Tatjana Trtić-Petrović

Characterization of drug-protein binding process by employing equilibrium sampling through hollow-fiber supported liquid membrane and Bjerrum and Scatchard plots

The technique equilibrium sampling through membrane (ESTM) was extended to measuring the free drug concentration in solutions of drug and protein. Bjerrum and Scatchard plots were employed for characterizing individual drug binding to pure human blood proteins. Four drugs were investigated as a model system: fluvoxamine and ropivacaine which dominantly bind to alpha-acid glycoprotein (AGP), and R,S-ibuprofen and S-ketoprofen which highly bind to human serum albumin (HSA). The level of drug binding to AGP and HSA relied on drug and protein concentrations. Bjerrum and Scatchard plots revealed high affinity constants (Ka) at low protein concentration. Both Bjerrum and Scatchard plots of fluvoxamine and ropivacaine binding to AGP showed one specific binding site (n1=1) with ropivacaine Ka value close to 5 times higher than the Ka of fluvoxamine at 22.9 microM AGP concentration. Bjerrum plots of ketoprofen and ibuprofen gave total number of binding sites or bound molecules of 6-7, which did not depend on the drug or protein concentration. Scatchard plots of ketoprofen and ibuprofen exhibited two binding sites (n1 and n2) at 0.15 microM and 0.75 microM HSA concentrations. On one hand, at 0.15 microM HSA, ketoprofen and ibuprofen were bound to site I at n1=1.2 and n1=1.0, respectively. However, at 0.75 microM HSA, ketoprofen and ibuprofen were bound to site I at n1=1.2 and n1=1.9, respectively. On the other hand, site II, at 0.15 microM HSA, interacted with ketoprofen and ibuprofen at n2=5.6 and 6.7, respectively. However, at 0.75 microM HSA, site II interacted with ketoprofen at n2=7.4 and ibuprofen at n2=6.2. It would be concluded that, upon mixing ketoprofen and ibuprofen in a HSA solution, a ketoprofen-ibuprofen interaction would most likely occur at site II in HSA.

Voltammetric determination of the herbicide Linuron using a tricresyl phosphate-based carbon paste electrode.

This paper summarises the results of voltammetric studies on the herbicide 3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea (Linuron), using a carbon paste electrode containing tricresyl phosphate (TCP-CPE) as liquid binder. The principal experimental conditions, such as the pH effect, investigated in Britton-Robinson buffer solutions (pH 2.0–7.0), the peak characteristics for the analyte of interest, or instrumental parameters for the differential pulse voltammetric mode were optimized for the method. As found out, the best electroanalytical performance of the TCP-CPE was achieved at pH 2.0, whereby the oxidation peak of Linuron appeared at ca. +1.3 V vs. SCE. The analytical procedure developed offers good linearity in the concentration range of 1.25–44.20 μg mL−1 (1.77 × 10−4–5.05 × 10−6 mol L−1), showing—for the first time—the applicability of the TCP-CPE for anodic oxidations in direct voltammetry (without accumulation). The method was then verified by determining Linuron in a spiked river water sample and a commercial formulation and the results obtained agreed well with those obtained by the reference HPLC/UV determination.

Application of SLM extraction for investigation of metal-humic acid bindings☆

Supported liquid membrane (SLM) extraction of Cu(II), with di(2-ethylhexyl) phosphate in kerosene as organic phase, has been studied using a flat PTFE membrane. The influence of donor phase flow rate on the extraction efficiency and the mass transfer coefficient was investigated. The dependence of extraction efficiency of Cu(II) on the presence of the humic acids (HA) in donor phase was also investigated. The extraction efficiency decreases with increasing of humic acids concentration in donor phase, due to interaction of copper ions with humic acids. Fraction of Cu(II) binding with humic acids in donor phase was calculated using the theory of mass transfer kinetics for analytical enrichment using SLM extraction formulated by Jonsson et al. We have shown that SLM extraction can be used as a method for investigation of metal-humic acid bindings. The obtained calculated values of the binding of copper to humic acids in presence of 10 and 20 mg(.)dm(-3) humic acids in donor phase are 25.6 and 55.8%, respectively. (Less)

Vortex-assisted ionic liquid based liquid-liquid microextraction of selected pesticides from a manufacturing wastewater sample

AbstractThe ionic liquid based vortex-assisted liquid-liquid microextraction (IL-VALLME) procedure was developed and validated for determination of four pesticides in a manufacturing wastewater sample: acetamiprid, imidacloprid, linuron and tebufenozide. The following ILs were tested as extractants: 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, 1-hexyl-3-methylimidazolium hexafluorophosphate, and 1-methyl-3-octylimidazolium hexafluorophosphate. The extraction efficiency and the enrichment factor dependencies on the type and amount of ionic liquids, extraction and centrifugation time, volume, pH and the ionic strength of the sample, were investigated. The concentration of pesticides in the aqueous and IL phases was determined by HPLC-DAD. The optimal conditions for extraction of the pesticides were determined: the aqueous sample volume of 10 mL with the addition of 0.58 g NaCl, 40 µL of the 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide as extractant, 2 min extraction under vigorous mixing applying the vortex agitator, and separation of the phases by centrifugation for 2 min at 1000 rpm. The calibration curves of the pesticides showed good linear relationship (r2 ≥ 0.9996) in the concentration range from 0.005 to 1.00 mg L−1. Determined LOD values are 1.8, 2.3, 4.8 and 8.6 µg L−1 for Tebf, Linr, Acet and Imid, respectively. The optimized IL-VALLME was applied for determination of the pesticides in the pesticide manufacturing wastewater.

Glassy carbon and boron doped glassy carbon electrodes for voltammetric determination of linuron herbicide in the selected samples

AbstactIn this study the application of home-made unmodified (GC) and bulk modified boron doped glassy carbon (GCB) electrodes for the voltammetric determination of the linuron was investigated. The electrodes were synthesized with a moderate temperature treatment (1000°C). Obtained results were compared with the electrochemical determination of the linuron using a commercial glassy carbon electrode (GC-Metrohm). The peak potential (Ep) of linuron oxidation in 0.1 mol dm−3 H2SO4 as electrolyte was similar for all applied electrodes: 1.31, 1.34 and 1.28 V for GCB, GC and GC-Metrohm electrodes, respectively. Potential of linuron oxidation and current density depend on the pH of supporting electrolyte. Applying GCB and GC-Metrohm electrodes the most intensive electrochemical response for linuron was obtained in strongly acidic solution (0.1 mol dm−3 H2SO4). Applying the boron doped glassy carbon electrode the broadest linear range (0.005–0.1 µmol cm−3) for the linuron determination was obtained. The results of voltammetric determination of the linuron in spiked water samples showed good correlation between added and found amounts of linuron and also are in good agreement with the results obtained by HPLC-UV method. This appears to be the first application of a boron doped glassy carbon electrode for voltammetric determination of the environmental important compounds.

Influence of module arrangements on solvent extraction of thallium(III) in hollow fiber contactors

The influence of module arrangements on solvent extraction of thallium(III) from NaCl/H 2 SO 4 solution into butyl acetate has been studied using two laboratory-made modules consisting of hydrophobic polypropylene hollow fibers. The aqueous phase was recirculated between the module(s) and a mixed reservoir, and the organic phase was stagnant on the shell side. It was found that the extraction of Tl(III) from aqueous phase strictly depends on aqueous flow rate and module arrangement. The results obtained are discussed in terms of the fraction of Tl(III) removed from the aqueous phase reservoir, the flux of Tl(III) through the interfacial area, and the best arrangement of modules for the production process of the radiopharmaceutical 201 TlCl.

Mass transfer resistance in a liquid‐phase microextraction employing a single hollow fiber under unsteady‐state conditions

In this study, the mass transport resistance in liquid-phase microextraction (LPME) in a single hollow fiber was investigated. A mathematical model has been developed for the determination of the overall mass transfer coefficient based on the acceptor phase in an unsteady state. The overall mass transfer coefficient in LPME in a single hollow fiber has been estimated from time-dependent concentration of extracted analyte in the acceptor phase while maintaining a constant analyte concentration in the donor phase. It can be achieved either using a high volume of donor to acceptor phase ratio or tuning the extraction conditions to obtain a low-enrichment factor, so that the analyte concentration in the sample is not significantly influenced by the mass transfer. Two extraction systems have been used to test experimentally the developed model: the extraction of Lu(III) from a buffer solution and the extraction of three local anesthetics from a buffer or plasma solution. The mass transfer resistance, defined as a reciprocal values of the mass transfer coefficient, was found to be 1.2 × 10(3) cm(-1) min for Lu(III) under optimal conditions and from 1.96 to 3.3 × 10(3) cm(-1) min for the local anesthetics depending on the acceptor pH and the hydrophobicity of the drug.

Extraction of lutetium(III) from aqueous solutions by employing a single fibre-supported liquid membrane

Transport behaviour of Lu(III) across a polypropylene hollow fibre-supported liquid membrane containing di(2-ethylhexyl)phosphoric acid (DEHPA) in dihexyl ether as a carrier has been studied. The donor phase was LuCl(3) in the buffer solution consisting of 0.2 M sodium acetate at pH 2.5-5.0. A miniaturised system with a single hollow fibre has been operated in a batch mode. The concentration of Lu(III) was determined by indirect voltammetric method using Zn-EDTA complex. The effect of pH and volume of the donor phase, DEHPA concentration in the organic (liquid membrane) phase, the time of extraction and the content of the acceptor phase on the Lu(III) extraction and stripping behaviour was investigated. The results were discussed in terms of the pertraction and removal efficiency, the memory effect and the mean flux of Lu(III). The optimal conditions for the removal of (177)Lu(III) from labelled (177)Lu-radiopharmaceuticals were discussed and identified. The removal efficiency of Lu(III) greater than 99% was achieved at pH of the donor phase between 3.5 and 5.0 using DEHPA concentration in the organic phase of 0.47 M and the ratio of the donor to the acceptor phase of 182.

Indirect determination of lutetium by differential pulse anodic stripping voltammetry at a hanging mercury drop electrode

Lutetium has been determined by differential pulse anodic stripping voltammetry in an acidic solution containing Zn-EDTA. Lutetium (III) ions liberated zinc (II), which was preconcentrated on a hanging mercury drop electrode and stripped anodically, resulting in peak current linearly dependent on lutetium (III) concentration. Less than 0.4 ng mL−1 lutetium could be detected after a 2 min deposition.

Determination of Carbendazim by an Ionic Liquid Modified Carbon Paste Electrode

ABSTRACT A new method for the electroanalytical determination of carbendazim is reported using a novel ionic liquid-based carbon paste electrode. 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, and 1-butyl-1-methylpyrrolidinium bis(trifluoromethyl-sulfonyl)imide were used as additives in the paste for electrode fabrication. The electrodes were characterized by cyclic voltammetry of the couple and scanning electron microscopy. The carbon paste electrode containing 19% 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide was selected for the electrochemical determination of carbendazim by differential pulse adsorptive stripping voltammetry. The influence of electrolyte pH, accumulation potential and time, and the presence of selected pesticides on electrochemical behavior of carbendazim were characterized. The optimal conditions for differential pulse adsorptive stripping voltammetry of carbendazim were determined to be a pH 5.0 Britton–Robinson buffer, an accumulation potential of −0.05 V, an accumulation time of 120 s, a start potential of −0.10 V vs. the reference; an end potential of +1.30 V, and a scan rate of 0.050 V s−1. The linear dynamic range of the method was from 0.010 to 0.247 mg L−1 with a correlation coefficient of 0.9995. The recovery was 104.1% in fortified tap water, demonstrating its suitability for the analysis of water.