Determination of Glyphosate and AMPA in Food Samples Using Membrane Extraction Technique for Analytes Preconcentration

The method for determining glyphosate (NPG) and its metabolite AMPA (aminomethyl phosphonic acid) in solid food samples using UAE-SLM-HPLC–PDA technique was developed. Firstly, ultrasonic-assisted solvent extraction (UAE) and protein precipitation step were used for the analyte isolation. Then, the supernatant was evaporated to dryness and redissolved in distilled water (100 mL). The obtained solution was alkalized to pH 11 (with 1 M NaOH) and used directly as donor phase in SLM (supported liquid membrane) extraction. The SLM extraction was performed using 2 M NaCl (5 mL) as an acceptor phase. The flow rate of both phases (donor and acceptor) was set at 0.2 mL/min. The membrane extraction took 24 h but did not require any additional workload. Finally, the SLM extracts were analyzed using the HPLC technique with photo-diode array detector (PDA) and an application of pre-column derivatization with p-toluenesulfonyl chloride. Glyphosate residues were determined in food samples of walnuts, soybeans, barley and lentil samples. The LOD values obtained for the studied food were 0.002 μg g−1 and 0.021 μg g−1 for NPG and AMPA, respectively. Recoveries values ranged from 32% to 69% for NPG, 29% to 56% for AMPA and depended on the type of sample matrix. In the case of buckwheat and rice flour samples, the content of NPG and AMPA was below the detection level of a used analytical method.

A low-voltage electro-membrane extraction for quantification of imatinib and sunitinib in biological fluids

Aim: Hollow-fiber-based supported liquid membrane was modified utilizing nanostructures such as graphite, graphene oxide or nitrogen-doped graphene oxide, for electro-membrane extraction (EME) of imatinib and sunitinib from biological fluids. By applying these conductive nanostructures, a low-voltage EME device (6.0 V) was fabricated. Materials & methods: A response surface methodology through central composite design was used to evaluate and optimize effects of various essential factors that influence on normalized recovery. Results: Optimal extraction conditions were set as, 1-octanol with 0.01 % (w/v) graphene oxide functioning as the supported liquid membrane, an extraction time of 17.0 min, pH of the acceptor and the donor phase of 2.8 and 7.9, respectively. Conclusion: The method was successfully applied to quantify imatinib and sunitinib in biological fluids.

Selective electromembrane extraction and sensitive colorimetric detection of copper(II)

In this study, an extremely effective electromembrane extraction (EME) method was developed for the selective extraction of Cu(II) followed by Red-Green-Blue (RGB) detection. The effective parameters optimized for the extraction efficiency of EME include applied voltage, extraction time, supported liquid membrane (SLM) composition, pH of acceptor/donor phases, and stirring rate. Under optimized conditions, Cu(II) was extracted from a 3 mL aqueous donor phase to 8 µL of 100 mM HCl acceptor solution through 1-octanol SLM using an applied voltage of 50 V for 15 min. The proposed method provides a working range of 0.1–0.75 µg·mL−1 with 0.03 µg·mL−1 limit for detection. Finally, the developed technique was applied to different environmental water samples for monitoring environmental pollution. Obtained relative recoveries were within the range of 93–106%. The relative standard deviation (RSD) and enhancement factor (EF) were found to be ≤4.8% and 100 respectively. We hope that this method can be introduced for quantitative determination of Cu(II) as a fast, simple, portable, inexpensive, effective, and precise procedure.

Hollow fiber based liquid phase microextraction with high performance liquid chromatography for the determination of trace carvedilol (β-blocker) in biological fluids

A hollow-fiber liquid-phase microextraction (HF-LPME), followed by high-performance liquid chromatography–ultraviolet (HPLC–UV) method for the trace determination of carvedilol (β-blocker) in biological fluids, has been described. The separation was achieved using Inertsil ODS-3 C18 (250 mm × 4.6 mm, 3 μm) column with a mobile phase composition of 10 mM phosphate buffer (pH 4.0)–acetonitrile (50:50, v/v) at a flow rate of 1.0 mL/min, under isocratic elution. Several parameters (i.e., type of organic solvent, donor phase pH, concentration of acceptor phase (AP), stirring rate, extraction time, and salt addition) that affect the extraction efficiency were investigated. The optimum HF-LPME conditions were as follows: dihexyl ether as an organic solvent; donor phase pH, 10.7; 0.1 M HCl (AP); 1100-rpm stirring rate; 60-min extraction time; and no salt addition. These parameters have been confirmed using design of experiments. Under these conditions, an enrichment factor of 273-fold was achieved. Good linearity and correlation coefficient were obtained over the range 5–1000 ng/mL (r2 = 0.9994). Limits of detection and quantitation were 1.2 and 3.7 ng/mL, respectively. The relative standard deviation at 3 different concentration levels (5, 500, and 1000 ng/mL) were less than 13.2%. Recoveries for spiked urine and plasma were in the range 80.7–114%. The proposed method is simple, sensitive, and suitable for the determination of carvedilol in biological fluids.

Calix[4]arene Embedded Polyamide Supported Liquid Membrane for Separation of Heavy Metals from Aqueous Solutions

In this study, we aimed to prepare new calixaren embedded mercapto groups supported liquid membranes and to use them in the transport of heavy metals. For this purpose 5,11,17,23-tetra-tert-butyl-25,27-bis(3-thiol-1-oxypropane)-26,28-dihydroxylcalix[4]arene was synthesized. The synthesized calixarene compounds were fully characterized by spectroscopic and the other techniques. The prepared compounds were supported polyamide liquid membranes and obtained calix[4]aren embedded supported liquid membranes (C@PSMs). The characterization of C@PSM was carried out by FTIR, TGA and elemental analysis techniques. Transport experiments were carried out with Pb(II), Cd(II) and Zn(II) as trace metals, to transport from donor phase to accept phase. From the results, it was calculated flux (J) and recovery (RF) values. The affinity (the percentage of metal ion transferred from the source solution) of a PIM towards a range of divalent cations was found to follow the order Zn(II)> Cd(II)> Pb(II).

Ionic Liquid-based Hollow Fiber Liquid–Liquid–Liquid Microextraction Combined with Capillary Electrophoresis for the Determination of Sulfonamides in Aquaculture Waters

Ionic liquid-based hollow-fiber liquid–liquid–liquid microextraction (IL-HF-LLLME) coupled to capillary electrophoresis (CE) has been developed for the determination of six sulfonamides (SAs) in aquaculture waters. A series of extraction parameters was optimized to enhance the extraction efficiency, which included type and pore size of hollow fiber, type and composition of extraction solvent, pH value of donor phase, the concentration of acceptor phase and the mass ratio of donor phase to acceptor phase along with extraction temperature and time. Under optimal conditions, the IL-HF-LLLME-CE method provided a wide liner range for six SAs from 2 to 1,000 μg L−1 (r2 ≥ 0.9995), the limits of the detection from 0.25 to 0.48 and the enrichment factors from 122 to 230, respectively. Relative standard deviations for intra- and interday precision were 1.4–5.3% and 1.8–7.5% (n = 5), respectively. The proposed method was successfully applied for the determination of trace-level SAs in seven real-world aquaculture water samples with good recoveries (80.4–100.7%). Also, sulfamerazine and sulfamethoxazole were detected at the level of 0.52–1.60 μg L−1 in two water samples. Due to its good sensitivity, simple operation, short analysis time and eco-friendliness, the developed method has a great application potential in analysis of trace SA residues in aquaculture waters.

Desalination using modified configuration of supported liquid membrane with enhancement of mass transfer of NaCl

Supported liquid membranes (SLM) suffer from very slow mass transfer of the solute from the donor phase (DP) to the receptor phase (RP) through the liquid membrane (LM). In the present work, an attempt was made to accelerate the mass transfer in SLM by creating a modified configuration in which the DP and RP are made to flow either co- or counter-currently to each other. Variables, which could affect the removal of NaCl, were the volume ratio of DP to RP, type and quantity of sequestering agent (SA), presence of mobile carrier (MC), type of LM, and flow rate of DP and RP. The results showed that the higher the flow rate of DP and RP, the higher the mass transfer of NaCl. Quantity and type of SA and type of LM were prime important factors. Remarkably, the time required for transfer of NaCl from DP to RP was reduced from several hours in the case of stagnant SLM to several minutes in the present work. The mass transfer of NaCl was analysed based on kinetic laws of two consecutive irreversible first-order reactions. The values achieved establish the process is diffusion controlled, and the membrane entrance rate constants increase directly with initial concentration (Ci) and inversely with quantity of SA.