Combination of magnetic dispersive micro solid-phase extraction and supramolecular solvent-based microextraction followed by high-performance liquid chromatography for determination of trace amounts of cholesterol-lowering drugs in complicated matrices.

A novel, efficient, rapid, simple, sensitive, selective, and environmentally friendly method termed magnetic dispersive micro solid-phase extraction combined with supramolecular solvent-based microextraction (Mdµ-SPE-SSME) followed by high-performance liquid chromatography (HPLC) with UV detection is introduced for the simultaneous microextraction of cholesterol-lowering drugs in complicated matrices. In the first microextraction procedure, using layered double hydroxide (LDH)-coated Fe3O4 magnetic nanoparticles, an efficient sample cleanup is simply and rapidly provided without the need for time-consuming centrifugation and elution steps. In the first step, desorption of the target analytes is easily performed through dissolution of the LDH-coated magnetic nanoparticles containing the target analytes in an acidic solution. In the next step, an emulsification microextraction method based on a supramolecular solvent is used for excellent preconcentration, ultimately resulting in an appropriate determination of the target analytes in real samples. Under the optimal experimental conditions, the Mdµ-SPE-SSME-HPLC-UV detection procedure provides good linearity in the ranges of 1.0-1500 ng mL-1, 1.5-2000 ng mL-1, and 2.0-2000 ng mL-1 with coefficients of determination of 0.995 or less, low limits of detection (0.3, 0.5, and 0.5 ng mL-1), and good extraction repeatabilities (relative standard deviations below 7.8%, n = 5) in deionized water for rosuvastatin, atorvastatin, and gemfibrozil, respectively. Finally, the proposed method is successfully applied for the determination of the target analytes in complicated matrices. Graphical Abstract Mdµ-SPE-SSME procedure.

Use of Chrysosporium/carbon nanotubes for preconcentration of ultra-trace cadmium levels from various samples after extensive studies on its adsorption properties.

Carbon nanotubes were used to immobilize Chrysosporium fungus for building an adequate adsorbent to be used as an desirable sorbent for preconcentration and measurement of cadmium ultra-trace levels in various samples. After characterization, the potential of Chrysosporium/carbon nanotubes for the sorption of Cd(II) ions was scrutinized by the aid of central composite design, and comprehensive studies of sorption equilibrium, kinetics and thermodynamic aspects were accomplished. Then, the composite was utilized for preconcentration of ultra-trace cadmium levels, by a mini-column packed with Chrysosporium/carbon nanotubes, before its determination with ICP-OES. The outcomes vouchsafed that (i) Chrysosporium/carbon nanotube has a high tendency for selective and rapid sorption of cadmium ion, at pH 6.1, and (ii) kinetic, equilibrium, and thermodynamic studies showed a high affinity of the Chrysosporium/carbon nanotubes for cadmium ion. Also, the outcomes displayed that cadmium can quantitatively be sorbed at a flow speed lesser than 7.0 mL/min and a 1.0 M HCl solution (3.0 mL) was sufficient to desorbe the analyte. Eventually, preconcentration and measurement of Cd(II) in different foods and waters were successfully accomplished with good accuracy, high precision (RSDs ≤5.65%), and low limit of detection (0.015 µg/L).

CO2-effervescence assisted dispersive micro solid-phase extraction based on a magnetic layered double hydroxide modified with polyaniline and a surfactant for efficient pre-concentration of heavy metals in cosmetic samples.

In this paper, a CO2-effervescence assisted dispersive micro solid-phase extraction procedure (CO2-EA-DµSPE) using a magnetic layered double hydroxide modified with polyaniline and a surfactant (Zn-Al-LDH-PA-DBSNa-Fe3O4) was applied for the pre-concentration of heavy metals (Ni2+, Pb2+, Co2+, and Cd2+). The final analysis of the analytes was carried out by atomic absorption spectroscopy. XRD, FTIR, and SEM studies were used for the characterization of the synthesized nanoadsorbent. For the maximum extraction efficiency, effective factors (including pH, nanoadsorbent dosage, and volume of the eluent) were investigated using the central composite design (CCD) method. Under the optimum conditions, the preconcentration factor was more than 20. The linear ranges for Ni2+, Pb2+, Co2+, and Cd2+ were obtained as (5-550), (7-750), (5-500), and (3-100) ng mL-1, respectively. The proposed method provided low detection limits (1.4, 2.1, 1.5, and 0.9 ng mL-1 for Ni2+, Pb2+, Co2+, and Cd2+, respectively) and suitable repeatability (relative standard deviation values (RSDs) below 6.1%, n = 6). Finally, the current method was successfully used for the extraction of heavy metals from cosmetic samples.

Coupling of two centrifugeless ultrasound-assisted dispersive solid/liquid phase microextractions as a highly selective, clean, and efficient method for determination of ultra-trace amounts of non-steroidal anti-inflammatory drugs in complicated matrices.

In this work, a new, simple, rapid, and environmentally friendly method with a high sample clean-up capability termed as centrifugeless ultrasound-assisted dispersive micro solid-phase extraction coupled with salting-out ultrasound-assisted liquid-liquid microextraction based on solidification of a floating organic droplet followed by high performance liquid chromatography is introduced for the first time. In this method, the three non-steroidal anti-inflammatory drugs diclofenac, ibuprofen, and mefenamic acid are first extracted based on an effective nanoadsorbent named as the layered double hydroxide-carbon nanotube nanohybrid. The first step provides a rapid and convenient way to separate the adsorbent from the sample matrix by a syringe nanofilter without additional centrifugation. In the next step, which is based upon the salting-out effect, after emulsification in the presence of ultrasonic irradiation, the phase separation is simply achieved through the salting-out phenomenon, and the extracting solvent is suspended on top of the sample solution. Under the optimal experimental conditions including the initial pH value of 6.0, 8.0 mg of the nanohybrid, 3 min ultrasonic time, 100 µL elution solvent (first step), secondary pH value of 3.0, 60 µL of 1-undecanol, 60 s ultrasonic time, and flow rate of 3 mL min-1 (second step), good responses were obtained for diclofenac, ibuprofen, and mefenamic acid in the concentration ranges of 0.8-2000, 0.8-2500, and 0.5-2000 ng mL-1, respectively, with low limits of detection ranging from 0.1 to 0.2 ng mL-1. The intra-day and inter-day precisions for the target analytes at the three concentration levels were in the ranges of 6.1-7.8% and 6.3-8.1%, respectively. The proposed method was also successfully applied to the biological and waste water samples, and excellent recoveries were obtained in the range of 92.9-103.1% even when the matrix was complex.

Centrifugeless dispersive liquid-liquid microextraction based on salting-out phenomenon followed by high performance liquid chromatography for determination of Sudan dyes in different species.

In this work, a novel method, namely centrifugeless dispersive liquid-liquid microextraction, is introduced for the efficient extraction of banned Sudan dyes from foodstuff and water samples. In this method, which is based upon the salting-out phenomenon, in order to accelerate the extraction process, the extraction solvent (1-undecanol, 75 µL) is dispersed into the sample solution. Then the mixture is passed through a small column filled with 5 g sodium chloride, used as a separating reagent. In this condition, fine droplets of the extraction solvent are floated on the mixture, and the phase separation is simply achieved. This method is environmentally friendly, simple, and very fast, so that the overall extraction time is only 7 min. Under the optimal experimental conditions, the preconcentration factors in the range of 90-121 were obtained for the analytes. Also good linearities were obtained in the range of 2.5-1200 ng mL-1 (r2 ≥ 0.993).

Dissolvable layered double hydroxide as an efficient nanosorbent for centrifugeless air-agitated dispersive solid-phase extraction of potentially toxic metal ions from bio-fluid samples.

In the present work, a novel nanosorbent namely layered double hydroxides with 4-amino-5-hydroxyl-2,7-naphthalendisulfonic acid monosodium salt interlayer anion (Mg-Al-AHNDA-LDH) was synthesized and applied as a dissolvable nanosorbent in a centrifugeless ultrasound-enhanced air-agitated dispersive solid-phase extraction (USE-AA-D-SPE) method. This method was used for the separation and preconcentration of some metal ions including Cd2+, Cr6+, Pb2+, Co2+, and Ni2+ prior to their determination using the micro-sampling flame atomic absorption spectrometry (MS-FAAS) technique. The most interesting aspect of this nanosorbent is its immediate dissolvability at pH values lower than 4. This capability drastically eliminates the elution step, leading to a great improvement in the extraction efficiency and a decrease in the extraction time. Also in this method, the use of a syringe nanofilter eliminates the need for the centrifugation step, which is time-consuming and essentially causes the analysis to be off-line. Several effective parameters governing the extraction efficiency including the sample solution pH, amount of nanosorbent, eluent condition, number of air-agitation cycles, and sonication time were investigated and optimized. Under the optimized conditions, the good linear dynamic ranges of 2-70, 6-360, 7-725, 7-370, and 8-450 ng mL-1 for the Cd2+, Cr6+, Pb2+, Co2+and Ni2+ ions, respectively, with the correlation of determinations (R2s) higher than 0.997 were obtained. The limits of detection (LODs) were found to be 0.6, 1.7, 2.0, 2.1, and 2.4 for the Cd2+, Cr6+, Pb2+, Co2+, and Ni2+ ions, respectively. The intra-day and inter-day precisions (percent relative standard deviations (%RSDs) (n = 5)) were below 7.8%. The proposed method was also successfully applied for the extraction and determination of the target ions in different biological fluid and tap water samples.

In-line micro-matrix solid-phase dispersion extraction for simultaneous separation and extraction of Sudan dyes in different spices.

A novel, simple, fast, and miniaturized method, termed in-line micro-matrix solid-phase dispersion (in-line MMSPD), coupled with high performance liquid chromatography (HPLC) was developed for the simultaneous extraction and determination of Sudan dyes (i.e. Sudan I-IV, Sudan orange G, Sudan black B, and Sudan red G) with the aid of an experimental design strategy. In this method, a matrix solid-phase dispersion (MSPD) column including a suitable mixture of polar sorbents was inserted in the mobile phase pathway, and while the interfering compounds were retained, the analytes were eluted and entered into the analytical column. In this way, the extraction, elution, and separation of the analytes were performed sequentially. Under the optimal experimental conditions (including the amount of sample, 0.0426g; amount of dispersant phase, 0.0216g of florisil, 0.0227g of silica, 0.0141g of alumina; and blending time, 112s), the limits of detection (LODs), limits of quantification, linear dynamic ranges, and recoveries were obtained to be 0.3-15.3µgkg(-1), 1-50µgkg(-1), 50-28,000µgkg(-1), and 94.5-99.1%, respectively. The results obtained showed that determination of the selected Sudan dyes in food samples using an enough sensitive and a simple analytically validated method like in-line MMSPD may offer a suitable screening method, which could be useful for food analysis and adulteration.