Sensitive, reliable and simultaneous determination of Fingolimod and Citalopram drug molecules used in multiple sclerosis treatment based on magnetic solid phase extraction and HPLC-PDA.

An analytical methodology has been developed for trace amounts of Fingolimod (FIN) and Citalopram (CIT) drug molecules based on magnetic solid phase extraction (MSPE) and high performance liquid chromatographic determination with photodiode array detector (HPLC-DAD). Fingolimod is used in treatment of Multiple sclerosis (MS) disease and sometimes antidepressant drugs such as citalopram accompany to treatment. Both simultaneous analysis of these molecules and application of MSPE with a new adsorbent has been performed for first times. Fe3O4@L-Tyrosine magnetic particles has been synthetized and characterized as a new magnetic adsorbent. Experimental variables of MPSE were examined and optimized step by step such as pH, adsorption and desorption conditions, time effect, etc. Analytical parameters of the proposed method were studied and determined under optimized conditions according to international guidelines. HPLC analysis of FIN and CIT molecules was performed by isocratic elution of a mixture of 50 % Acetonitrile, 40 % pH:3 phosphate buffer and 10 % methanol with flow rate 1.0 mL min-1. The chosen wavelengths in PDA was determined as 238 nm for FIN and 213 nm for CIT. The limits of detection (LOD) for proposed method were 6.32 ng mL-1 for FIN and 6.85 ng mL-1 for CIT molecules. RSD % values were lower than 5.5 % in analysis of model solutions including 250 and 500 ng mL-1 of target molecules. Recovery values by means of synthetic urine and saliva samples were in the range of 95.7-105.4 % for both molecules.

Titania-based fabric phase sorptive extraction approach for the determination of antiepileptic drugs, levetiracetam and lamotrigine in urine samples using high-performance liquid chromatography-photo diode array detection.

A new fabric phase sorptive extraction (FPSE) based separation and enrichment method was developed for sensitive determination of two antiepileptic drug molecules, Levetiracetam (LEV) and Lamotrigine (LTG). The analysis of these drug molecules was performed with high-performance liquid chromatography equipped with photodiode array detector (HPLC-PDA) after FPSE. HPLC analysis was carried out by using phenyl hexyl column, under isocratic conditions with the mobile phase composed of pH 3.0 buffer-acetonitrile (77:23 v: v). All parameters affecting the separation and enrichment process were studied and optimized step by step. The linear working range of the developed method was calculated in the range of 10.0-1000.0 ng mL-1 for both the drug molecules (LEV and LTG). The limits of detection of the method (LODs) were calculated as 2.72 and 3.64 ng mL-1, respectively. The relative standard deviation (%RSD) values of the developed method as an indicator of precision were varied between 4.0 and 7.3. The accuracy of the optimized FPSE method was determined by the recovery tests utilizing spiked samples and results were assessed in the range from 94.6 to 106.3%. This is the first application of sol-gel Titania polycaprolactone-polydimethylsiloxane-polycaprolactone (Ti-PCAP-PDMS-PCAP) based FPSE membrane in the determination of antiepileptic drug molecules.

Applications of electrophoresis for small enantiomeric drugs in real-world samples: Recent trends and future perspectives.

Separation and identification of chiral molecules is a topic widely discussed in the literature and of fundamental importance, especially in the pharmaceutical and food fields, both from industrial and laboratory points of view. Several techniques are used to carry out these analyses, but high-performance liquid chromatography is often the "gold standard." The high costs of chiral columns, necessary for this technique, led researchers to look for an alternative, and capillary electrophoresis (CE) is a technique capable of overcoming some of the disadvantages of liquid chromatography, often providing comparable results in terms of sensitivity and robustness. We addressed this topic, already widely discussed in the literature, providing an overview of the last 6 years of the most frequent and recent applications of CE. To make the manuscript more effective, we decided to divide it into paragraphs that represent the main field of application, from enantioseparation in complex matrices (pharmacokinetic studies or toxicological dosage of drugs, analysis of environmental pollutants, and analyses of foods) to quality control analyses on pharmaceutical formulas. About these, which are the fields of most meaningful use, we mentioned some of the most innovative and performing methods, with a look to the future on the application of new materials used, such as chiral selectors, that can make these types of analyses accessible to all, reducing cost, time, and excessive use of toxic solvents.

A facile fabric phase sorptive extraction method for monitoring chloramphenicol residues in milk samples.

Determination of pharmaceutical active molecules in the biological matrices is crucial in various fields of clinical and pharmaceutical chemistry, e.g., in pharmacokinetic studies, developing new drugs, or therapeutic drug monitoring. Chloramphenicol (CP) is used for treating bacterial infections, and it's one of the first antibiotics synthetically manufactured on a large scale. Fabric phase sorptive extraction (FPSE) was used to determine Chloramphenicol antibiotic residues in milk samples by means of validated HPLC-DAD instrumentation. Cellulose fabric phases modified with polyethylene glycol-block-polypropylene glycol-block-polyethylene glycol triblock copolymer was synthesized using sol-gel synthesis approach (Sol-gel PEG-PPG-PEG) and used for batch-type fabric phase extractions. Experimental variables of the FPSE method for antibiotic molecules were investigated and optimized systematically. The HPLC analysis of chloramphenicol was performed using a C18 column, isocratic elution of trifluoroacetic acid (0.1%), methanol, and acetonitrile (17:53:30) with a flow rate of 1.0 mL/min. The linear range for the proposed method for chloramphenicol (r2 > 0.9982) was obtained in the range of 25.0-1000.0 ng/mL. The limit of detections (LOD) is 8.3 ng/mL, while RSDs% are below 4.1%. Finally, the developed method based on FPSE-HPLC-DAD was applied to milk samples to quantitatively determine antibiotic residues.

Use of newly synthetized magnetic Fe3O4 nanoparticles modified with hexadecyl trimethyl ammonium bromide for the sensitive analysis of antidepressant drugs, duloxetine and vilazodone in wastewater and urine samples.

A new enrichment and determination method involving HPLC-DAD analysis following magnetic solid-phase extraction (MSPE) was developed to detect trace amounts of two antidepressant drugs, namely, duloxetine (DUL) and vilazodone (VIL). In this study, a solid-phase sorbent was newly synthesized for use in the MSPE and its characterization was carried out by scanning electron microscopy (SEM), Fourier transform infrared (FTIR) spectroscopy, Raman spectroscopy and X-ray diffraction (XRD) techniques. In this proposed method, DUL and VIL molecules were enriched using newly synthesized magnetic-based nanoparticles in the presence of pH 10.0 buffer and desorbed with acetonitrile to a smaller volume prior to chromatographic determinations. After experimental variables were optimized, the VIL and DUL molecules were analyzed at wavelengths of 228 nm for DUL and 238 nm for VIL with isocratic elution of methanol, trifluoroacetic acid (TFA) (0.1%), and acetonitrile (10 : 60 : 30). The detection limits obtained under optimized conditions were 1.48 ng mL-1 and 1.43 ng mL-1, respectively. The %RSD values were found to be lower than 3.50% with model solutions containing 100 ng mL-1 (N:5). Finally, the developed method was successfully applied to wastewater samples and simulated urine samples, and quantitative results were obtained in the recovery experiments.

Application of magnetic solid-phase extraction for sensitive determination of anticancer drugs in urine by means of diamino benzidine tetrachlorohydrate modified magnetic nanoparticles.

BACKGROUND: The analysis of drug active molecules and residues in the treatment of cancer is important for the sustainability of human life and therapeutic effects. For this purpose, a new magnetic sorbent was developed to use in solid phase extraction prior to conventional high-performance liquid chromatography (HPLC) analysis of Paclitaxel (PAC) and Gemcitabine (GEM) molecules. METHODS: In this study, a separation and pre-concentration approach based on magnetic solid phase extraction (MSPE) was proposed for PAC and GEM by means of using a newly synthesized magnetic sorbent. After the MSPE procedure, an HPLC system with a diode array detector (DAD) was used to analyze trace amounts of PAC and GEM anticarcinogenic drugs in urine samples. Surface modification of magnetic Fe3O4 nanoparticles was carried out by diaminobenzidinetetrachloro hydrate (DABTC) for the first time and a useful sorbent was obtained for MSPE experiments. RESULTS: In the proposed method, PAC and GEM molecules were retained on the c in the presence of a pH 5.0 medium and desorbed to 300 µL of acetonitrile: methyl alcohol (1:1) eluent phase before HPLC-DAD analysis. Under the optimized conditions, the limit of detection (LOD) values for PAC and GEM were 1.38 and 1.44 ng mL-1 while the enhancement factor for PAC and GEM were 139.5 and 145.3, respectively. The relative standard deviations (RSD %) for PAC and GEM were below 3.50% in inter-day repeated experiments by means of model solutions containing 100 ng mL-1 drug active ingredients. CONCLUSIONS: Synthesis and characterization of DABTC-Fe3O4 nanoparticles were performed using suitable methodologies. Optimization of MSPE was done step by step. And finally, the developed method was successfully applied to urine samples with quantitative recoveries in the range of 99.0% and 105.0%.

Determination of chloramphenicol and tetracycline residues in milk samples by means of nanofiber coated magnetic particles prior to high-performance liquid chromatography-diode array detection.

A magnetic solid phase extraction (MSPE) coupled with high-performance liquid chromatography-diode array detection (HPLC-DAD) methodology was developed for the determination of chloramphenicol (CP) and tetracycline (TET) antibiotic residues in milk samples. As a solid phase sorbent, C-nanofiber coated magnetic nanoparticles were synthesized and extensively characterized using Field Emission Scanning Electron Microscopy (FE-SEM), Raman Spectroscopy and X-ray Powder Diffraction (XRD) analysis. Experimental variables of MSPE method for both antibiotic analytes were investigated and optimized systematically. After MSPE, the linear range for both the analytes (r2 > 0.9954) were obtained in a range 10.0-600.0 ng mL-1. The limit of detections (LODs) for CP and TET were 3.02 and 3.52 ng mL-1, respectively while RSDs % were below than 4.0%. Finally, the developed method based on MPSE-HPLC-DAD was applied to real milk samples to quantify the antibiotic residues. Recovery values for each antibiotic compound were found in the range of 94.6-105.4% (n = 3) by using spiked model solution.

Sensitive determination of Fluoxetine and Citalopram antidepressants in urine and wastewater samples by liquid chromatography coupled with photodiode array detector.

A new analyte separation and preconcentration method for the trace determination of antidepressant drugs, Fluoxetine (FLU) and Citalopram (CIT) in urine and wastewaters, was developed based on HPLC-DAD analysis after magnetic solid phase extraction (MSPE). In the proposed method, FLU and CIT were retained on the newly synthetized magnetic sorbent (Fe3O4@PPy-GO) in the presence of buffer (pH 10.0) and then were desorbed into a lower volume of acetonitrile prior to the chromatographic determinations. Before HPLC analysis, all samples were filtered through a 0.45 µm PTFE filter. Experimental parameters such as interaction time, desorption solvent and volume, and pH were studied and optimized in order to establish the detection limit, linearity, enrichment factor and other analytical figures of merit under optimum operation conditions. In the developed method, FLU and CIT were analyzed by diode array detector at the corresponding maximum wavelengths of 227 and 238 nm, respectively, by using an isocratic elution of 60% pH 3.0 buffer, 30% acetonitrile, and 10% methanol. By using the optimum conditions, limit of detections for FLU and CIT were 1.58 and 1.43 ng mL-1, respectively, while the limit of quantifications was 4.82 and 4.71 ng mL-1, respectively. Relative standard deviations (RSD%) for triplicate analyses of model solutions containing 100 ng mL-1 target molecules were found to be less than 5.0 %. Finally, the method was successfully applied to urine (both simulated and real healthy human) and wastewater samples, and quantitative results were obtained in recovery experiments.

The Presence of Polycyclic Aromatic Hydrocarbons (PAHs) in Grilled Beef, Chicken and Fish by Considering Dietary Exposure and Risk Assessment.

Polycyclic aromatic hydrocarbons (PAHs) are dangerous chemical compounds that can be formed by cooking foods at high temperatures. The aim of this study is to determine the level of contamination of PAH compounds with high performance liquid chromatography (HPLC) on heat treated meat samples and the consumption of PAH compounds in meat samples, as well as the dietary exposure status and possible health risk estimation. In five different heat treated meat samples (meat doner, chicken doner, meatballs, grilled chicken, and fish), the total PAH (Σ16PAH) contamination level was 6.08, 4.42, 4.45, 4.91, and 7.26 µg/kg, respectively. Benzo[a]pyrene (BaP) in meatballs and grilled fish samples had a level 0.70 and 0.73 µg/kg. All of the samples analyzed were found to be below the EU permitted limit (5 µg/kg) in terms of BaP. Estimates of daily intake (EDI) for a total of 16PAH in heat treated meat doner, chicken doner, meatballs, grilled chicken and fish samples were 3.41, 3.71, 2.49, 4.12, and 1.77 ng/kg bw/day, respectively. In this study, the average margin of exposure (MOE) value calculated was found in the range of 179.487 and 425.000 for BaP and PAH4. This study is the first study to provide important information in terms of evaluating the possible health risk that PAH compounds can create in people's diets due to heat treatment of meat and meat products in Sivas, Turkey.

Fabric phase sorptive extraction followed by HPLC-PDA detection for the monitoring of pirimicarb and fenitrothion pesticide residues.

A sensitive and readily deployable analytical method has been reported for the simultaneous analysis of pirimicarb (PRM) and fenitrothion (FEN) pesticide residues in environmental water samples using fabric phase sorptive extraction (FPSE) followed by high-performance liquid chromatography combined with photodiode array (HPLC-PDA) detector. Both pesticides were successfully determined with a Luna omega C18 column under isocratic elution mode by means of acetonitrile and phosphate buffer (pH 3.0) as the mobile phase. The quantitative data for PRM and FEN were obtained at their maximum wavelengths of 310 nm and 268 nm, respectively. The calibration plots were linear in the range 10.00-750.00 ng mL-1 and 10.00-900.00 ng mL-1 with correlation coefficient of 0.9984 and 0.9992 for PRM and FEN, respectively. Major FPSE experimental variables were investigated in detail, such as contact time with the FPSE membrane, pH and electrolyte concentration, and the volume and type of desorption solvent. Under the optimized conditions, the developed method showed satisfactory reproducibility with relative standard deviations less than 2.5% and low limits of detection of 2.98 and 3.02 ng mL-1 for PRM and FEN, respectively. The combined procedure allows for enhancement factors ranging from 88 to 113, with pre-concentration values of 125 for both analytes. The chromatographic resolutions were approx. 12 for FEN (retention factor of 3.52) and PRM (retention factor of 6.09), respectively, with a selectivity factor of 1.73. Finally, the validated method was successfully applied to real environmental water samples for the determination of these pesticides. Graphical abstract.

Analytical Methodology for Trace Determination of Propoxur and Fenitrothion Pesticide Residues by Decanoic Acid Modified Magnetic Nanoparticles.

A sensitive, rapid, reliable, and easily applicable method based on magnetic solid phase extraction (MSPE) combined with HPLC-PDA was developed for monitoring propoxur (PRO) and fenitrothion (FEN) pesticides in environmental water samples. The effect of major experimental variables on the extraction efficiency of both the pesticides was investigated and optimized systematically. For this purpose, a new magnetic material containing decanoic acid on the surface of particles was synthesized and characterized by XRD, FT-IR, SEM, EDX, and TGA analysis in detail. The simultaneous determination of pesticide molecules was carried out by using a Luna Omega C18 column, isocratic elution of acetonitrile (ACN): Water (70:30 v/v) with a flow rate of 1.2 mL min-1. After MSPE, the linear range for pesticide molecules (r2 > 0.9982) was obtained in the range of 5-800 and 10-800 ng mL-1, respectively. The limit of detections (LOD) are 1.43 and 4.71 ng mL-1 for PRO and FEN, respectively while RSDs % are below 3.5%. The applicability of the proposed method in four different environmental samples were also investigated using a standard addition-recovery procedure. Average recoveries at two spiking levels were over the range of 91.3-102.5% with RSD < 5.0% (n = 3). The obtained results show that decanoic acid grafted magnetic particles in MSPE combined with HPLC-PDA is a fast and simple method for the determination of PRO and FEN in environmental water samples.

Novel MIPs-Parabens based SPE Stationary Phases Characterization and Application.

In this work, the synthesis, characterization, and application of novel parabens imprinted polymers as highly selective solid-phase extraction (SPE) sorbents have been reported. The imprinted polymers were created using sol-gel molecular imprinting process. All the seven parabens were considered herein in order to check the phase selectivity. By means of a validated HPLC-photodiode array detector (PDA) method all seven parabens were resolved in a single chromatographic run of 25 min. These SPE sorbents, in-house packed in SPE empty cartridges, were first characterized in terms of extraction capability, breakthrough volume, retention volume, hold-up volume, number of theoretical plates, and retention factor. Finally, the device was applied to a real urine sample to check the method feasibility on a very complex matrix. The new paraben imprinted SPE sorbents, not yet present in the literature, potentially encourage the development of novel molecularly imprinted polymers (MIPs) to enhance the extraction efficiency, and consequently the overall analytical performances, when the trace quantification is required.

FPSE-HPLC-PDA analysis of seven paraben residues in human whole blood, plasma, and urine.

This work describes a new, fast and sensitive method for the simultaneous determination of seven paraben residues including methyl paraben (MPB), ethyl paraben (EPB), propyl paraben (PPB), isopropyl paraben (iPPB), butyl paraben (BPB), isobutyl paraben (iBPB) and benzyl paraben (BzPB) in human whole blood, plasma and urine. The analytes were extracted from the biological matrices by an innovative technique, fabric phase sorptive extraction (FPSE) and subsequently analyzed by high-performance liquid chromatography (HPLC) coupled with photo diode array detector (PDA). The separation was carried out with a Spherisorb C18 column using methanol and phosphate buffer as mobile phases. Ketoprofen was used as the internal standard (IS). The analytical method has been validated according to the International Guidelines in terms of calibration curves for each biological matrix, precision (intra and inter day), trueness, selectivity, LODs, LOQs and ruggedness. Subsequently, the performance of the analytical method was evaluated on real biological samples. The proposed innovative method allows simultaneous analysis of seven paraben residues in three different biological matrices, including whole blood, plasma and urine and therefore it is easily applicable to monitor these substances in different biological samples. Furthermore, extraction technique used in this work is fast, easy to use and in accordance with the modern green analytical chemistry (GAC) principles.

FPSE-HPLC-DAD method for the quantification of anticancer drugs in human whole blood, plasma, and urine.

The present work describes a fast, sensitive and selective procedure for the analyses of aromatase inhibitors including anastrozole, letrozole and exemestane used in the treatment of metastatic breast cancer by high performance liquid chromatography (HPLC) in human whole blood, plasma, and urine samples succeeding an extraction by innovative fabric phase sorptive extraction (FPSE). These drugs were successfully determined using a Luna C18 column at 25 °C using acetonitrile and phosphate buffer. The analytical method was validated, using weighted-matrix matched standard calibration curves. The intra- and inter-day accuracy values (precision and trueness) fulfill the criteria of International Guidelines on Bioanalytical Methods Validation. The analytical performances were further tested on real human biological samples. To the best of our knowledge, this is the first FPSE procedure applied to human whole blood, plasma, and urine samples for the concurrent analysis of aromatase inhibitors possessing a wide range of polarity index values and could be easily adopted as a rapid and green analytical protocol for clinical and pharmaceutical applications. The proposed HPLC method is very innovative since in the literature there are only methods dealing with a single antitumoral drug, and no process has been described so far for these three antitumoral drugs together directly from the whole blood.

A new magnetic nanodiamond/graphene oxide hybrid (Fe3O4@ND@GO) material for pre-concentration and sensitive determination of sildenafil in alleged herbal aphrodisiacs by HPLC-DAD system.

A sensitive analytical methodology was investigated to concentrate and determine of sildenafil citrate (SLC) present at trace level in herbal supplementary products. The proposed method is based on simple and sensitive pre-concentration of SLC by using magnetic solid phase extraction with new developed magnetic nanodiamond/graphene oxide hybrid (Fe3O4@ND@GO) material as a sorbent. Experimental variables affecting the extraction efficiency of SLC like; pH, sample volume, eluent type and volume, extraction time and amount of adsorbent were studied and optimized in detail. Determination of sildenafil citrate after magnetic solid phase extraction (MSPE) was carried out by HPLC-DAD system. The morphology, composition, and properties of the synthesized hybrid material was characterized by Fourier transform infrared spectrometry (FT-IR), Raman spectrometry (Raman), X-ray diffraction spectrometry (XRD), scanning electron microscopy (SEM), mapping photographs, zeta potential analyzer, and BET surface area analysis. Under optimized conditions, linear range was ranged from 5.00 to 250.00 ng mL-1 with R2 of 0.9952. The limit of detection (LOD) was 1.49 ng mL-1 and the recoveries at two spiked levels were ranged from 94.0 to 104.1% with the relative standard deviation (RSD) < 7.1% (n = 5). The enhancement factor (EF) was 86.9. The results show that the combination MSPE with HPLC-DAD is a suitable and sensitive method for the determination of SLC in real samples.

Synthesis and characterization of a composite polymeric material including chelating agent for adsorption of uranyl ions.

In this study, a versatile polymeric material was synthesized by grafting Calcon Carboxylic Acid (CCA), which is known as a chelating agent for some metal ions, to polyacrylamide (PAA) structure. Thus, the adsorptive properties of inert PAA polymer were significantly improved owing to this procedure. The obtained new material, CCA-g-PAA, was characterized by point zero charge (PZC), FTIR, SEM, and UV-VIS-NIR analysis. The adsorption properties of new material were investigated comprehensively and experimental variables were optimized such as pH, temperature, time, and concentration. Experimental data were evaluated by using theoretical adsorption models. The maximum adsorption capacity of material was calculated as 0.079molkg-1 by considering Langmuir equation. The constants calculated from Freundlich and DR model were found as 6.98 and 0.441, respectively. Adsorption kinetic was also explained with pseudo second order and intra particular diffusion models. Experimental studies were showed that adsorption was endothermic and occurred spontaneously. The developed material has important advantages such as reusability, cost-effective synthesis procedure, high adsorption capacity, and selectivity.

Determination of trace inorganic mercury species in water samples by cloud point extraction and UV-vis spectrophotometry.

A new micelle-mediated extraction method was developed for preconcentration of ultratrace Hg(II) ions prior to spectrophotometric determination. 2-(2'-Thiazolylazo)-p-cresol (TAC) and Ponpe 7.5 were used as the chelating agent and nonionic surfactant, respectively. Hg(II) ions form a hydrophobic complex with TAC in a micelle medium. The main factors affecting cloud point extraction efficiency, such as pH of the medium, concentrations of TAC and Ponpe 7.5, and equilibration temperature and time, were investigated in detail. An overall preconcentration factor of 33.3 was obtained upon preconcentration of a 50 mL sample. The LOD obtained under the optimal conditions was 0.86 microg/L, and the RSD for five replicate measurements of 100 microg/L Hg(II) was 3.12%. The method was successfully applied to the determination of Hg in environmental water samples.

Removal of uranyl ions in aquatic mediums by using a new material: gallocyanine grafted hydrogel.

A new material containing gallocyanine (GC) grafted polyacyril amide (PAA) was synthesized and its adsorption ability was examined for the removal of uranyl ions from aqueous media. The new developed adsorbent was characterized by FTIR, SEM, and PZC analysis. Adsorption of UO2(2+) ions from aqueous solution as a function of ion concentration, pH, ionic strength, temperature, and reusability of adsorbent was investigated in detail. The adsorption data were analyzed by using the Langmuir, Freundlich and Dubinin-Radushkevich (DR) models. The adsorption of UO2(2+) increased with pH and reached a plateau value in the pH range 5-6. The adsorption of UO2(2+) ions were not affected by increasing ionic strength. The adsorption mechanism followed an endothermic and spontaneous process with increased disorderliness at adsorbate/adsorbent interface. The adsorption process followed a pseudo-second-order kinetics. The new developed material is a potential adsorbent for effective removal of uranyl ions from aquatic solutions.

A micellar improved method for trace levels selenium quantification in food samples, alcoholic and nonalcoholic beverages through CPE/FAAS.

A useful preconcentration and determination method was proposed for trace selenium in food samples. The procedure is based on complex formation of Pyronine B with Se(IV) ions in the presence of sodium dodecyl sulphate (SDS) and Ponpe 7.5. The variables affecting complex formation, extraction and phase separation were studied and optimised. Under the experimental conditions used, the calibration graph was linear in the range of 20-1700 µg L(-1) for Se(IV) ions. The limit of detection was 3.81 µg L(-1) of Se(IV) and the relative standard deviation for 5 replicate determinations at 250 µg L(-1) concentration level was 2.45%. Recovery values were obtained between 97.8% and 102.8% for spiked samples. The method was successfully applied to the determination of total selenium in some food samples and alcoholic and nonalcoholic beverages. Its validity was checked by the analysis of four certified reference materials. The results obtained by the proposed method were quantitatively in good agreement with the certified values.

Cloud point extraction and spectrophotometric determination of mercury species at trace levels in environmental samples.

A new micelle-mediated separation and preconcentration method was developed for ultra-trace quantities of mercury ions prior to spectrophotometric determination. The method is based on cloud point extraction (CPE) of Hg(II) ions with polyethylene glycol tert-octylphenyl ether (Triton X-114) in the presence of chelating agents such as 1-(2-pyridylazo)-2-naphthol (PAN) and 4-(2-thiazolylazo) resorcinol (TAR). Hg(II) ions react with both PAN and TAR in a surfactant solution yielding a hydrophobic complex at pH 9.0 and 8.0, respectively. The phase separation was accomplished by centrifugation for 5 min at 3500 rpm. The calibration graphs obtained from Hg(II)-PAN and Hg(II)-TAR complexes were linear in the concentration ranges of 10-1000 µg L(-1) and 50-2500 µg L(-1) with detection limits of 1.65 and 14.5 µg L(-1), respectively. The relative standard deviations (RSDs) were 1.85% and 2.35% in determinations of 25 and 250 µg L(-1) Hg(II), respectively. The interference effect of several ions were studied and seen commonly present ions in water samples had no significantly effect on determination of Hg(II). The developed methods were successfully applied to determine mercury concentrations in environmental water samples. The accuracy and validity of the proposed methods were tested by means of five replicate analyses of the certified standard materials such as QC Metal LL3 (VWR, drinking water) and IAEA W-4 (NIST, simulated fresh water).