Electrochemical detection of methyl parathion using calix[6]arene/bismuth ferrite/multiwall carbon nanotube-modified fluorine-doped tin oxide electrode.

A highly sensitive electrochemical sensor using a calix[6]arene/bismuth ferrite/multiwall carbon nanotube-modified fluorine-doped tin oxide electrode (CA6/BFO/MWCNTs/FTO) was fabricated for the detection of methyl parathion. The MWCNTs, BFO, and CA6 were consecutively cast onto the FTO electrode surface to enhance the surface area, electron transfer, and selectivity of sensors. The electrochemical behavior of CA6/BFO/MWCNTs/FTO was studied via cyclic voltammetry and electrochemical impedance spectroscopy. MP was detected via cyclic voltammetry in a phosphate buffer solution at pH 7.0. The working principle of the sensor involves a linear decrease in the anodic peak current of BFO with increasing MP concentration. The linear working ranges are 0.005-0.05 nM and 0.07-1.5 nM. The CA6/BFO/MWCNTs/FTO sensor provides a low detection limit (S/N = 3) of 5 pM and a high electrochemical sensitivity of 1.23 A µM-1 cm-2. The fabricated sensor was successfully applied to assess the presence and amount of MP in vegetables and fruits (recoveries of 82.0-106.8%), with results comparable to high-performance liquid chromatography.

Facile liquid colorimetric sensor using high-density deep eutectic solvent for trace detection and speciation of iron in milk.

An efficient colorimetric sensor was developed using a high-density deep eutectic solvent (HD-DES) for the trace detection and speciation of iron in various milk samples. A liquid colorimetric probe was fabricated by dissolving ferrozine (FZ) in HD-DES prepared from TBABr and PBA. The prederivatization of Fe2+ via complexation with FZ on the HD-DES/FZ probe provided the [Fe(FZ)3]4- complex, which led to a color change from pale yellow to purple before it was simultaneously extracted by HD-DES. The Fe3+ content was calculated by subtracting the amount of Fe2+ from the total Fe content following the reduction of Fe3+ to Fe2+ by L-ascorbic acid in an acid buffer. Under the optimized conditions, the proposed colorimetric sensor exhibited appreciable linearity in the concentration range of 0.003-0.04 mg L-1, a low limit of detection (0.95 µg L-1), high enrichment factor (50), and outstanding repeatability. The liquid colorimetric probe was successfully applied for the determination and speciation of iron in milk samples, and the results were compared with those obtained using the standard atomic absorption spectrometry method. Moreover, quantitative analysis was performed on a smartphone using the Image J application to estimate the color intensity change, which eliminated the requirement of sophisticated scientific instruments.

Co-precipitation based on layered double hydroxides and anionic surfactants for preconcentration of six benzoylurea insecticides in soft drinks before simultaneous analysis by high-performance liquid chromatography.

Layered-double hydroxides (LDHs) modified with anionic surfactants via a co-precipitation method were developed for preconcentrating and simultaneous analysis of six benzoylurea insecticides (BUs) by high-performance liquid chromatography (HPLC). The anionic surfactants with different chain lengths, including sodium dodecylbenzene sulfonate (SDBS), sodium dodecyl sulfate (SDS), sodium 1-nonane sulfonate (SNS), and sodium 1-hexane sulfonate monohydrate (SHS) were investigated to improve the extraction efficiency of LDHs. The SDBS-LDHs provided the highest efficiency for the enrichment of the BUs studied. Under the chosen conditions, enrichment factors in the range of 38-69 and detection limits in the range of 0.1-0.3 µg L-1 were achieved. Good reproducibilities (RSD < 13.8%) and recoveries (71.4-118.7%) were also obtained. The proposed preconcentration method, used as an in situ procedure offers rapid and simple simultaneous preparation of LDHs and extraction of BUs. The method was successfully applied for residue analysis of BUs in fruit- and flower-derived soft drink samples.

An electrochemical sensor for voltammetric detection of ciprofloxacin using a glassy carbon electrode modified with activated carbon, gold nanoparticles and supramolecular solvent.

A highly sensitive and novel electrochemical sensor for ciprofloxacin (CIP) has been developed using gold nanoparticles deposited with waste coffee ground activated carbon on glassy carbon electrode (AuNPs/AC/GCE) and combined with supramolecular solvent (SUPRAS). The fabricated AuNPs/AC/GCE displayed good electrocatalytic activity for AuNPs. The addition of SUPRAS, prepared from cationic surfactants namely didodecyldimethylammonium bromide (DDAB) and dodecyltrimethylammonium bromide (DTAB), increased the electrochemical response of AuNPs. The detection of CIP was based on the decrease of the cathodic current of AuNPs. The electrochemical behavior of the modified electrode was investigated using cyclic voltammetry, differential pulse voltammetry and electrochemical impedance spectroscopy. Under optimum conditions, the calibration plot of CIP exhibited a linear response in the range 0.5-25 nM with a detection limit of 0.20 nM. The fabricated electrochemical sensor was successfully applied to determine CIP in milk samples with achieved recoveries of 78.6-110.2% and relative standard deviations of <8.4%. The developed method was also applied to the analysis of pharmaceutical formulation and the results were compared with high-performance liquid chromatography.Graphical abstract.

A rapid and simple method for the removal of dyes and organophosphorus pesticides from water and soil samples using deep eutectic solvent embedded sponge.

A new treatment method using a deep eutectic solvent embedded melamine sponge (DES-MS) was studied for the removal of organic pollutants from water and soil samples. Five organophosphorus pesticides (OPPs) consisting of azinphos-methyl (AZP), parathion-methyl (PRT), fenitrothion (FNT), diazinon (DIZ) and chlorpyrifos (CPF), and two dyes including acid blue 29 (AB29) and malachite green (MG) were used as the model pollutants. DESs were easily prepared from tetrabutylammonium bromide (TBABr) and various fatty acids. The synthesised DESs were loaded into the sponge before being utilized for the removal of the studied pollutants. After the removal, the residual OPPs or dyes in the supernatant was quantified by high performance liquid chromatography or derivative spectrophotometry, respectively. The proposed method was simple, rapid, environmentally friendly and effective with the removal efficiency higher than 70% for various samples. Moreover, the removal of various dyes was successfully achieved with the efficiency greater than 65% under the optimum condition.

Supramolecular Solvent-Based Liquid Phase Microextraction Combined with Ion-Pairing Reversed-Phase HPLC for the Determination of Quats in Vegetable Samples.

In this study, we used anion supramolecular solvent (SUPRAS) prepared from a mixture of an anionic surfactant, sodium dodecyl sulfate (SDS), and a cationic surfactant, tetrabutylammonium bromide (TBABr), as the extraction solvent in liquid phase microextraction (LPME) of paraquat (PQ) and diquat (DQ). The enriched PQ and DQ in the SUPRAS phase were simultaneously analyzed by ion-pairing reversed-phase high performance liquid chromatography. PQ and DQ were successfully extracted by LPME via electrostatic interaction between the positive charge of the quats and the negative charge of SUPRAS. PQ, DQ, and ethyl viologen (the internal standard) were separated within 15 min on a C18 column, with the mobile phase containing 1-dodecanesulfonic acid and triethylamine, via UV detection. The optimized conditions for the extraction of 10 mL aqueous solution are 50 µL of SUPRAS prepared from a mixture of SDS and TBABr at a mole ratio of 1:0.5, vortexed for 10 s at 1800 rpm, and centrifugation for 1 min at 3500 rpm. The obtained enrichment factors were 22 and 26 with limits of detection of 1.5 and 2.8 µg L-1 for DQ and PQ, respectively. The precision was good with relative standard deviations less than 3.86%. The proposed method was successfully applied for the determination of PQ and DQ in vegetable samples and recoveries were found in the range of 75.0% to 106.7%.

Vesicular supramolecular solvent-based microextraction followed by high performance liquid chromatographic analysis of tetracyclines.

A simple liquid phase microextraction (LPME) using a vesicular supramolecular solvent (SUPRAS) as the green extraction solvent has been developed for the enrichment of tetracycline antibiotics (TCs) prior to their analysis by reversed phase high performance liquid chromatography. SUPRAS was prepared from a mixture of cationic surfactants: didodecyldimethylammonium bromide (DDAB) and dodecyltrimethylammonium bromide (DTAB) under salt (NaCl) addition for coacervation. The LPME is based on electrostatic interaction between TCs and SUPRAS under salt induced phase separation. Under the optimum conditions, high enrichment factors (EFs) of 48-198, low limits of detection (LODs) in the range of 0.7-3.4 µg L-1 and good precisions with relative standard deviations (RSDs) less than 7.85% were obtained. The applicability of the proposed method was demonstrated for the determination of TCs in milk, egg and honey samples. In addition, morphology, particle sizes and zeta potential of SUPRAS were also investigated.

The alternative use of layered double hydroxides as extraction medium coupled with microcomplexation for determination of phosphate in water samples.

A simple, rapid, in situ, and green extraction combined with a microcomplexation has been developed for the spectrophotometric determination of phosphate in water samples. Through their formation, layered double hydroxides (LDHs) were employed as the extraction medium, instantly commenced by a rapid addition of a mixed solution of Mg2+ and Al3+ ions into alkaline phosphate solution. After the extraction, LDH precipitate containing phosphate was dissolved by sulfuric acid and the released phosphate was subsequently detected via its complexation with molybdate in the presence of antimonyl and ascorbic acid. Under optimum conditions, the linearity in the range of 5-200µgL-1, with the correlation coefficient (r2) of 0.9969, and the enrichment factor (EF) of 14 were obtained. The limit of detection (LOD) of 5µgL-1 and good precision, with the relative standard deviations (RSDs) less than 8.16%, were achieved. The proposed method was successfully applied to determine phosphate in water samples and the relative recoveries of 72.97-115.32% were obtained.