Innovative separation and preconcentration technique of coagulating homogenous dispersive micro solid phase extraction exploiting graphene oxide nanosheets

A uniquely novel, fast, and facile technique is introduced for the first time in which a scant amount of graphene oxide (GO), without modification, has been utilized in dispersive mode of solid phase extraction (SPE) for an efficient yet simple separation. The proposed method of coagulating homogenous dispersive micro solid phase extraction (CHD-µSPE) is based on coagulation of homogeneous GO solution with the aid of polyetheneimine (PEI). CHD-µSPE use full adsorption capacity of GO because in this method was used GO solution obtained from synthesis process without drying step and stacking nanosheets. In optimized condition, 30 µL GO solution (7 mg mL⁻¹), obtained in synthesis process, was injected into 1.5 mL the sample solution followed by immediate injection of 53 µL PEI solution (1 mg mL⁻¹). After inserting PEI, GO sheets aggregate and can be readily separated by centrifugation. PEI not only cause aggregation of GO, but also form three-dimensional network of GO with easy handling in following separation steps. Lead, cadmium, and chromium were selected as model analytes and the effecting parameters including the amount of GO, concentration of PEI, sample pH, extraction time, and type of desorption solvent were investigated and optimized. The results indicate that the proposed CHD-µSPE method can be successfully applied GO in dispersive mode of SPE without effecting on good capability adsorption of GO. The novel method was applied in determination of lead, cadmium, and chromium in water, human saliva, and urine samples by electrothermal atomic absorption spectrometry. The detection limits are as low as 0.035, 0.005, and 0.012 µg L⁻¹ for Pb, Cd, and Cr respectively. The intra-day precisions (RSDs) were lower than 3.8%. CHD-µSPE method showed a good linear ranges of 0.24–15.6, 0.015–0.95 and 0.039–2.33 µg L⁻¹ for Pb, Cd and Cr respectively. Method performance was investigated by determination of mentioned metal ions in river water, human urine and saliva sample with good recoveries in range of 94.2–103.0%. The accuracy of the method was underpinned by correct analysis of a standard reference material (SRM: 2668 level I, Urine).     

Optimization of solid phase dispersive field‐assisted ultrasonication for the extraction of auramine O and crystal violet dyes using central composite design

Simultaneous preconcentration and determination of auramine o (AO) and crystal violet (CV) dyes from aqueous solution was conducted by ultrasound assisted (dispersive) solid phase microextraction (UASPME) based on SnO₂/SnS composite loaded activated carbon (SnO₂/SnS‐NCs‐AC). The prepared of SnO₂/SnS‐NCs‐AC was characterized by FESEM and XRD analysis. Main and interaction influences of operational parameters such as pH, sonication time, amounts of sorbent, and type of eluent on extraction efficiency were investigated by central composite design and optimized with desirability function approach (DFA). ANOVA was conducted and shows that optimized values were found at 15.33 min sonication time, 0.019 g SnO₂/SnS‐NCs‐AC mass, pH 5.46 and among different solvents, dimethyl formamide was selected as an efficient eluent. Under this conditions recoverees percentage were obtained 82.85% and 86.70% for AO and CV, respectively. Based on F‐test under ANOVA all main effect and interaction effect of understudy parameters has the significant effect on the responses. At optimum conditions, limit of detection (0.0015 and 0.001 mg/l), limit of quantitation (0.4 and 0.4 mg/l), limit of linearity (9.0 and 9.0 mg/l), enrichment factor (33.48 and 83.71) and percent relative standard deviation (3.44 and 4.20) were found to be for auramine o and crystal violet dyes, respectively. Finally, the method was successfully applied for the preconcentration and determination of AO and CV in water samples and ER% of 89.0‐97.0 and 96.2–98.0% as acceptable range were found to be for AO and CV samples, respectively.     

Selective and sensitive determination of silver ions at trace levels based on ultrasonic‐assisted dispersive solid‐phase extraction using ion‐imprinted polymer nanoparticles

We describe ultrasonic‐assisted dispersive solid‐phase extraction based on ion‐imprinted polymer (UA‐DSPE‐IIP) nanoparticles for the selective extraction of silver ions. Ultrasound is a good and robust method to facilitate the extraction of target ions in the sorption step and elution of the target ions in the desorption step. The IIP nanoparticles used in the UA‐DSPE‐IIP were prepared by precipitation polymerization. To prepare the IIP nanoparticles, 2‐vinylpyridine, ethylene glycol dimethacrylate, 2,2′‐azobisisobutyronitrile, 2‐picolinic acid, silver and chloroform–methanol (50:50) solution were used as functional monomer, cross‐linker, initiator, silver‐binding ligand, template ion and porogen, respectively. The IIP nanoparticles were characterized using Fourier transformed infrared spectroscopy, thermogravimetric and differential thermal analysis, X‐ray diffraction and scanning electron microscopy. A Box–Behnken design was used for optimization of sorption and desorption steps in UA‐DSPE‐IIP. In the sorption step: pH of solution, IIP amount (mg), sonication time for sorption (min); in the desorption step: concentration of eluent (mol l⁻¹), volume of eluent (ml), sonication time (min) for desorption were investigated and optimized by Box–Behnken design. The optimum conditions for the method were: pH of solution, 7; sonication time for sorption, 7 min; IIP amount, 17 mg; type and concentration of eluent, HCl 1.5 mol l⁻¹; volume of eluent, 2 ml; sonication time for desorption, 140 s. Under the optimized conditions the limit of detection and relative standard deviation for the detection of silver ions using UA‐DSPE‐IIP were found to be 0.09 μg l⁻¹ and <3%, respectively.     

Development of a novel mixed hemimicelles dispersive micro solid phase extraction using 1-hexadecyl-3-methylimidazolium bromide coated magnetic graphene for the separation and preconcentration of fluoxetine in different matrices before its determination by fiber optic linear array spectrophotometry and mode-mismatched thermal lens spectroscopy

This study aims at developing a novel, sensitive, fast, simple and convenient method for separation and preconcentration of trace amounts of fluoxetine before its spectrophotometric determination. The method is based on combination of magnetic mixed hemimicelles solid phase extraction and dispersive micro solid phase extraction using 1-hexadecyl-3-methylimidazolium bromide coated magnetic graphene as a sorbent. The magnetic graphene was synthesized by a simple coprecipitation method and characterized by X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy and scanning electron microscopy (SEM). The retained analyte was eluted using a 100 μL mixture of methanol/acetic acid (9:1) and converted into fluoxetine-β-cyclodextrin inclusion complex. The analyte was then quantified by fiber optic linear array spectrophotometry as well as mode-mismatched thermal lens spectroscopy (TLS). The factors affecting the separation, preconcentration and determination of fluoxetine were investigated and optimized. With a 50 mL sample and under optimized conditions using the spectrophotometry technique, the method exhibited a linear dynamic range of 0.4–60.0 μg L⁻¹, a detection limit of 0.21 μg L⁻¹, an enrichment factor of 167, and a relative standard deviation of 2.1% and 3.8% (n = 6) at 60 μg L⁻¹ level of fluoxetine for intra- and inter-day analyses, respectively. However, with thermal lens spectrometry and a sample volume of 10 mL, the method exhibited a linear dynamic range of 0.05–300 μg L⁻¹, a detection limit of 0.016 μg L⁻¹ and a relative standard deviation of 3.8% and 5.6% (n = 6) at 60 μg L⁻¹ level of fluoxetine for intra- and inter-day analyses, respectively. The method was successfully applied to determine fluoxetine in pharmaceutical formulation, human urine and environmental water samples.