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.

A simple solvent based microextraction for high performance liquid chromatographic analysis of aflatoxins in rice samples.

This paper describes the development of a simple solvent based microextraction, namely vortex assisted low density solvent-microextraction (VALDS-ME), followed by high performance liquid chromatography-fluorescence detection (HPLC-FD) for the simultaneous determination of four aflatoxins (AFs) including AFB1, AFB2, AFG1 and AFG2 in rice samples. In VALDS-ME, a mixture of low density solvents (1-octanol and toluene) was used as the extraction solvent. The extraction was rapidly achieved with the assistance of vortex agitation and phase separation was easily obtained after the addition of Na2SO4. The effects of various parameters on the extraction efficiency were optimized. Under the optimum conditions, high enrichment factors (42-132), low limits of detection (LODs) in the range of 0.0011-0.17µgkg-1 and good precisions (RSDs lower than 6.2%) were obtained. AFB1 and AFG1 were detected in berry rice sample at 0.26 and 2.1µgkg-1, respectively. The recoveries in AFs-spiked rice samples ranged from 70% to 104%. Moreover, the present method was comparable to the conventional immunoaffinity chromatography method.

Determination of six pyrethroid insecticides in fruit juice samples using dispersive liquid-liquid microextraction combined with high performance liquid chromatography.

Dispersive liquid-liquid microextraction (DLLME) coupled to high performance liquid chromatography (HPLC) with UV detection was applied for the determination of six pyrethroids (tetramethrin, fenpropathrin, cypermethrin, deltamethrin, fenvalerate and permethrin) in various fruit juices including apple, red grape, orange, kiwi, passion fruit, pomegranate and guava juice. Six pyrethroids were separated within 30 min using a Waters Atlantis T3 column under an isocratic elution of acetonitrile-water (72:28). The parameters affecting extraction efficiency of the DLLME method such as type of disperser and extraction solvent, volume of disperser and extraction solvent and centrifugation time were investigated. Under the optimum conditions, 5.00 mL of sample solution, 300 µL of chloroform as extraction solvent and 1.25 mL of methanol as dispersive solvent gave high enrichment factor in the range of 62-84. Good linearity was obtained from 2 to 1,500 µg/L (r(2)>0.995). The mean recoveries of the pyrethroids evaluated by fortification of real samples were in the range of 84-94%. The limits of detection ranging from 2 to 5 µg/L are sufficient to analyze pyrethroid residues at the maximum residue limits (MRLs) established by the European Union (EU) in fruit juices. The proposed method can be applied to direct determination of pyrethroid residues in fruit juices.

New polymeric membrane cadmium(II)-selective electrodes using tripodal amine based ionophores.

Fabrication of PVC membrane electrodes incorporating selective neutral carriers for Cd(2+) was reported. The ionophores were designed to have different topologies, donor atoms and lipophilicity by attaching tripodal amine (TPA) units to the lipophilic anthracene (ionophore I) and p-tert-butylcalix[4]arene (ionophores II, III and IV). The synthesized ionophores were incorporated to the plasticized PVC membranes to prepare Cd(II) ion selective electrodes (ISEs). The membrane electrodes were optimized by changing types and amounts of ionic sites and plasticizers. The selectivity of the membranes fabricated from the synthesized ionophores was evaluated, the relationship between structures of ionophores and membrane characteristics were explored. The ionophore IV which composed of two opposites TPA units on the calix[4]arene compartment showed the best selectivity toward Cd(2+). The best membrane electrode was fabricated from ionophore IV (10.2 mmol kg(-1)) with KTpClPB (50.1 mol% related to the ionophore) as an ion exchanger incorporated in the DOS plasticized PVC membrane (1:2; PVC:DOS). The Cd-ISE fabricated from ionophore IV exhibited good properties with a Nernstian response of 29.4±0.6 mV decade(-1) of activity for Cd(2+) ions and a working concentration range of 1.6×10(-6)-1.0×10(-2)M. The sensor has a fast response time of 10s and can be used for at least 1 week without any divergence in potential. The electrode can be used in the pH range of 6.0-9.0. The proposed electrodes using ionophores III and IV were employed as a probe for determining Cd(2+) from the oxidation of CdS QDs solution and the real treatment waste water sample with excellent results.

Mixed micelle-cloud point extraction for the analysis of penicillin residues in bovine milk by high performance liquid chromatography.

A mixed micelle-cloud point extraction (MM-CPE) has been developed for the analysis of penicillin antibiotics (ampicillin, penicillin G, oxacillin, and cloxacillin) in milk samples using Triton X-114 (TX-114) and cethyl trimethylammonium bromide (CTAB) as the mixed micellar extractant. The parameters affecting the MM-CPE that were investigated including solution pH, CTAB concentration, TX-114 concentration, electrolyte salt, equilibration temperature and incubation time. The optimum MM-CPE conditions were: 10 mmol L(-1) phosphate buffer pH 8, 0.06% (w/v) CTAB, 1.5% (w/v) TX-114, and 7% (w/v) Na(2)SO(4), and 5 min equilibration at 40 degrees C. The separation of penicillins was achieved within 8 min under the HPLC conditions: a Vydac C(18) column, isocratic elution of 5 mmol L(-1) phosphate buffer (pH 6.6) and methanol (55:45, v/v), and a flow rate of 1 mL min(-1), with photodiode array detection at 215 and 244 nm. Under the selected condition, the proposed method gave linear calibrations in the range 0.002-10 microg mL(-1) with correlation coefficients greater than 0.999. Limits of detection (LOD) were 2-3 ng mL(-1), and 15-40-fold enhancement compared to that without preconcentration. Good reproducibility was achieved with relative standard deviation <5% for peak area and <3% for retention time. High accuracy, with recoveries higher than 80%, was obtained. The proposed mixed micelle-CPE-HPLC method has shown to be of high potential for the analysis of penicillin residues in milk with LOD comparable to the established maximum residue limits (4-30 ng mL(-1)).