Exploring the impact of polyvinylidenefluoride membrane physical properties on the enrichment efficacy of microfluidic electro-membrane extraction of acidic drugs.

Membrane technology has revolutionized various fields with its energy efficiency, versatility, user-friendliness, and adaptability. This study introduces a microfluidic chip, comprised of silicone rubber and polymethylmethacrylate (PMMA) sheets to explore the impacts of polymeric support morphology on electro-membrane extraction efficiency, representing a pioneering exploration in this field. In this research, three polyvinylidenefluoride (PVDF) membranes with distinct pore sizes were fabricated and their characteristics were assessed through field-emission scanning electron microscopy (FESEM), and atomic force microscopy (AFM). This investigation centers on the extraction of three widely prescribed non-steroidal anti-inflammatory drugs: aspirin (ASA), naproxen (NAP), and ibuprofen (IBU). Quantitative parameters in the extraction process including voltage, donor phase flow rate, and acceptor phase composition were optimized, considering the type of membrane as a qualitative factor. To assess the performance of the fabricated PVDF membranes, a comparative analysis with a commercially available Polypropylene (PP) membrane was conducted. Efficient enrichment factors of 30.86, 23.15, and 21.06 were attained for ASA, NAP, and IBU, respectively, from urine samples under optimal conditions using the optimum PVDF membrane. Significantly, the choice of the ideal membrane amplified the purification levels of ASA, NAP, and IBU by factors of 1.6, 7.5, and 40, respectively.

Molecular separation of ibuprofen and 4-isobutylacetophenone using octanol organic solution by porous polymeric membranes.

Molecular separation of pharmaceutical contaminants from water has been recently of great interest to alleviate their detrimental impacts on environment and human well-being. As the novelty, this investigation aims to develop a mechanistic modeling approach and consequently its related CFD-based simulations to evaluate the molecular separation efficiency of ibuprofen (IP) and its metabolite 4-isobutylacetophenone (4-IBAP) from water inside a porous membrane contactor (PMC). For this purpose, octanol has been applied as an organic phase to extract IP and 4-IBAP from the aqueous solution due to high solubility of solutes in octanol. Finite element (FE) technique is used as a promising tool to simultaneously solve continuity and Navier-Stokes equations and their associated boundary conditions in tube, shell and porous membrane compartments of the PMC. The results demonstrated that the application of PMC and liquid-liquid extraction process can be significantly effective due to separating 51 and 54% of inlet IP and 4-IBAP molecules from aqueous solution, respectively. Moreover, the impact of various operational / functional parameters such as packing density, the number of fibrous membrane, the module length, the membrane porosity / tortuosity, and ultimately the aqueous solution flow rate on the molecular separation efficiency of IP and 4-IBAP is studied in more details.

TiO2 nanoparticles and C-Nanofibers modified magnetic Fe3O4 nanospheres (TiO2@Fe3O4@C-NF): A multifunctional hybrid material for magnetic solid-phase extraction of ibuprofen and photocatalytic degradation of drug molecules and azo dye.

Accurate sensitive analysis of drug ingredient substances in biological, pharmaceutical and environmental samples and removal of drug ingredient substances in environmental samples owngreat importance for sustaining viability. The realization of these processes using a single material offers significant advantages in terms of cost, time and ease of use. In this study, TiO2 nanoparticles and C-Nanofibers modified magnetic Fe3O4 nanospheres (TiO2@Fe3O4@C-NFs) synthesized as a multifunctional material employing a simple hydrothermal synthesis method. This innovative material was exploited in the magnetic solid-phase extraction (MSPE) method for the preconcentration of ibuprofen and photocatalytic degradation of antibiotics, non-steroidal anti-inflammatory drugs (NSAIDs), and azo dye. To our knowledge, no studies have been previously conducted using the same material as magnetic solid-phase extraction adsorbent and magnetically separable photocatalyst. The characterization of TiO2@Fe3O4@C-NFs was carried out by XRD, FE-SEM, EDX and Raman techniques. The main analytical parameters affecting MSPE performance of ibuprofen such as pH, sorbent amount eluent type and volume and sample volume were optimized. The optimum values of the method were determined at the following parameters: pH 4.0, adsorbent amount 150 mg and eluent 2 mL of acetone. Ibuprofen analysis after MSPE was carried out using a high-performance liquid chromatography diode array detection system (HPLC-DAD). The photocatalytic degradation efficiencies of TiO2@Fe3O4@C-NF hybrid material for probe-analytes reached 80-100% and the complete degradation attained within the range of 8-125 min under UV irradiation. Simple preparation, practical isolation from solutions, high efficiency, reproducibility, and sustainability are the main advantages of the TiO2@Fe3O4@C-NFs for MSPE and photocatalytic degradation applications.

Hybrid monoliths with metal-organic frameworks in spin columns for extraction of non-steroidal drugs prior to their quantitation by reversed-phase HPLC.

A (glycidyl methacrylate)-co-(ethylene glycol dimethacrylate) polymer (poly(GMA-co-EDMA)) was functionalized with metal-organic frameworks (MOF) and used as a sorbent for solid-phase extraction (SPE). The polymeric sorbent was prepared in-situ by photopolymerization in a previously wall-modified spin column, and then modified with an amino-modified MOF of type NH2-MIL-101(Cr). The sorbents were used for the extraction of nonsteroidal anti-inflammatory drugs (NSAIDs) from human urine samples. The sorbent was compared with the parent monolith and embedded approach, where the MOF particles are admixed in the polymerization mixture before the in-situ polymerization in the modified spin column. SPE is performed by percolating the sample solutions in a centrifuge, which streamlines the SPE steps. The hybrid composites were characterized by scanning electron microscopy and nitrogen intrusion porosimetry. Three NSAIDs (ketoprofen, flurbiprofen, and ibuprofen) were tested. They were eluted from the sorbent with acidified water-acetonitrile mixtures and subsequently analyzed by reversed-phase HPLC with UV detection. The detection limits varied in the range from 0.1 to 7 µg·L-1, and the precisions (relative standard deviation) were <14% in all the cases. The recoveries were between 71.0 and 78.0% in spiked urine samples. Graphical abstractA hybrid monolith modified with amino-modified MOF [named NH2-MIL-101(Cr)] in wall-modified spin columns was prepared. The resulting micro-extraction device was applied to the extraction and preconcentration of non-steroidal anti-inflammatory drugs.

Mesoporous silica from batik sludge impregnated with aluminum hydroxide for the removal of bisphenol A and ibuprofen.

The present study reports the removal of Bisphenol A (BPA) and Ibuprofen (IBP) using adsorbents prepared from batik sludge. The calcite sludge-aluminum hydroxide (CAl) adsorbent was prepared by calcination and followed by aluminum hydroxide impregnation. The batik sludge and prepared adsorbents were characterized by FESEM, TGA, XRD, FTIR and BET techniques. The maximum adsorption capacity, adsorption time, different initial solution pH, ionic strength and regeneration study of the adsorbents were also investigated. Furthermore, the sorption behavior of the pollutants were studied by the Langmuir and Freundlich isotherms. The deposition of Al(OH)3 enhanced the BPA and IBP adsorption capacity on the CAl surface. The maximum removal capacity of BPA and Ibuprofen were 83.53 mg g-1 and 34.96 mg g-1 for the CAl adsorbent. In addition, the kinetic data for BPA and IBP were fitted to the pseudo first order, pseudo second order, Elovich, parabolic diffusion and power function equations to understand the sorption behavior. The adsorption behavior of BPA and IBP was mainly chemisorption. This study shows that CAl is a promising adsorbent for the removal of BPA and IBP.

Determination of ibuprofen enantiomers in breast milk using vortex-assisted matrix solid-phase dispersion and direct chiral liquid chromatography.

A mixture of ß-cyclodextrin (ß-CD) and primary and secondary amine (PSA) sorbents was employed for the extraction and quantification of ibuprofen enantiomers from human breast milk, combining a vortex-assisted matrix solid-phase dispersion method (MSPD) and direct chiral liquid chromatography (CLC) with ultraviolet detection (UV). The MSPD sample preparation procedure was optimized focusing on both the type and amount of dispersion/sorption sorbents and the nature of the elution solvent, in order to obtain acceptable recoveries and avoiding enantiomer conversion. These MSPD parameters were optimized with the aid of an experimental design approach. Hence, a factorial design was used for identification of the main variables affecting the extraction process of ibuprofen enantiomers. Under optimum selected conditions, MSPD combined with direct CLC-UV was successfully applied for ibuprofen enantiomeric determination in breast milk at enantiomer levels between 0.15 and 6.0µgg-1. The proposed analytical method also provided good repeatability, with relative standard deviations of 6.4% and 8.3% for the intra-day and inter-day precision, respectively.

Biosorption-based dispersive liquid-liquid microextraction combined with polypyrrole-coated magnetic nanoparticles as an effective sorbent for the extraction of ibuprofen from water samples using magnetic solid-phase extraction.

In this paper, biosorption-based dispersive liquid-liquid microextraction (BioDLLME) in combination with magnetic solid-phase extraction (MSPE) has been developed as a sample pretreatment method with high enrichment factor for the sensitive determination of ibuprofen in water samples. At first, magnetic Fe3 O4 /polypyrrole nanoparticles were synthesized and employed as sorbent for the MSPE of ibuprofen. After the elution of the desired compound from the sorbent by using methanol, BioDLLME technique was performed on the obtained solution. After MSPE, the eluent of MSPE was used as the disperser solvent for BioDLLME, so that the extra preconcentration factor could be achieved. The properties of the prepared magnetic sorbent were characterized using field emission scanning electron microscopy, Fourier transform infrared spectroscopy and X-ray diffraction methods. Experimental parameters affecting the extraction efficiency were studied and optimized. Under optimum conditions, the enrichment factor was 274. The linear dynamic range and limit of detection are 0.25-80 and 0.083 µg/L, respectively. The relative standard deviations for six replicate measurements are 3.82%.

High-repetition rate laser ablation coupled to dielectric barrier discharge postionization for ambient mass spectrometry.

Most ambient sample introduction and ionization techniques for native mass spectrometry are highly selective for polar agents. To achieve a more general sensitivity for a wider range of target analytes, a novel laser ablation dielectric barrier discharge (LA DBD) ionization scheme was developed. The approach employs a two-step mechanism with subsequent sample desorption and post-ionization. Effective ablation was achieved by the second harmonic output (λ=532nm) of a diode pumped Nd:YVO4 laser operating at a high-repetition rate of several kHz and pulse energies below 100µJ. The ejected analyte-containing aerosol was consecutively vaporized and ionized in the afterglow of a DBD plasma jet. Depending on their proton affinity the superexcited helium species in this afterglow produced analyte ions as protonated and ammoniated species, as well as radical cations. The optimization procedure could corroborate underlying conceptual consideration on the ablation, desorption and ionization mechanisms. A successful detection of a variety of target molecules could be shown from the pharmaceutical ibuprofen, urea, the amino acids l-arginine, l-lysine, the polymer polyethylene glycol, the organometallic compound ferrocene and the technical mixture wild mint oil. For a reliable evaluation of the introduced detection procedure spectra from the naturally abundant alkaloid capsaicin in dried capsicum fruits were recorded.

Fabrication of aluminum terephthalate metal-organic framework incorporated polymer monolith for the microextraction of non-steroidal anti-inflammatory drugs in water and urine samples.

Polymer monolith microextraction (PMME) based on capillary monolithic column is an effective and useful technique to preconcentrate trace analytes from environmental and biological samples. Here, we report the fabrication of a novel aluminum terephthalate metal-organic framework (MIL-53(Al)) incorporated capillary monolithic column via in situ polymerization for the PMME of non-steroidal anti-inflammatory drugs (NSAIDs) (ketoprofen, fenbufen and ibuprofen) in water and urine samples. The fabricated MIL-53(Al) incorporated monolith was characterized by X-ray powder diffractometry, scanning electron microscopy, Fourier transform infrared spectrometry, and nitrogen adsorption experiment. The MIL-53(Al) incorporated monolith gave larger surface area than the neat polymer monolith. A 2-cm long MIL-53(Al) incorporated capillary monolith was applied for PMME coupled with high-performance liquid chromatography for the determination of the NSAIDs. Potential factors affecting the PMME were studied in detail. Under the optimized conditions, the developed method gave the enhancement factors of 46-51, the linear range of 0.40-200µgL(-1), the detection limits (S/N=3) of 0.12-0.24µgL(-1), and the quantification limits (S/N=10) of 0.40-0.85µgL(-1). The recoveries for spiked NSAIDs (20µgL(-1)) in water and urine samples were in the range of 77.3-104%. Besides, the MIL-53(Al) incorporated monolith was stable enough for 120 extraction cycles without significant loss of extraction efficiency. The developed method was successfully applied to the determination of NSAIDs in water and urine samples.

Parallel artificial liquid membrane extraction of acidic drugs from human plasma.

The new sample preparation concept "Parallel artificial liquid membrane extraction (PALME)" was evaluated for extraction of the acidic drugs ketoprofen, fenoprofen, diclofenac, flurbiprofen, ibuprofen, and gemfibrozil from human plasma samples. Plasma samples (250 µL) were loaded into individual wells in a 96-well donor plate and diluted with HCl to protonate the acidic drugs. The acidic drugs were extracted as protonated species from the individual plasma samples, through corresponding artificial liquid membranes each comprising 2 µL of dihexyl ether, and into corresponding acceptor solutions each comprising 50 µL of 25 mM ammonia solution (pH 10). The liquid membranes and the acceptor solutions were located in a 96-well filter plate, which was sandwiched with the 96-well donor plate during extraction. Parallel extraction of several samples was performed for 15 to 60 min, followed by high-performance liquid chromatography-ultraviolet detection of the individual acceptor solutions. Important PALME parameters including the chemical composition of the liquid membrane, extraction time, and sample pH were optimized, and the extraction performance was evaluated. Except for flurbiprofen, exhaustive extraction was accomplished from plasma. Linearity was obtained for all six drugs in the range 0.025-10 µg/mL, with r (2) values ranging between 0.998 and 1.000. Precision data were in the range 3-22% RSD, and accuracy data were within 72-130% with spiked plasma samples. Based on the current experiences, PALME showed substantial potential for future high-throughput bioanalysis of non-polar acidic drugs.

Determination of non-steroidal anti-inflammatory drugs in urine by hollow-fiber liquid membrane-protected solid-phase microextraction based on sol-gel fiber coating.

A new rapid, simple and effective cleanup procedure is demonstrated for the determination of ibuprofen, naproxen and diclofenac in urine samples by using hollow-fiber liquid membrane-protected solid-phase microextraction (HFLM-SPME) based on sol-gel technique and gas chromatography-flame ionization detector (GC-FID). In this technique, a sol-gel coated fiber was protected with a length of porous polypropylene hollow fiber membrane which was filled with water-immiscible organic phase. Subsequently the whole device was immersed into urine sample for extraction. Poly(ethylene glycol) (PEG) grafted onto multi-walled carbon nanotubes (PEG-g-MWCNTs) was used as extraction phase to prepare the sol-gel SPME fiber. Important parameters influencing the extraction efficiency such as desorption temperature and time, organic solvent, extraction temperature and time, pH, stirring speed and salt effect were investigated and optimized. Under the optimal conditions, the method detection limits (S/N=3) were in the range of 0.03-0.07ngmL(-1) and the limits of quantification (S/N=10) between 0.08 and 0.15ngmL(-1). Relative standard deviations for intra-day and inter-day precisions were 4.8-9.0% and 4.9-8.1%, respectively. Subsequently, the method was successfully applied to human urine fractions after administration of ibuprofen, naproxen and diclofenac.

Determination of non-steroidal anti-inflammatory drugs in water samples by solid-phase microextraction based sol-gel technique using poly(ethylene glycol) grafted multi-walled carbon nanotubes coated fiber.

In this study, poly(ethylene glycol) (PEG) grafted multi-walled carbon nanotubes (PEG-g-MWCNTs) were synthesized by the covalent functionalization of MWCNTs with hydroxyl-terminated PEG chains. PEG-g-MWCNTs was used as a novel stationary phase to prepare the sol-gel solid-phase microextraction (SPME) fiber in combination with gas chromatography-flame ionization detector (GC-FID) for the determination of ibuprofen, naproxen and diclofenac in real water samples. Some parameters which influencing the extraction efficiency were such as desorption temperature and time, extraction temperature and time, pH, salt effect and stirring speed that were investigated and optimized. Under the optimal conditions, the method detection limits (S/N=3) were in the range of 0.007-0.03 ng mL(-1) and the limits of quantification (S/N=10) between 0.05 and 0.07 ng mL(-1). The relative standard deviations (RSDs) for one fiber (repeatability) (n=5) were obtained from 5.9 up to 8.1% and between fibers or batch to batch (n=3) (reproducibility) in the range of 7.2-9.1%. The developed method was successfully applied to real water samples while the relative recovery percentages obtained for the spiked water samples at 0.2 ng mL(-1) were from 84 to 107%.

Hollow fiber-based liquid-phase microextraction (HF-LPME) of ibuprofen followed by FIA-chemiluminescence determination using the acidic permanganate-sulfite system.

Hollow fiber-based liquid-phase microextraction (HF-LPME) is a relatively new technique employed in analytical chemistry for sample pretreatment which offers more selectivity and sensitivity than any traditional extraction technique. This paper describes a three-phase HF-LPME method for ibuprofen using a polypropylene membrane supporting dihexyl ether followed by a chemiluminescence (CL) determination using the CL enhancement on the acidic permanganate-sulfite system in a FIA configuration which is the first time that both techniques have been combined for analytical purposes. The CL intensity (peak area) was proportional to the log of ibuprofen concentration in the donor phase over the range 0.1-20 microg mL(-1). The detection limit was 0.03 microg mL(-1) of ibuprofen in the donor phase. The method was satisfactory reproducible and has been applied to the ibuprofen determination in pharmaceuticals and in real human urine samples.

Determination of widely used non-steroidal anti-inflammatory drugs in water samples by in situ derivatization, continuous hollow fiber liquid-phase microextraction and gas chromatography-flame ionization detector.

The aim of this study was to develop an analytical procedure which allows the quantification of pharmaceuticals in water at the ng L(-1) level. Hence, it is reported research on the application of a rapid, inexpensive and simple continuous hollow fiber liquid-phase micro extraction (CHF-LPME) for the pre-concentration and determination of non-steroidal anti-inflammatory drugs (NSAIDs), such as ibuprofen (IBP), naproxen (NAP), and ketoprofen (KEP), in wastewater. In this method, a 2.50 cm end sealed piece of a polypropylene hollow fiber was immersed into the organic solvent, octanol, for 30 s. After solvent impregnation with the pores of the fiber, the excess amounts of solvent were removed from inside the fiber, and 4.0 microL of octanol, as the acceptor phase, was injected into the fiber carefully. The fiber was settled using a microsyringe into a 10.0 mL glass test tube, and 20.00 mL of the aqueous solution (the donor phase), was circulated by a pump around it. After analyte extraction for an optimized period of time (20 min), 2 microL of the organic solvent was withdrawn into the microsyringe and injected into the GC-FID for further analysis. Finally, based on the optimized analytical conditions, the method was linear in the range of 2.5-500 ng L(-1). The limits of detection were 1-2 ng L(-1). Repeatability of this method on an intra-day scale was 3.4-10.2% (RSD%). NSAIDs have been detected in several municipal wastewater samples, and the concentration range was 9.0-19.0 ng L(-1).

Preparation and characterization of poly(methyltetradecylsiloxane) stationary phases immobilized by gamma radiation onto zirconized silica.

The preparation of stationary phases with enhanced chemical stability in alkaline eluents has been the principal objective of many chromatographers. New and improved silica substrates and advanced chemical modification methods are among the possibilities being investigated to reach this objective. The present work has evaluated these two possibilities for new stationary phases. First, the silica surface was modified by reaction with zirconium tetrabutoxide to produce zirconized silica particles having about 21% (w/w) of zirconium. Then poly(methyltetradecylsiloxane) (PMTDS) was immobilized onto this surface using different doses (50-120 kGy) of gamma radiation. These new phases were characterized using elemental analysis and infrared and solid-state (29)Si-nuclear magnetic resonance (NMR) spectroscopies. These new stationary phases presented column efficiencies of about 68,000 plates m(-1), symmetric peaks for apolar compounds and retention factors that depend on the irradiation dose and show improved stability in high pH mobile phases. The separation of several pharmaceuticals at pH 11 is presented.

Two-step liquid-liquid-liquid microextraction of nonsteroidal antiinflammatory drugs in wastewater.

A simple and novel two-step liquid-liquid-liquid microextraction technique combined with reversed-phase HPLC has been developed for the determination of the nonsteroidal antiinflammatory drugs ibuprofen and 2-(4-chlorophenoxy)-2-methylpropionic acid in wastewater samples. In the first step, the analytes were extracted from an acidified sample (donor solution) into 1-octanol immobilized in the pores of 10 pieces of polypropylene hollow fiber and further into a basic acceptor phase inside the hollow fiber channels. This first extraction step, using 0.01 M NaOH as the acceptor phase and 0.1 M HCl within the donor phase, had a 100% relative recovery with an enrichment factor of 100-fold. The extract in the first step was then adjusted to acidic condition with HCl. It now represented the donor phase for the second step of the extraction, using a single piece of hollow fiber, with 2 microL of 0.01 M NaOH solution as the acceptor phase. This analyte-enriched acceptor phase was subsequently withdrawn into a microsyringe and directly injected into an HPLC system for analysis. With this two-step microextraction, sensitivity enhancement of >15,000-fold could be obtained. Detection limits of < or =100 ng/L could be achieved for both compounds. The method was applied to the analysis of wastewater.

Directed control of electroosmotic flow in nonaqueous electrolytes using poly(ethylene glycol) coated capillaries.

Poly(ethylene glycol) (PEG)-coated capillaries exhibit unique properties in nonaqueous electrolytes. Immobilized PEG interacts significantly with different cations present in nonaqueous electrolytes. This can induce a positive surface charge on PEG-coated capillaries and results in an adjustable anodic electroosmotic flow (EOF) in nonaqueous electrolytes whereas a reduced cathodic EOF is observed in aqueous electrolytes. The EOF can reversibly be adjusted by the variation of the electrolyte constitution, namely the type of the solvent used and the nature and concentration of background cations. In methanol and especially in acetonitrile electrolytes the magnitude and also the direction of EOF is strongly dependent on the water content. Using different alkali metal cations, the EOF can be increased, reduced, or even reversed depending on the nature of the cation. The directed manipulation of EOF in methanolic electrolytes using PEG-coated capillaries was applied for optimization of nonaqueous capillary electrophoretic separations of acidic compounds with regard to reproducibility, resolution, and analysis time.

Liquid-phase microextraction and capillary electrophoresis of acidic drugs.

Vial liquid-phase microextraction (LPME) combined with capillary electrophoresis (CE) was evaluated for the determination of the acidic drugs ibuprofen, naproxen, and ketoprofen present in water samples and in human urine. The 2.5 mL samples containing the drugs were filled into conventional vials and subsequently acidified by 250 microL of 1-10 M HCl. Porous hollow fibers of polypropylene containing 25 microL of an aqueous solution of 0.01-0.1 M NaOH (acceptor solution) and with dihexyl ether immobilized in the pores of the wall were placed into each of the samples. The acidic drugs were extracted from the acidified sample solutions into the dihexyl ether phase, in the pores of the hollow fiber, and further into the alkaline acceptor solution forced by high partition coefficients. The drugs were extracted almost quantitatively (75-100% extraction efficiency) from the 2.5 mL samples and into the 25 microL acceptor solutions, providing 75-100 times preconcentration. The acceptor solutions were collected for automated CE analysis, which enabled the drugs to be detected down to the 1 ng/mL level.

Preparation, characterization, and dissolution studies of ibuprofen solid dispersions using polyethylene glycol (PEG), talc, and PEG-talc as dispersion carriers.

Solid dispersions of ibuprofen (IBF) were prepared by solvent evaporation method using polyethylene glycol 10000 (PEG), talc, and PEG-talc as dispersion carriers. The drug-carrier(s) interactions in the solid state were investigated using scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and x-ray diffraction analysis. Interactions in the solution were studied by performing dissolution experiments. No important and well-defined chemical interaction was found between the ingredients. The increase in the IBF dissolution rate from the solid dispersions with the carriers used in this study could be attributed to several factors such as improved wettability, local solubilization, and drug particle size reduction.