons. The recognition rate for the training set reached 100%. In the validating set, 95.8 and 92.9% of people were correctly classified into cancer patients and healthy persons when urine and serum were used as the sample for measuring the nucleosides. The results show that the artificial neural network technique is better than principal component analysis for the classification of healthy persons and cancer patients based on nucleoside data. (C) 2002 Elsevier Science B.V. All rights reserved.

Spatial variability in water quality and surface sediment diatom assemblages in a complex lake basin,lake of the woods,ontario,canada

Lake of the Woods (LOW) is an international waterbody spanning the Canadian provinces of Ontario and Manitoba, and the U.S. state of Minnesota. In recent years, there has been a perception that water quality has deteriorated in northern regions of the lake, with all increase in the frequency and intensity of toxin-producing cyanobacterial blooms. However, given the lack of long-term data these trends are difficult to verify. As a first step, we examine spatial and seasonal patterns in water quality in this highly complex lake on the Canadian Shield. Further, we examine surface sediment diatom assemblages across multiple sites to determine if they track within-take differences in environmental conditions. Our results show that there are significant spatial patterns in water quality in LOW. Principal Component Analysis divides the lake into three geographic zones based primarily on algal nutrients (i.e., total phosphorus, TP), with the highest concentrations at sites proximal to Rainy River. This variation is closely tracked by sedimentary diatom assemblages, with [TP] explaining 43% of the variation in diatom assemblages across sites. The close correlation between water quality and the surface sediment diatom record indicate that paleoecological models could be used to provide data on the relative importance of natural and anthropogenic sources of nutrients to the lake.

Electron self-exchange reaction of viologen and its derivatives in poly(ethylene glycol)

The electron self-exchange rates (k(ex)) of viologen and its derivatives are estimated by using microelectrode voltammetry in poly(ethylene glycol) films. The dependences of supporting electrolyte concentration and sizes of viologen and its derivatives on k(ex) and diffusion coefficients (D) are discussed. Results show that k(ex) increases with the decrease of supporting electrolyte concentration and sizes of reactants. (C) 2000 Elsevier Science S.A. All rights reserved.

Effect of LB monolayers on the mixed crystals of Lead and barium sulfate

The effect of LB monolayers on the mixed crystal was investigated by using X-ray photoelectron spectroscopy (XPS), Transmission electron microscopy (TEM), and Inductively coupled plasma-atomic emission spectroscopy (ICP-AES). The results show that LB monolayer has selectivity for the different nucleation ions with equal charge numbers and about the same ion radius. The selectivity is dependent on the head groups of monolayer. The monolayer and the doped ions have also an effect on the crystal morphology. (C) 2000 Published by Elsevier Science B.V. All rights reserved.

Layer-by-layer assembly of multilayer films consisting of silicotungstate and a cationic redox polymer on 4-aminobenzoic acid modified glassy carbon electrode and their electrocatalytic effects

A novel 4-aminobenzoic acid (4-ABA) monolayer film is formed on glassy carbon electrode (GCE) by amino cation radical method. Silicotungstic heteropolyanion (SiW12O404-, denoted as SiW12)-containing multilayer films have been fabricated on the 4-ABA modified GCE surface by alternate deposition with a quaternized poly(4-vinylpyridine) partially complexed with [Os(bpy)(2)Cl](2+/+) (denoted as QPVP-Os). Cyclic voltammetry (CV), X-ray photoelectron spectroscopy (XPS) and X-ray reflectivity (XR) have been used to characterise the as-prepared multilayer films. It is proved that the multilayer films are uniform and stable. The average thickness for a bilayer of QPVP-Os/SiW12 in the multilayer film is 30.2 Angstrom. The electrocatalytic activities of the multilayer films have been investigated on the reduction of three substrates of important analytical interests, HNO2, BrO3- and H2O2. Especially, the influence of layer number of the multilayer films on the electrocatalytic reduction of HNO2 has been investigated in detail. (C) 2000 Elsevier Science B.V. All rights reserved.

Radiation effects on the immiscible polymer blend of nylon1010 and high-impact polystyrene (HIPS) I: Gel/dose curves, mathematical expectation theorem and thermal behaviour

This paper studies the radiation properties of the immiscible blend of nylon1010 and HIPS. The gel fraction increased with increasing radiation dose. The network was found mostly in nylon1010, the networks were also found in both nylon1010 and HIPS when the dose reaches 0.85 MGy or more. We used the Charleby-Pinner equation and the modified Zhang-Sun-Qian equation to simulate the relationship with the dose and the sol fraction. The latter equation fits well with these polymer blends and the relationship used by it showed better linearity than the one by the Charleby-Pinner equation. We also studied the conditions of formation of the network by the mathematical expectation theorem for the binary system. Thermal properties of polymer blend were observed by DSC curves. The crystallization temperature decreases with increasing dose because the cross-linking reaction inhibited the crystallization procession and destroyed the crystals. The melting temperature also reduced with increasing radiation dose. The dual melting peak gradually shifted to single peak and the high melting peak disappeared at high radiation dose. However, the radiation-induced crystallization was observed by the heat of fusion increasing at low radiation dose. On the other hand, the crystal will be damaged by radiation. A similar conclusion may be drawn by the DSC traces when the polymer blends were crystallized. When the radiation dose increases, the heat of fusion reduces dramatically and so does the heat of crystallization. (C) 1999 Elsevier Science Ltd. All rights reserved.

Morphology of conductive blend fibers of polyaniline and polyamide-11

Polyaniline (PANI), a member of the intrinsically conducting polymer (ICPs) family, was blended with polyamide-11 (polyco-aminoundecanoyle) in concentrated sulfuric acid. The above solution was used to spin conductive PANI/polyamide-11 fibers by wet-spinning technology. Scanning electron microscope (SEM) and transmission electron microscope (TEM) were employed to study the two-phase morphology of the conductive PANI/polyamide-11 fibers. The micrographs of the cross-section, the axial section and the surface of the monofilament demonstrated that the two blend components were incompatible. The morphology of PANI in the fibers was of fibrillar form, which was valuable for producing conducting channels. The electrical conductivity of the fibers was from 10(-6) to 10(-1) S/cm with the different PANI fraction and the percolation threshold was about 5 wt.%. By comparing the two blend systems of PANI/Polyamide-11 fibers and carbon black filled poly(ethylene terephthalate) (PET) fibers, it was shown that the morphology of the conductive component had an influence on electrical conductivity, The former had higher conductivity and lower percolation threshold than the latter. (C) 2001 Elsevier Science B.V. All rights reserved.

Determination of allopurinol and its active metabolite oxypurinol by capillary electrophoresis with end-column amperometric detection

A simple method was proposed for the separation of allopurinol (AP) and its active metabolite oxypurinol (OP) by capillary electrophoresis with end-column amperometric detection. A running buffer composed of 15 rum Na2HPO4/NaH2PO4 at a pH 9.55, electrokinetic injection 7 s at 5 kV, separation voltage at 15 kV and detection potential at 1.20 V were investigated to be the optimal condition for the separation. The method exhibited low detection Emit (S/N = 3) as 1 x 10(-8) mol/l for AP and OP, wide linearity range of 2 x 10(-7) to 1 x 10(-4) mol/l, 1 x 10(-7) to 1 x 10(-4) and high efficiency of 1.2 x 10(5) and 1.8 x 10(5) N/m for AP and OP, respectively. The potential application examined for the method was the determination of the spiked urine sample, which was proved to be sensitive and efficient. (C) 2001 Elsevier Science B.V. All rights reserved.

Radiation effects on the immiscible polymer blend of nylon1010 and high-impact strength polystyrene (II): mechanical properties and morphology

The paper studies the morphology and mechanical properties of immiscible binary blends of the nylon 1010 and HIPS through the radiation crosslinking method. In this blend, the HIPS particles were the dispersed phases in the nylon 1010 matrix. With increasing of dose, the elastic modulus increased, However, the tensile strength. elongation at bleak and the energy of fracture increased to a maximum at a dose of 0.34 MGy, then reduced with the increasing of dose. SEM photographs show that the hole sizes are not changed obviously at low dose and at high dose, remnants that cannot be dissolved in formic acid and THF can be observed in the holes and on the surface. TEM photographs showed that radiation destroys the rubber phases in the polymer blend. (C) 2001 Elsevier Science Ltd. All rights reserved.

In-situ FTIR study on adsorption and oxidation of native and thermally denatured calf thymus DNA at glassy carbon electrodes

In-situ Fourier transform infra-red (FTIR) spectra of native and thermally denatured calf thymus DNA (CT DNA) adsorbed and/or oxidized at a glassy carbon (GC) electrode surface are reported. The adsorption of native DNA occurs throughout the potential range (-0.2 similar to 1.3 V) studied, and the adsorbing state of DNA at electrode surface is changed from through the C=O band of bases and pyrimidine rings to through the C=O of cytosine and imidazole rings while the potential shifts negatively from 1.3 V to -0.2 V. An in-situ FTIR spectrum of native CT DNA adsorbed at GC electrode surface is similar to that of the dissolved DNA, indicating that the structure of CT DNA is not distorted while it is adsorbed at the GC electrode surface. In the potential range of -0.2 similar to 1.30 V, the temperature-denatured CT DNA is adsorbed at the electrode surface first, then undergoes electrochemical oxidation reaction and following that, diffuses away from the electrode surface. (C) 2001 Elsevier Science B.V. All rights reserved.