Development of core-shell magnetic molecularly imprinted polymer-based electrochemical sensor for sensitive and selective detection of ezetimibe.

A sensitive electrochemical molecularly imprinted polymer (MIP) sensor was fabricated for detection of ezetimibe (Eze) as an effective cholesterol absorption inhibitor on the surface of a screen-printed carbon electrode based on a magnetic nanoparticle decorated with MIP (Fe3O4@MIP). Placing the magnetic nanoparticle inside the MIP increases the biocompatibility, surface-to-volume ratio, and sensitivity of the sensor. Methacrylic acid (MAA) was used as a monomer, ethylene glycol dimethacrylate (EGDMA) as a cross-linker, and Eze as a template. The fabricated Fe3O4@MIP was characterized using Fourier-transform infrared spectroscopy (FTIR), Transmission electron microscopy (TEM), and scanning electron microscopy (SEM). Detection of Eze was achieved by differential pulse voltammetry. Using this sensor, Eze can be sensitively detected in the range of 1.0 nM-10 µM and detection limit of 0.7 nM. In addition, we have shown that the proposed sensor successfully detects different concentrations of Eze in human serum samples and thus proves its practical application.

Synthesis of magnetic nanoparticle-based molecularly imprinted polymer as a selective sorbent for efficient extraction of ezetimibe from biological samples.

In the present study, a novel and efficient adsorbent constructed of molecularly imprinted polymer on the surface of modified magnetic nanoparticles with oleic acid (MNPs) was applied for the selective extraction of ezetimibe. The magnetic molecularly imprinted polymer (MMIP) was polymerized at the surface of modified MNPs using methacrylic acid as functional monomer, ezetimibe as template and ethylene glycol dimethacrylate as cross-linker. The resulting MMIP showed high adsorption capacity, good selectivity and fast kinetic binding for the template molecule. It was characterized by Fourier transform infrared analysis, scanning electron microscopy and transmission electron microscopy methods. The maximum adsorption capacity of MMIP was obtained as 137.1 mg g-1 and it took about 20 min to achieve the equilibrium state. The adsorption model of the adsorbent was fitted with the Freundlich and Langmuir isotherm equations. The assay exhibited a linear range of 0.003-20.000 mg L-1 for ezetimibe with a correlation coefficient of 0.995. The relative standard deviations for the recoveries were <5.2. The method was also examined for the analysis of ezetimibe in the biological samples.

In-syringe reversed dispersive liquid-liquid microextraction for the evaluation of three important bioactive compounds of basil, tarragon and fennel in human plasma and urine samples.

In the present study, an efficient and environmental friendly method (called in-syringe reversed dispersive liquid-liquid microextraction (IS-R-DLLME)) was developed to extract three important components (i.e. para-anisaldehyde, trans-anethole and its isomer estragole) simultaneously in different plant extracts (basil, fennel and tarragon), human plasma and urine samples prior their determination using high-performance liquid chromatography. The importance of choosing these plant extracts as samples is emanating from the dual roles of their bioactive compounds (trans-anethole and estragole), which can alter positively or negatively different cellular processes, and necessity to a simple and efficient method for extraction and sensitive determination of these compounds in the mentioned samples. Under the optimum conditions (including extraction solvent: 120 µL of n-octanol; dispersive solvent: 600 µL of acetone; collecting solvent: 1000 µL of acetone, sample pH 3; with no salt), limits of detection (LODs), linear dynamic ranges (LDRs) and recoveries (R) were 79-81 ng mL(-1), 0.26-6.9 µg mL(-1) and 94.1-99.9%, respectively. The obtained results showed that the IS-R-DLLME was a simple, fast and sensitive method with low level consumption of extraction solvent which provides high recovery under the optimum conditions. The present method was applied to investigate the absorption amounts of the mentioned analytes through the determination of the analytes before (in the plant extracts) and after (in the human plasma and urine samples) the consumption which can determine the toxicity levels of the analytes (on the basis of their dosages) in the extracts.

Ionic-liquid-based hollow-fiber liquid-phase microextraction method combined with hybrid artificial neural network-genetic algorithm for speciation and optimized determination of ferro and ferric in environmental water samples.

A novel and environmentally friendly ionic-liquid-based hollow-fiber liquid-phase microextraction method combined with a hybrid artificial neural network (ANN)-genetic algorithm (GA) strategy was developed for ferro and ferric ions speciation as model analytes. Different parameters such as type and volume of extraction solvent, amounts of chelating agent, volume and pH of sample, ionic strength, stirring rate, and extraction time were investigated. Much more effective parameters were firstly examined based on one-variable-at-a-time design, and obtained results were used to construct an independent model for each parameter. The models were then applied to achieve the best and minimum numbers of candidate points as inputs for the ANN process. The maximum extraction efficiencies were achieved after 9 min using 22.0 µL of 1-hexyl-3-methylimidazolium hexafluorophosphate ([C6MIM][PF6]) as the acceptor phase and 10 mL of sample at pH = 7.0 containing 64.0 µg L(-1) of benzohydroxamic acid (BHA) as the complexing agent, after the GA process. Once optimized, analytical performance of the method was studied in terms of linearity (1.3-316 µg L(-1), R (2) = 0.999), accuracy (recovery = 90.1-92.3%), and precision (relative standard deviation (RSD) <3.1). Finally, the method was successfully applied to speciate the iron species in the environmental and wastewater samples.

Synthesis of molecularly imprinted polypyrrole as an adsorbent for solid-phase extraction of warfarin from human plasma and urine.

The aim of this work was to develop a method for the clean-up and preconcentration of warfarin from biological sample employing a new molecularly imprinted polymer (MIP) as a selective adsorbent for solid-phase extraction (SPE). This MIP was synthesized using warfarin as a template, pyrrole as a functional monomer and vinyl triethoxysilane as a cross-linker. The molar ratio of 1:4:20 (template-functional monomer-cross-linker) showed the best results. Nonimprinted polymers (NIPs) were prepared and treated with the same method, but in the absence of warfarin. The prepared polymer was characterized by Fourier transmission infrared spectrometry and scanning electron microscopy. An adsorption process (SPE) for the removal of warfarin using the fabricated MIPs and NIPs was evaluated under various conditions. Effective parameters on warfarin extraction, for example, type and volume of elution solvent, pH of sample solution, breakthrough volume and maximum loading capacity, were studied. The limits of detection were in the range of 0.0035-0.0050 µg mL(-1). Linearity of the method was determined in the range of 0.0165-10.0000 µg mL(-1) for plasma and 0.0115-10.0000 µg mL(-1) for urine with coefficients of determination (R(2)) ranging from 0.9975 to 0.9985. The recoveries for plasma and urine samples were >95%.

Extraction optimization of Loratadine by supramolecular solvent-based microextraction and its determination using HPLC.

Optimization of supramolecular solvent-based microextraction (SSME) of Loratadine and its determination with high-performance liquid chromatography (HPLC) with ultra violet (UV) detection were investigated. A factorial design (FD) and a central composite face-centered (CCF) were applied to evaluate the SSME procedure. The effect of four parameters on extraction efficiency was investigated. The factors studied were decanoic acid amount, percentage of tetrahydrofuran (THF) (v/v), pH and extraction time. According to half factorial design results, the effective parameters were decanoic acid amount, THF percentage (v/v) and pH. Then, a CCF was applied to obtain optimal condition. The optimized conditions were obtained at 110mg of decanoic acid, 10% of THF and pH=3. The limits of detection were in the range of 0.3-0.4ng/ml. Linearity of the method was determined to be in the range of 1.0-400.0ng/ml for distilled water and 1.3-400.0ng/ml for plasma. The extraction recovery was >92%. RSD for intra and inter day (n=5) of extraction of Loratadine were 3.1% and 6.2%, respectively. The developed method was successfully applied for the determination of Loratadine in distilled water and plasma samples.

HPLC determination of hesperidin, diosmin and eriocitrin in Iranian lime juice using polyamide as an adsorbent for solid phase extraction.

Solid phase extraction (SPE) and HPLC were used for simultaneous determination of hesperidin, diosmin and eriocitrin in Iranian lime juice samples. The method involved very simple efficient SPE with polyamide cartridge, the use of mixture of water/acetonitrile/acetic acid (78:19:3, v/v) as a mobile phase at a flow rate of 0.8 mL/min and UV detection at 280 nm. Optimum conditions for SPE were achieved using 8 mL water/methanol (85:15, v/v, pH=3) as the washing solution and 4 mL methanol for elution. SPE parameters, such as maximum loading capacity and breakthrough volume, were also determined for each analyte. Good clean-up and high>90% were observed for all analytes. Limits of detection, limits of quantification, linear range, recovery, repeatability of retention times, and peak areas for hesperidin, diosmin and eriocitrin were 0.0283-0.0512 µg/mL, 0.0857-0.155 µg/mL, 0.0283-105.0 µg/mL (R² > 0.99), 93.3-98.1%, 3.2-4.7% and 2.8-3.6%, respectively. The method was applied to analysis of lime juice samples obtained from different locations of Iran.

Comparison of C18 silica and multi-walled carbon nanotubes as the adsorbents for the solid-phase extraction of Chlorpyrifos and Phosalone in water samples using HPLC.

A comparison between C(18) silica and multi-walled carbon nanotubes (MWCNTs) in the extraction of Chlorpyrifos and Phosalone in environmental water samples was carried out using HPLC. Parameters affecting the extraction were type and volume of elution solvent, pH and flow rate of sample through the adsorbent. The optimum conditions obtained by C(18) cartridge for adsorption of these pesticides were 4 mL dichloromethane as elution solvent, sample pH of 5, flow rate of 1 mL/min, and those for MWCNT cartridge were 3 mL dichloromethane, pH of 5 and flow rate of 10 mL/min, respectively. Optimized mobile phase for separation and determination of these compounds by HPLC was methanol/water (80:20 v/v) with pH=5 (adjusted with phosphate buffer). Under optimal chromatographic and SPE conditions, LOD, linear range and precision (RSD n=8) were 3.03x10(-3), 0.01-5.00 microg/mL and 2.7% for Chlorpyrifos and 4.03x10(-4), 0.01-5.00 microg/mL and 2.3% for Phosalone, in C(18) cartridge, respectively. These values for MWCNT were 4.02x10(-6), 0.001-0.500 microg/mL and 1.8% for Chlorpyrifos and 1.02x10(-6), 0.001-0.500 microg/mL and 1.5% for Phosalone, respectively.