Comparison of Dye Adsorption of Chitosan and Polyethylenimine Modified Bentonite Clays: Optimization, Isotherm, and Kinetic Studies.

The aim of this study was to compare the effect of modifying calcium bentonite (Bent-Ca) clay with two cationic polymers, chitosan (Chi) and polyethylenimine (PEI), on the removal of remazol black B (RB-B) dye from an aqueous solution. The samples were characterized by using scanning electron microscopy, X-ray diffraction, and Fourier-transform infrared spectroscopy. The fractional factorial design of 2(6-1) was applied to investigate the effects of pH, temperature, amount of adsorbent, initial dye concentration, contact time, and shaking rate on the adsorption process. To further optimize RB-B removal from an aqueous solution, a Box-Behnken design with three factors and a response surface methodology was used. The optimum conditions were a pH of 3.77, a temperature of 40.45 °C, and an initial RB-B concentration of 77.27 mg L-1 for Bent-Ca-Chi, whereas for Bent-Ca-PEI, the optimum conditions were a pH of 5.53, a temperature of 41.06 °C, and an initial dye concentration of 238.89 mg L-1. To understand the adsorption behavior, the Langmuir and Freundlich isotherms were fitted to the experimental data. It was found that the Langmuir isotherm model matched well with the dye adsorption by Bent-Ca-Chi and Bent-Ca-PEI. The kinetics study was performed using three kinetic models: pseudo-first-order, pseudo-second-order, and intraparticle diffusion models. Among these models, the RB-B dye kinetics were best represented by the pseudo-second-order model equation for the adsorbents.

Separation and quantification of the urinary enantiomers of 2-hydroxyglutaric acid by capillary electrophoresis with capacitively coupled contactless conductivity detection: Application to the diagnosis of D- and L-2-hydroxyglutaric aciduria.

2-hydroxyglutaric aciduria is an inherited neurometabolic disorder with two major types: D-2-hydroxyglutaric aciduria and L-2-hydroxyglutaric aciduria. An easy and fast capillary electrophoresis system combined with a capacitively coupled contactless conductivity detection method was developed for the enantioseparation and determination of D- and L-2-hydroxyglutaric acid in urine. D- and L-2-hydroxyglutaric acids were separated using vancomycin as the chiral selector. The optimal separation conditions for enantiomers were achieved by the use of a buffer containing 50 mM 4-(N-morpholino) butane sulfonic acid solution (pH 6.5), an electroosmotic flow modifier (0.001% [w/v] polybrene), and 30 mM vancomycin as chiral selector. The analysis time was 6 min under optimal conditions. The optimized and validated method was successfully implemented for quantifying D- and L-2-hydroxyglutaric aciduria in patients' urine, without any pretreatment step. The linearity of the method was determined to be in the range of 2-100 mg/L for D- and L-2-hydroxyglutaric acid in urine. The precision (relative standard deviation%) was obtained at about 7%. For D- and L-2-hydroxyglutaric acids, the limits of detection were 0.567 and 0.497 mg/L, respectively.

Capillary electrophoresis with capacitively coupled contactless conductivity detection for the determination of urinary ethylmalonic acid for the diagnosis of ethylmalonic aciduria.

Ethylmalonic acid is a metabolic organic acid, and its accumulation in urine is diagnostic of ethylmalonic aciduria. In this study, a simple and fast method employing capillary electrophoresis equipped with capacitively coupled contactless conductivity detection was developed for the detection of ethylmalonic acid in urine samples. The optimized electrophoretic separation was performed in 50 mmol/L 2-(N-morpholino)ethanesulfonic acid solution, buffered at a pH of 6.5, and contained 0.13 mmol/L cetyltrimethylammonium bromide as an electroosmotic modifier. Electrophoresis was run at 28 kV in reversed polarity. The linear range of ethylmalonic acid concentration was between 1 and 100 mg/L with a regression coefficient of 0.9998. This method had good intra- and interday precision with <5% relative standard deviations. The detection limit (signal-to-noise ratio = 3) and the quantification limit (signal-to-noise ratio = 10) values were 0.139 and 0.466 mg/L, respectively. Using our optimized conditions, the method was successfully employed for the detection of ethylmalonic acid in urine sample of ethylmalonic aciduria patient.

Determination of homogentisic acid in urine for diagnosis of alcaptonuria: Capillary electrophoretic method optimization using experimental design.

Homogentisic acid (HGA) is a diagnostic metabolite that accumulates in the urine and tissues of patients with alkaptonuria which is a rare autosomal recessive disease. HGA is a specific metabolite in urine and serum, which is used for diagnosis of alkaptonuria. This study presents an inexpensive and easy capillary electrophoretic method for the quantitative determination of HGA in urine samples. The method was optimized using full factorial experimental design. The optimal separation electrolyte and separation voltage were revealed as 45 mmol/L phosphate buffer at pH 7.0 and 22 kV, respectively. Under these conditions the presence of HGA was detected in 6 min. Repeatability of migration times and corrected peak areas of HGA (as RSD) were 0.37 and 1.99, respectively. The detection limit was 0.56 µg/mL, 3 times of the average noise, and the quantification limit was 1.85 µg/mL, 10 times the average noise for HGA. Urine samples were directly injected to the capillary without any pretreatment step.

Separation and Sensitive Detection of Lanthanides by Capillary Electrophoresis and Contactless Conductivity Detection.

A rapid and sensitive capillary zone electrophoresis method for the simultaneous separation and determination of lanthanide ions, combined with capacitively coupled contactless conductivity detection (C4D), is reported. The influence of experimental parameters on separation was investigated. The optimal separation conditions were obtained when 4.5 mM 2-hydroxyisobutyric acid and 1 mM acetic acid (HAc) at pH 4.5 were used as buffer solution. Under these conditions, complete separation of all 14 lanthanide ions was achieved in 6 min. With the use of the C4D detector, the sensitive detection of non-UV active lanthanide ions was achieved without the need of a UV active ligand or a visualization agent. The sensitivities were further enhanced with a sample stacking procedure. The limits of detection were to be found between 2.77 and 8.26 nmol/L and the limits of quantification were between 9.29 and 27.5 nmol/L for 14 lanthanide ions.

Voltammetric determination of nitrite in meat products using polyvinylimidazole modified carbon paste electrode.

A simple and sensitive voltammetric method was developed to determine the amount of nitrite by using Carbon Paste Electrode (CPE) which is modified with polyvinylimidazole (PVI). A buffer solution of phosphate with a pH 4 value was used in the experiments. The amount of the nitrite-ion was determined by cyclic voltammetry (CV). The electro-chemical behaviour of nitrite-ion was investigated by using CV on the PVI modified CPE. A well-defined oxidation peak was obtained at 0.83 V against a reference Ag/AgCl electrode. Differential pulse voltammetry (DPV) was applied for the calibration plot and for the detection limit. The optimisation procedure was done in two steps: using a two-level factorial design for preliminary evaluation of the contributing factors, and the Box-Behnken Design (BBD) to assess the optimal experimental conditions. These are done with the analysis of 3 different factors in 15 runs of DPV. The optimum conditions are obtained within a linear response range of 5×10(-7)-1×10(-4) mol L(-1). Regression analysis is performed within this range showed the linear equation of y=0.028x+3.93×10(-7) with r(2)=0.9982, and for n=7. Limit of Detection (LOD) was 9×10(-8) mol L(-1) with S/N=3, and Limit of Quantification (LOQ) was 3×10(-7) mol L(-1) with S/N=10. The procedure was used successfully to detect the amount of nitrite in meat products.

Determination of amino acids in pomegranate juices and fingerprint for adulteration with apple juices.

A new chiral micellar electrokinetic chromatography-laser induced fluorescence (MEKC-LIF) method was developed using sodium dodecylbenzene sulphonate (SDBS) as surfactant for the determination of chiral amino acids in pomegranate juices. The use of SDBS as the micellar medium enhanced the fluorescence intensities of amino acids derivatised with fluorescein isothiocyanate (FITC). The amino acid profile of pomegranate juices was compared to apple amino acids and l-Asn was proposed as a marker for the adulteration of pomegranate juices with apple juices.

Non-ionic micellar electrokinetic chromatography with laser-induced fluorescence: a new method tested with biogenic amines in brined and dry-salted fish.

A non-ionic micellar electrokinetic chromatography method coupled to laser-induced fluorescence detection was developed for the quantitative determination of biogenic amines. Complete resolution of six biogenic amines - FITC derivatives - was achieved in less than 10 min, employing 10 mM Brij 35 in 75 mM borate buffer and at pH 9.7 as the running electrolyte. Relative fluorescence intensities of biogenic amines enhanched considerably and separation time decreased considerably when Brij 35 was substituted for SDS in the same buffer. The detection limits of the method for biogenic amines were found between 0.416 and 1.26 nM. The precisions for the corrected peak areas were calculated as between 1.63 and 3.24 %RSD. The applicability of the method was demonstrated by analyzing biogenic amines in the processed, brined, and dry-salted fish samples. The method is simple and rapid, and widely applicable for the determination of biogenic amines in food samples.

Isolation and analysis of bioactive diterpenoids in Salvia species (Salvia chionantha and Salvia kronenburgiii) by micellar electrokinetic capillary chromatography.

In the present work, we isolated two bioactive diterpenoids, horminone and 7-O-acetylhorminone and developed a micellar electrokinetic chromatography (MEKC) method for the simultaneous quantitative analysis of them in Turkish Salvia species. The optimal separation electrolyte was 50 mmol/L SDS and 25% methanol at pH 11.5. The limits of detection (S/N=3) were 3.269 and 4.518 microg/mL for horminone and 7-O-acetylhorminone, respectively. The method has been applied successfully to analyze these two components in Salvia chionantha and Salvia kronenburgii acetone extracts.

Determination of alginate copolymer in pharmaceutical formulations by micellar electrokinetic chromatography.

A micellar electrokinetic chromatography method was developed for the determination and quantification of sodium alginate. The alginate peak migrated in the very short time of 1.33 min and calibrated easily though the polydisperse properties of alginates. The minimum detection limit (LOD) of the method was calculated as 0.393 mg/ml. This analysis method was successfully applied to the alginate quantification in an antacid pharmaceutical formulation. Precise and reproducible analysis results were obtained, with liquid formulations injected directly without any pre-separation process.

Effect of cationic surfactant adsorption on the rheological and surface properties of bentonite dispersions.

In this study, the adsorption, bridging, and intercalation effects of a cationic surfactant, benzyldimethyltetradecyl ammonium chloride (BDTDACl), on bentonite clay suspensions was investigated. The adsorption, rheological behaviors, and colloidal properties of the clay dispersions were determined as a function surfactant concentration. Adsorption isotherms were obtained using the batch-equilibrium technique. The rheological behavior of the clay suspensions was obtained by shear stress-shear rate measurements within 0-350 s-1 shear rates. The structure of the composite particles was analyzed by using X-ray diffraction analysis and it was found that the expansions of basal d-spacings are less than 16.80 A, suggesting a monolayer structure.

Determination of cationic surfactants as the preservatives in an oral solution and a cosmetic product by capillary electrophoresis.

In this study, a capillary electrophoresis method was developed for the determination of cationic surfactants, benzethonium and cetylpyridinium ions, which are commonly used as preservatives in various pharmaceutical and cosmetic products. Determination was performed in a fused-silica capillary using a mixed 75 mmol/L phosphoric acid and 50% acetonitrile electrolyte at pH 2.5. Analysis of benzethonium and cetylpyridinium ions was achieved in around 5 min. Repeatability in migration times (R.S.D.%) for benzethonium and cetylpyridinium ions were 0.3. The calibration curves were linear from 0.0125 to 0.400 mmol/L for benzethonium ions and from 0.025 to 0.400 mmol/L for cetylpyridinium ions. The minimum detection limits (signal-to-noise ratio=3) are 1.47 and 4.30 microg/mL for benzethonium and cetylpyridinium ions, respectively. The method was applied to the analysis of benzethonium ion in a cosmetic product and cetylpyridinium ion in a mouthwash.

Direct determination of bromide ions in seawater by capillary zone electrophoresis using polyethyleneimine-coated capillaries.

A rapid and simple capillary electrophoretic method was developed for the direct determination of bromide ion in seawater. We have found an effective method, based on the use of polyethyleneimine-coated capillaries and the addition of sodium chloride to the background electrolyte. The use of coated capillaries with a cationic polymer changes the direction of the electroosmotic flow in the capillary, which favors the migration speed of the bromide ion and enables the use of low salt concentrations in the separation electrolyte. Bromide ion in seawater can be determined within 2 min using this system and 20 mmol L(-1)NaCl-containing separation electrolyte. The detection limit for the bromide ion was 0.45 microg ml(-1). The method was applied to the determination of bromide ion in seawater samples collected from the Bosphorus and the Black Sea. Bromide contents in samples from 0 to 72 m depths varied between 33.2 and 72.8 mg L(-1) with a mean 3.0% RSD.