Güleren Alsancak

Mercury removal from synthetic solutions using poly(2-hydroxyethylmethacrylate) gel beads modified with poly(ethyleneimine)

In this study, the Hg2+ adsorption–desorption properties of poly(ethyleneimine) (PEI)-attached poly(2-hydroxyethylmethacrylate) (PHEMA) beads were investigated. Spherical PHEMA beads with an average size of 150–200 μm were obtained by suspension polymerization of 2-hydroxyethylmethacrylate conducted in an aqueous dispersion medium. Owing to the reasonably rough character of the bead surface, PHEMA beads had a specific surface area of 14.8 m2/g. PEI chains could be covalently attached onto the PHEMA beads with equilibrium binding capacities up to 50 mg PEI/g beads. PEI-attached PHEMA beads were utilized as adsorbent in the adsorption–desorption of Hg2+ ions from synthetic solutions. The adsorption process was fast; 90% of adsorption occurred within 45 min and equilibrium was reached at around 1 h. The maximum Hg2+ adsorption capacity obtained was 1.67 mmol/g at a pH of about pH 5.0. Adsorption behavior can be described at least approximately by the Langmuir equation. The metal-chelating beads can be easily regenerated by 0.1 M HNO3 with higher effectiveness. Adsorption of heavy metal ions from artificial wastewater was also studied. The adsorption capacities were 1.32 mmol/g for Hg2+, 0.34 mmol/g for Ni2+ and 0.42 mmol/g for Cu2+.

Voltammetric Behaviour of Sulfamethoxazole on Electropolymerized-Molecularly Imprinted Overoxidized Polypyrrole

In this work, preparation of a molecularly imprinted polymer (MIP) film and its recognition properties for sulfamethoxazole were investigated. The overoxidized polypyrrole (OPPy) film was prepared by the cyclic voltammetric deposition of pyrrole (Py) in the presence of supporting electrolyte (tetrabutylammonium perchlorate-TBAP) with and without a template molecule (sulfamethoxazole) on a pencil graphite electrode (PGE). The voltammetric behaviour of sulfamethoxazole on imprinted and non-imprinted (NIP) films was investigated by differential pulse voltammetry (DPV) in Britton-Robinson (BR) buffer solutions prepared in different ratio of acetonitrile-water binary mixture, between the pH 1.5 and 7.0. The effect of the acetonitrile-water ratio and pH, monomer and template concentrations, electropolymerization cycles on the performance of the MIP electrode was investigated and optimized. The MIP electrode exhibited the best reproducibility and highest sensitivity. The results showed that changing acetonitrile-water ratio and pH of BR buffer solution changes the oxidation peak current values. The highest anodic signal of sulfamethoxazole was obtained in BR buffer solution prepared in 50% (v/v) acetonitrile-water at pH 2.5. The calibration curve for sulfamethoxazole at MIP electrode has linear region for a concentration range of 25.10-3 to 0.75 mM (R2=0.9993). The detection limit of sulfamethoxazole was found as 3.59.10-4 mM (S/N=3). The same method was also applied to determination of sulfamethoxazole in commercial pharmaceutical samples. Method precision (RSD<1%) and recoveries (>87%) were satisfactory. The proposed method is simple and quick. The polypyrrole (PPy) electrodes have low response time, good mechanical stability and are disposable simple to construct.

Combined effect of polarity and pH on the chromatographic behavior of some angiotensin II receptor antagonists and optimization of their determination in pharmaceutical dosage forms

In the present study, the combined effect of mobile phase polarity and pH on retention behavior of some ARA-IIs (irbesartan, losartan, valsartan and telmisartan) is investigated. The linear relationships established between retention factors of the species and the polarity parameter of the mobile phase has proved to predict accurately retention in LC as a function of the acetonitrile content (50%, 55%, 60%, v/v). The suggested model uses the pH value in the acetonitrile-water mixture as mobile phase instead of pH value in water and takes into account the effect of activity coefficients. Moreover, correlation between retention and the mobile phase pH can be established allowing prediction of the retention behavior as a function of the mobile phase pH. The model can be used to estimate the pKa in an acetonitrile percentage between 50% and 60%, at 30 degrees C. The developed method was successfully applied to both the simultaneous separation of these drug-active compounds and individual determination in their commercial pharmaceutical dosage forms.

Determination of protonation constants of some tetracycline antibiotics by potentiometry and lc methods in water and acetonitrile-water binary mixtures

An accurate estimation of dissociation constants of tetracycline antibiotics in acetonitrile-water binary mixtures is very important for several separation techniques such as liquid chromatography and capillary electrophoresis that use these solvent mixtures. In this study, the pKa values of five tetracyclines (tetracycline, oxytetracycline, chlortetracycline, doxycycline and metacycline), have been determined in water and acetonitrile-water binary mixtures (10%, 20% and 30% (v/v)) by potentiometry and liquid chromatography (LC). The obtained results show a similar trend for the pKa1 values of five tetracycline antibiotics as they increase with increasing concentration of organic modifier, which allows a linear relationship between pKa1 values and mole fraction of acetonitrile to be obtained. The pKa values obtained in aqueous medium have been compared with the values predicted by the SPARC on-line pKa calculator.

Determination of pKa values of nonsteroidal antiinflammatory drug-oxicams by RP-HPLC and their analysis in pharmaceutical dosage forms.

In this study, pK(a) values were determined by using the dependence of the capacity factor on the pH of the mobile phase for four ionizable substances, namely, tenoxicam, piroxicam, meloxicam, and naproxen (I.S.). The effect of the mobile phase composition on the ionization constant was studied by measuring the pK(a) at different ACN concentrations, ranging from 30 to 40%. The adequate condition for the chromatographic determination of these compounds in pharmaceutical dosage forms was established based on the different retention behaviors of the species. An octadecylsilica Nucleosil C18 column (150 x 4.6 mm, 5 microm) was used for all the determinations. The chromatographic separation of oxicams was carried out using acetonitrile (ACN)/water at 35% v/v, containing 65 mM phosphoric acid and UV detection at a wavelength of 355 nm. The method developed was successfully applied to the simultaneous determination of these drug compounds in laboratory-prepared mixtures and their commercial pharmaceutical dosage forms. Each analysis requires no longer than 12 min.

Optimization of the experimental conditions for macrolide antibiotics in high performance liquid chromatography by using response surface methodology and determination of tylosin in milk samples

The simple, rapid and sensitive liquid chromatographic separation of five macrolides (tilmicosin, erythromycin, tylosin, roxithromycin and josamycin) widely used in food producing animals was developed. Response surface methodology was used as an optimization method of mobile phase, column temperature and pH to provide the best resolution of these analytes. The separation was performed by using an end-capped X-Terra RP-18 column (250 × 4.6 mm I.D × 5 m) with an isocratic system of 15 mM hydrochloric acid (pH 2.5)-acetonitrile as the mobile phase at a temperature of 30°C and flow-rate of 1.0 mL/min. The suitability of the method for multi-residue determination of the macrolides is demonstrated by the analysis of milk samples spiked with tylosin. Roxithromycin was used as internal standard. The recovery of tylosin was quite good as 90.8%. The limit of quantification and detection limit were 0.024 and 0.007 μg/mL, respectively. The method was successfully applied to determination of macrolides at levels below the maximum concentration legally allowed in milk samples.

Electroanalytical Determination of Some Sulfonamides on Overoxidized Polypyrrole Electrodes

The electrochemical behaviours of five sulfonamides (sulfanilamide, sulfadiazine, sulfamerazine, sulfamonomethoxine, sulfamethoxazole) were investigated with overoxidized polypyrrole (OPPy) modified pencil graphite electrodes. The performance of the OPPy electrode was evaluated by differential pulse voltammetry in Britton–Robinson buffer solutions prepared in different ratio of acetonitrile-water binary mixture, between pH 1.5 and 7.0. The highest anodic signals of sulfonamides were obtained in Britton–Robinson buffer solution prepared in 50% (v/v) acetonitrile-water at pH 2.5 and 3.0. The OPPy electrodes exhibited good performance for sulfonamides with wide linear ranges (≈10–5–10–3 M), highly reproducible responses (RSD% ≤0.92) and correlation coefficients (≥0.9990). The calculated limits of detection were ~10–6 or 10–7 M at 3σ. In order to verify the reliability of the OPPy electrode as a sensor, it is used for determination of sulfamethoxazole in a pharmaceutical tablet. The recovery was found as 95.96% with the RSD% of 0.68. The overoxidized polypyrrole modified pencil graphite electrode showed a stable and reproducible response without any influence of interferent commonly existing in pharmaceutical containing sulfamethoxazole.

Determination of chromatographic dissociation constants of some carbapenem group antibiotics and quantification of these compounds in human urine

The dissociation constant values (s (s) pKa ) of some carbapenem group drugs (ertapenem, meropenem, doripenem) in different percentages of methanol-water binary mixtures (18, 20 and 22%, v/v) were determined from the mobile phase pH dependence of their retention factor. Evaluation of these data was performed using the NLREG program. From calculated pKa values, the aqueous pKa values of these subtances were calculated by different approaches. Moreover, the correlation established between retention factor and the pH of the water-methanol mobile phase was used to determine the optimum separation conditions. In order to validate the optimized conditions, these drugs were studied in human urine. The chromatographic separation was realized using a Gemini NX C18 column (250 × 4.6 mm i.d., 5 µm particles) and UV detector set at 220 and 295 nm.

Determination of sulfamethoxazole in pharmaceutical formulations by flow injection system/HPLC with potentiometric detection using polypyrrole electrode

In this work, it was used a polypyrrole (PPy) electrode as a potentiometric electrochemical detector in a flow injection system in order to determine sulfamethoxazole in pharmaceutical formulations. The PPy electrode was prepared by cyclic voltammetry in acetonitrile solution. A linear relationship was observed over the concentration range of 2.5 × 10-5-1.25 × 10-3 mol L-1 with a correlation coefficient of 0.9977 and limit of detection (LOD) of 1.03 × 10-6 mol L-1 (S/N = 3). The recoveries in tablet and syrup formulations were found as 97.4 and 90.8% with the relative standard deviations of 0.62 and 1.04%, respectively, which closely agree with those measured by high performance liquid chromatography (HPLC) with UV detector. Therefore, it was concluded that the PPy electrode can be used as an alternative novel potentiometric detector material for determination of sulfamethoxazole in pharmaceuticals with the advantages of easy preparation and regeneration capability of the electrode surface.