Micelle‐Mediated Extraction for Direct Spectrophotometric Determination of Trace Uranium(VI) in Water Samples

Abstract

The possibility of using Dibenzoylmethane (DBM) for uranium(VI) concentrating by the way of micellar extraction at cloud point temperature and later spectrophotometric determination was investigated. Under the optimum conditions, preconcentration of 50 mL of water samples in the presence of 0.2% (w/v) octylphenoxypolyethoxy ethanol (Triton X‐114), 2×10^?4 mol L^?1 DBM and 2×10^?3 mol L^?1 buffer solution (pH=9) gave a limit of detection 11 ng mL^?1, and the calibration graph was linear in the range of 15–300 ng mL^?1. The recovery under optimum working conditions was higher than 98%.

The proposed method has been applied to the spectrophotometric determination of uranium(VI) in natural water samples after cloud point extraction with satisfactory results.     

INTERACTION OF HYDROXYLATED POLYCYCLIC AROMATIC HYDROCARBONS TO ESTROGEN RECEPTOR

Binding activities and estrogenic/antiestrogenic activities of polycyclic aromatic hydrocarbons (PAHs) and hydroxylated PAHs (OHPAHs) having 2 to 6 rings were evaluated by competition assay and yeast two-hybrid assay expressing human estrogen receptor (hER), respectively. PAHs did not bind to hER and did not show any activity. On the other hand, OHPAHs bound to hER and several OHPAHs showed estrogenic or antiestrogenic activity. Relative estrogenic activity (REP _E ) and antiestrogenic activity (REP _AE ) were calculated from the values of E ₂ and 4-hydroxytamoxyfen as positive controls, respectively. Several OHPAHs having 4 rings showed strongly estrogenic activity. 4-Hydroxybenzo[a]anthracene exhibited the strongest estrogenic activity (REP _E = 7.5 × 10^?3 ) followed by 3-hydroxybenzo[a]anthracene and 2-hydroxychrysene (REP _E = 4.2 × 10^?3 ). Several other 4-ring OHPAHs showed strongly antiestrogenic activity. 3-Hydroxybenzo[c]phenanthrene exhibited the strongest antiestrogenic activity (REP _AE = 190) followed by 2-hydroxybenzo[c]phenanthrene (REP _AE = 69) and 2- hydroxybenz [a]anthracene (REP _AE = 0.42). The results suggested that there is a strong structure – activity relationship.     

Multiwalled carbon nanotube-4-tert-butyl calix[6]arene composite electrochemical sensor for clenbuterol hydrochloride determination by means of differential pulse adsorptive stripping voltammetry

The electrochemical behavior of clenbuterol hydrochloride (CLB) was studied at a multiwalled carbon nanotube-4-tert-butyl calix[6]arene composite chemically modified electrode by means of cyclic voltammetry, electron impedance spectroscopy, and differential pulse adsorptive stripping voltammetry. Surface characterization of the electrode was carried out by means of SEM. The results revealed that 4-tert-butyl calix[6]arene along with multiwalled carbon nanotubes demonstrated a high sensitivity for determination of CLB. Employing differential pulse adsorptive stripping voltammetry allowed a linear response over the concentration range of 1.99?×?10^?8–4.76?×?10^?5?M with a detection limit of 1.38?×?10^?9?M for CLB. The described method has been applied for the estimation of CLB in biological fluids such as urine and serum.     

POLYCYCLIC AROMATIC HYDROCARBONS ANALYZED IN RAINWATER COLLECTED ON TWO SITES IN EAST OF FRANCE (STRASBOURG AND ERSTEIN)

Polycyclic Aromatic Hydrocarbons (naphtalene, acenaphtene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benzo[a]anthracene, chrysene, benzo[j]fluoranthene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, dibenzo[a,h]anthracene, benzo[g,h,i]perylène, indeno[1,2,3-c,d]pyrene and coronene) have been consecutively analyzed in rainwater sampled in Strasbourg (urban site) and Erstein (rural site) between January 2002 and June 2003 and between April 2002 and June 2003 on a weekly basis respectively. For the sampling of rainwater, a wet-only rainwater sampler was used together with an open collector to take the measurements of precipitation.

PAHs in rainwater were extracted by using SPE cartridges and analyzed by HPLC-fluorescence following a method developed in the laboratory.

Mean concentrations of all PAHs (Σ 16 HAPs) varied between 0.15 and 79.60 ng·L^?1 in Erstein, and between 3.70 and 1596.45 ng·L^?1 in Strasbourg. Naphtalene, phenanthrene, fluoranthene, pyrene, chrysene, benzo[j]fluoranthne and benzo[a]pyrene were the most concentrated PAHs analyzed. Benzo[a]pyrene was frequently detected. Seasonal effects were observed with a maximum of concentrations of PAHs during cold periods. Some spatial influences were also reported. The calculation of some PAH ratios show that diesel exhaust could be the main source of PAHs in rainwater on the two sites.     

Synthetic Cis-Jasmone Exposure Induces Wheat and Barley Volatiles that Repel the Pest Cereal Leaf Beetle, Oulema melanopus L.

The plant semiochemical cis-jasmone primes/induces plant resistance that deters herbivores and attracts natural enemies. We studied the induction of volatile organic compounds (VOCs) in winter wheat and spring barley after exposure of plants to three synthetic cis-jasmone doses (50 μl of 1, 100, and 1?×?10⁴ ng μl^?1) and durations of exposure (1, 3, and 6 h). Cereal leaf beetle, Oulema melanopus, adult behavioral responses were examined in a Y-tube olfactometer to cis-jasmone induced plant VOC bouquets and to two synthetic blends of VOCs (3 green leaf volatiles (GLVs); 4 terpenes?+?indole). In both cereals, eight VOCs [(Z)-3-hexanal, (Z)-3-hexanol, (Z)-3-hexanyl acetate, (Z)-β-ocimene, linalool, β-caryophyllene, (E)-ß–farnesene, and indole] were induced 100- to 1000-fold after cis-jasmone exposure. The degree of induction in both cereals was usually positively and linearly associated with increasing exposure dose and duration. However, VOC emission rate was only ~2-fold greater from plants exposed to the highest vs. lowest cis-jasmone exposure doses (1?×?10⁴ difference) or durations (6-fold difference). Male and female O. melanopus were deterred by both cereal VOC bouquets after plant exposure to the high cis-jasmone dose (1?×?10⁴ ng μl^?1), while females were also deterred after plant exposure to the low dose (1 ng μl^?1) but attracted to unexposed plant VOC bouquets. Both O. melanopus sexes were repelled by terpene/indole and GLV blends at two concentrations (25 ng?·?min^?1; 125 ng?·?min^?1), but attracted to the lowest dose (1 ng?·?min^?1) of a GLV blend. It is possible that the biologically relevant low cis-jasmone dose has ecological activity and potential for inducing field crop VOCs to deter O. melanopus.     

Electrochemical determination of malachite green at graphene quantum dots–gold nanoparticles multilayers–modified glassy carbon electrode

A graphene quantum dots–gold nanoparticles–modified glassy carbon electrode was used to investigate the electrochemical behaviors of malachite green (MG). Cyclic voltammetry curves of MG at the modified electrode exhibited a pair of quasi-reversible adsorption-controlled redox peaks at 0.502 V (E _pa) and 0.446 V (E _pc) in a 0.05 mol L^?1 H₂SO₄ solution. Under the optimal conditions, by using differential pulse voltammetry as the detection method, a linear relationship was obtained between the oxidation peak current and the MG concentration in the range of 4.0 × 10^?7 to 1.0 × 10^?5 mol L^?1 with the detection limit as 1.0 × 10^?7 mol L^?1 (signal-to-noise ratio of 3). The modified electrode was applied in the determination of MG in fish samples, and the results were satisfactory with recoveries from 96.25 to 98.00 %. Furthermore, the modified electrode showed very good reproducibility and stability.     

Calixarenes 30. Calixquinones

Chlorine dioxide and thallium trifluoroacetate are shown to be useful reagents for the preparation of calixquinones. p-H-Calix[4]arene( 1a ),p-H-calix[5]arene ( 1b ), and p-H-calix[6]arene ( 1c ) are oxidized in modest yields by ClO₂ to the fully quinonoid compounds calix[4]tetraquinone ( 2a ), calix[5]pentaquinone ( 2b ), and calix[6]hexaquinone ( 2c ), respectively. Although Tl(OCOF₃)₃ is less effective for the oxidation of 1a-c , it proves to be the reagent of choice for converting partially etherified or esterified calixarenes carrying p-tert-butyl groups directly to partially quinonoid calixarenes. Thus, monosubstituted calix[4]arenes yield triquinones; disubstituted calix[4]arenes yield diquinones; trisubstituted calix[4]arenes yield monquinones; and tetrasubstituted calix[6]arenes yield diquinones. The structures of the calixquinones have been established by elemental analysis, ¹H NMR spectroscopy, mass spectroscopy, and in the case of 2c by X-ray crystallography. Since the starting materials are readily accessible, the calixquinones become easily available compounds for further study.     

Analysis by GC-MS of Polycyclic Aromatic Hydrocarbons in a Cream Containing Coal Tar

Qualitative and quantitative PAHs composition of a cream containing coal tar (5%), used in cutaneous diseases treatment, was studied. Eleven PAHs were analysed in pure coal tar and in the cream by GC-MS, after ultrasonic extraction by pyridine. Ten PAHs were found in pure coal tar: naphthalene, biphenyl, acenaphthylene, fluorene, phenanthrene, anthracene, carbazole, fluoranthene, pyrene and benzo[a]pyrene. No traces of 2,3-benzofluorene were detected. Seven PAHs were identified in the cream: naphthalene, biphenyl, acenaphthylene, fluorene, phenanthrene, fluoranthene and pyrene. 2,3-benzofluorene was also absent in the cream. Anthracene, carbazole and benzo[a]pyrene (one of the most toxic) were present in coal tar and not detected in the cream.

The seven PAHs found in the cream and in coal tar were quantified. Hydrocarbons concentrations were between 0.107 ± 0.0038 mg.g^?1 (for biphenyl) and 0.734 ± 0.0438 mg.g^?1 (for phenanthrene) in the cream and between 4.31 ± 0.23 mg.g^?1 (for biphenyl) and 21.9 ± 0.57 mg.g^?1 (for fluorene) in coal tar.     

The synthesis of (N1E,N4E)-N1,N4-bis(pyridine-2-YL) ethylene benzene-1,4-diamine and investigation of its efficiency as new binuclear catalyst complex in copper-based ATRP

(N¹E,N⁴E)-N¹,N⁴-bis(pyridin-2-yl) ethylene benzene-1,4-diamine (BPEBD) was synthesized by condensation of 2-acetyl pyridine and 1,4-diaminobenzene and its efficiency as a catalyst in Cu-based atom transfer radical polymerizations (ATRP) of methyl methacrylate (MMA) and styrene (S) was investigated. Linear first-order kinetic plots were obtained. However, there were induction periods. The apparent rate constant values of ATRP of MMA with CuCl/BPEBD catalyst system in toluene were found to be between 2.10 × 10^?5 and 9.83 × 10^?5 s^?1, while they were between 6.67 × 10^?6 and 3.30 × 10^?5 s^?1 in the case of acetonitrile, indicating the presence of a low radical concentration throughout the polymerizations. Low apparent rate constant values denote a good control over ATRP in general. Apparent rate constant vs [ligand]/[catalyst] ratio plots showed a maximum at the [ligand]/[catalyst] ratio of 1. In the ATRP of MMA in toluene, M _n,GPC values increased linearly with conversion and these molecular weight values were close to M _n,th in comparison to that of in acetonitrile. In the polymerization of S, the control of molecular weights was not good, although the reactions were first-order kinetics. Cyclic voltammetry measurements confirmed that CuCl/BPEBD complex in acetonitrile gives quasi-reversible redox couples, and copper (I) centers in CuCl/BPEBD binuclear catalyst complexes are readily oxidized and it potentially suits to facile ATRP.     

Polycyclic Aromatic Hydrocarbons Determination in Grilled Beef and Chicken

ABSTRACT

Polycyclic aromatic hydrocarbons (PAHs) are principally formed as a result of thermal treatment of food, especially grilling or barbecuing. In the present study, two types of Iranian popular grilled beef and chicken dishes (kebab) were analyzed for toxic PAHs, i.e., naphthalene, fluoranthene, phenanthtrene, anthracene, pyrene, and benzo(a)pyrene applying GC/MS. The differences in PAHs concentrations among grilled beef and chicken (kebab koobide and juje kebab) were found to be significant (p < 0.05), ranging from 0.29 to 21.95 ng·g^?1. Benzo(a)pyrene was found in nearly all samples; the maximum concentration of total PAHs was 21.95 ng·g^?1 found in grilled beef (koobide Khalij fars) and the lowest was 0.29 ng·g^?1 in grilled chicken (juje kebab) of Sahel restaurant.     

SAMPLING AND ANALYSIS OF POLYCYCLIC AROMATIC HYDROCARBONS IN URBAN AND RURAL ATMOSPHERES: SPATIAL AND GEOGRAPHICAL VARIATIONS OF CONCENTRATIONS

Atmospheric sampling (gas and particles) of PAHs (naphthalene, acenaphthene, fluorene, anthracene, phenanthrene, fluoranthene, pyrene, benz[a]anthracene, chrysene, benzo[b]fluoranthene, benzo[j]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, benzo[ghi]perylene, dibenz[a,h]anthracene, indeno[1,2,3-cd]pyrene, coronene) on XAD-2 resin (20 g) and glass fiber filters respectively, were performed in 2002 by using Digitel DA80 high-volume samplers equipped with a PM10 head. Samplings were performed in Strasbourg (east of France) and its vicinity (Schiltigheim and Erstein). Sites were chosen to be representative of urban (Strasbourg), suburban (Schiltigheim), and rural (Erstein) conditions. Field campaigns were undertaken simultaneously in urban, and suburban, urban and rural sites during spring and autumn during 4 h at a flow rate of 60 m³/h^?1 which gives a total of 240 m³ · h^?1 of air per sample. The period of sampling varied between 06:00 to 10:00, 11:00 to 15:00, 17:00 to 21:00 in order to evaluate a variation of concentration during automobile traffic between urban, suburban, and rural areas. Gas and particle samples were separately Soxhlet extracted for 12 h with a mixture of CH₂Cl₂/n-hexane (50:50 v/v), concentrated to about 1 mL with a rotary evaporator and finally dried under nitrogen. Dry extracts were dissolved in 1 mL of CH₃CN before analysis. Before use, traps were Soxhlet cleaned for 24 h with the same mixture as used for the extraction. Analysis of each extract was performed by reverse phase HPLC, and fluorescence detection and quantification was done with respect to triphenylene used as internal standard. Results shows that automobile traffic seems to be the main source of PAHs in urban areas whatever the period (autumn and spring) while in autumn other sources, especially coming from combustion, influence the atmospheric contamination by PAHs.     

Response surface methodology for optimization and determination of Riluzole by microfunnel magnetic stirring-assisted liquid–liquid microextraction coupled with high-performance liquid chromatography

ABSTRACT

A rapid, simple, and highly sensitive microfunnel magnetic stirring-assisted liquid–liquid microextraction coupled with HPLC was developed for determination of Riluzole (RLZ). The main extraction parameters were screened using the Plackett–Burman design and optimized by central composite design. Under optimum conditions, the calibration curve was linear over the range of 0.2–400 ng mL^?1, and RSD of 3.21% (n = 14, 20 ng mL^?1) proved to have good reproducibility. The detection limit was 0.023 ng mL^?1 and 1.5 ng mL^?1 for aqueous and biological samples, respectively. The tap water, human plasma, and urine samples showed excellent recoveries for RLZ (97.09–101.92%) via this method.     

Indoor Polycyclic Aromatic Hydrocarbon Concentration in Central India

The indoor burning of different materials like fuels, incense, mosquito coil, candles etc. results in generation of polycyclic aromatic hydrocarbons (PAHs) in an uncontrolled manner. The PAH, i.e., Benzo(a)pyrene (BaP) is considered as most toxic or carcinogenic and the toxicity of other PAHs is related to this compound. Therefore, the concentration and emission fluxes of polycyclic aromatic hydrocarbons (PAHs) emitted during burning of commonly used indoor materials, i.e., 15 fuels (i.e., biomass (BM), coal (C), cow dung (CD), kerosene (K)), 4 incense (IS) and mosquito coil (MC) in Raipur district, Chhattisgarh, central India is described. The samples were taken in September 2013 in indoor environments and respective smoke emitted were collected using high volume United State of America (USA) air sampler on quartz fiber filters. The concentration of total 13 PAHs (∑PAH₁₃) (i.e., phenanthrene, anthracene, fluoranthene, pyrene, benz(a)anthracene, chrysene, benzo(b)fluoranthene, benzo(k)fluoranthene, benzo(a)-pyrene, dibenz(ah)anthracene, benzo(ghi) perylene, indeno1,2,3-(cd)pyrene, and coronene) in particulate matter (PM₁₀) in the indoor air during burning of the fuels, IS and MC materials ranged from 367–92052 ng m^?3, 4089–14047 ng m^?3, and 66–103 ng m^?3 with mean values of 7767 ± 11809 ng m^?3, 9977 ± 4137 ng m^?3, and 74 ± 20 ng m^?3, respectively. The mean concentration of the ∑PAH₁₃ present in indoor environment is much higher than the WHO limit value of 1.0 ng m^?3. The sources and toxicities of PAHs are discussed.     

Copolymerization of styrene and methyl methacrylate mediated by iron wire/N,N,N′,N′-tetramethyl-1,2-ethanediamine as catalyst in the presence of air

Random copolymers of P(MMA-co-styrene) were synthesized via single electron transfer-living radical polymerization (SET LRP) at 25 °C in N,N-dimethylformamide (DMF) and benzene using CCl₄ as initiator and Fe(0) wire/N,N,N′,N′-tetramethyl-1,2-ethanediamine (TMEDA)/hydrazine (NH₂NH₂) complexes as catalyst in the presence of air. Fe(0) wire-mediated single electron transfer-living radical copolymerization of MMA and styrene represented a robust and versatile technique to synthesize the well-defined copolymers. The copolymerization rate was faster in DMF than in benzene, as determined by the apparent rate constants. The results showed that the copolymerization followed first-order kinetics model in the presence of polar DMF and non-polar benzene. The molecular weights increased linearly with the increase of monomer conversion with a narrow polydispersity index when the conversion was beyond 25 %. The polarity and the quantity of solvent had significant effects on the polymerization, and the apparent rate constants were 1.28 × 10^?4, 1.21 × 10^?4, and 9.23 × 10^?5 s^?1 in the order of DMF amount, 5, 10, and 15 mL. The conversion increased from 29.3 to 48.5 % and the polydispersity index (PDI) changed from 1.24 to 1.21 with [CCl₄]₀/[TMEDA]₀ molar ratio changing from 1:0.5 to 1:5. The chain extension experiment demonstrated that the copolymerization exhibited a living characteristic.     

Evaluation of Novel Solvent Systems Containing Calix-crown-6 Ligands in A Fluorinated Solvent for Cesium Extraction from Nitric Acidic Feeds

Several commercial calix-crown-6 ligands such as: calix[4]arene-bis-crown-6 (CC), calix[4]arene-bis-benzo-crown-6 (CBC), calix[4]arene-bis-naphtho-crown-6 (CNC), and bis-(octyloxy)calix[4]arene-mono-crown-6 (CMC) have been evaluated for their Cs uptake ability from nitric acid feed solutions in a novel solvent system. The calix-crown-6 ligands were made soluble in phenyl trifluoromethyl sulphone (PTMS) and 1 × 10^?3 M solutions were used for metal ion extraction from nitric acid feed solutions. The extraction efficiency of the calix-crown-6 ligands was found out to be: CBC > CNC > CMC ? CC, which was attributed to trends of their partition coefficients. CNC was considered to be the most suitable extractant in view of its better organophilicity. The effects of concentrations of nitric acid and Cs carrier in feed were also investigated. Studies carried out using variation of ligand concentration yielded an extracted species of the type [CsL⁺][NO₃^?]_org. Stripping of Cs(I) from the loaded organic phase was found to be possible when the organic phase contained minute quantities of Alamine 336. Co-current extraction and stripping studies were also carried out using CNC as the extractant.     

Separation and Preconcentration of Silver Ion using Multiwalled Carbon Nanotubes as Solid Phase Extraction Sorbent

Abstract

A new method has been developed for the determination of silver ion based on separation and preconcentration with a microcolumn packed with multiwalled carbon nanotubes (MWNTs) prior to its determination by flame atomic absorption spectrometry (FAAS). The optimum experimental parameters for separation and preconcentration of silver, `such as sample pH, sample flow rate and volume, elution conditions, and interfering ions, have been investigated. Silver ion can be quantitatively retained by MWNTs in the pH range 7～9, and then eluted completely with 1.0 M HNO₃. The detection limit of this method for Ag was 0.60 ng mL^?1, and the relative standard deviation (RSD) was 3.8% at the 10 ng mL^?1 Ag level. The method has been successfully applied for the determination of trace silver in geological and water samples.     

2,6-Bis-benzimidazolylpyridines as new catalyst in copper-based ATRP

The ligands, 2,6-bis(NH-benzimidazol-2-yl)pyridine (L1) and 2,6-bis(N-methyl-benzimidazol-2-yl)pyridine (L2), were synthesized by a one-step reaction of 2,6-pyridinedicarboxylic acid with a diamine (o-phenylenediamine or N-methyl-1,2-phenylenediamine), respectively, in syrupy phosphoric acid at ca. 200 °C. Their efficiency as a catalyst in Cu-based atom transfer radical polymerizations (ATRP) of methylmethacrylate (MMA) was investigated. The linear first-order kinetic plots were observed; indicating that the number of active species is constant during the polymerization and termination reactions are limited. The apparent rate constant values of ATRP of MMA with CuCl/L1 catalyst system at 90 °C in acetonitrile were found to be between 3.83 × 10^?5 and 1.33 × 10^?4 s^?1, while they were between 1.86 × 10^?4 and 4.40 × 10^?4 s^?1 in the case of CuCl/L2 catalyst, indicating the presence of lower radical concentration throughout the polymerization of MMA using CuCl/L1 catalyst system. In both the cases, low apparent rate constant values are obtained. This indicates that ATRP proceeded at reasonable rates and a good control over ATRP in general. Apparent rate constant vs [ligand]/[catalyst] ratio plots showed a maximum at the [ligand]/[catalyst] ratio of two. M _n,GPC values increased slightly linearly with conversion and molecular weight values were closer to M _n,th in the case of ATRP of MMA using CuCl/L2 catalyst complex. Cyclic voltammetry measurements confirmed that CuCl/L1 and CuCl/L2 complexes in acetonitrile give reversible redox couples and copper(I) centers in CuCl/L1 and CuCl/L2 catalyst complexes that are readily oxidized and they potentially suit to facile ATRP.     

Nanostructured catalysts for oxygen electroreduction based on bimetallic monoethanolamine complexes of Co(III) and Ni(II)

Oxygen reduction electrocatalysts based on the monoethanolmine complexes {[CoEtm]₂(μ-Etm)₄Ni(NO₃)₂} and {[CoEtm]₂(μ-Etm)₄Ni(NO₃)₂} + activated carbon AG-3 have been obtained by high-temperature synthesis. The nature of active centers on the synthesized electrocatalysts was described. Using potentiostatic and cyclic potentiodynamic voltammetry, the kinetic characteristics of catalysts in the oxygen electroreduction reaction were determined. Thermal decomposition of the thermally unstable complexes was described and character of the active centers formed was discussed. The optimal synthesis temperature of electrocatalysts is 600 °C in an inert atmosphere. The calculated exchange current densities for the oxygen electroreduction reaction at the catalysts in 1 M KOH at 20 °C was j ₀  = 1.01 × 10^?3 A g^?1–3.3 × 10^?3 A g^?1. The Tafel slopes of stationary polarization curves are 0.054–0.063 V for b ₁ and 0.106–0.125 V for b ₂ . The prepared electrocatalysts can be recommended only for electrochemical systems with alkaline electrolyte.     

Utilization of a montmorillonite-Ca-modified carbon paste electrode for the stripping voltammetric determination of diflunisal in its pharmaceutical formulations and human blood

A highly sensitive square-wave adsorptive anodic stripping voltammetric method was described for the determination of diflunisal in its formulations and human blood, utilizing a developed montmorillonite-Ca-modified carbon paste electrode (CPE). The peak current was significantly enhanced due to the strong adsorptive properties of montmorillonite-Ca clay. The optimal procedural parameters were frequency f = 80 Hz, scan increment ΔE _a = 10 mV, pulse-amplitude ΔE _i = 25 mV, and an accumulation potential E _acc of 0.0 V versus Ag/AgCl/3M KCl in acetate buffer of pH 5.0 using 10% (w/w) MMT-Ca-modified CPE. The described method was successfully applied for assay of diflunisal in different pharmaceutical formulations (Doloban^®, Dolozal^®, and Maxipan^® tablets) with mean percentage recoveries of 98.72 ± 0.35, 99.24 ± 0.89, and 98.20 ± 1.38, respectively. Furthermore, the method was successfully applied for assay of diflunisal in spiked human serum without the necessity of sample pretreatment or time-consuming extraction prior to the analysis. Mean percentage recovery of diflunisal in human serum was 99.16 ± 1.03 with a limit of detection of 3.0 × 10^?9 M (0.75 ng mL^?1). Due to this extremely low limit of detection, the proposed method was used to follow up the concentration of drug in blood samples of two male volunteers after oral administration of a single dose of Dolozal^®, 500 mg tablet.     

Cloud Point Extraction and Preconcentration for the Determination of Cu and Ni in Natural Water by Flame Atomic Absorption Spectrometry

Abstract

In this work, a new cloud point extraction (CPE) method was developed for the separation and preconcentration of copper and nickel. The analyte was complexed with 3‐[(8‐{[(E)‐2‐hydroxyimino‐1‐methylpropylidene] amino}‐1‐naphthyl) imino]‐2‐butanone oxime (H₂mdo) in the initial aqueous solution and octylphenoxy polyethoxy ethanol (Triton X‐114) was added as a surfactant. After phase separation, based on the cloud point in the mixture, and dilution of the surfactant‐rich phase with methanol containing 0.1 mol l^?1 HNO₃, the enriched analytes were determined by flame atomic absorption spectrometry. After optimization of the complexation and extraction conditions (i.e. pH=8.5, H₂mdo=3×10^?4 mol l^?1, Triton X‐114=0.1% (w/v)) the enhancement factors of 65 and 59 and detection limits of 0.14 and 0.2 ng ml^?1 were obtained for copper and nickel respectively. The proposed method was applied to the determination of copper and nickel in several natural water samples with satisfactory results.