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.

Overloading behavior of fenoprofen and naproxen as two model compounds on a non-porous silicon pillar array column.

In this study, the adsorption behavior of naproxen and fenoprofen as two model compounds on a non-porous pillar array column (NPAC) was investigated under reverse phase liquid chromatography conditions. Band profiles of both analytes were recorded in overloaded concentrations using 30% methanol/water (v/v) as the mobile phase. Breakthrough experiments under the same chromatographic condition were carried out to measure the adsorption isotherms. Single-component adsorption isotherm data were acquired by frontal analysis for each analyte. The isotherms were found to be concave upward and downward for naproxen and fenoprofen, respectively. To find the best agreement between the experimental data points and the adsorption isotherm models, the obtained isotherms were modeled using several isotherm models. The Langmuir-Freundlich and anti-Langmuir models provided the best fitting for fenoprofen and naproxen, respectively. The solute and stationary phase properties determine the appropriate model. Adsorbate-adsorbate interaction is important in the case of naproxen, while the adsorbate- adsorbent (stationary phase) plays the main role in retention of fenoprofen on the NPAC. The validity of the selected isotherm models were checked by comparing calculated and experimental band profiles and plate heights. An excellent agreement was observed for the whole concentration range of both analytes, which confirmed the accuracy of the selected models.

Simultaneous separation of naproxen and 6-O-desmethylnaproxen metabolite in saliva samples by liquid chromatography-tandem mass spectrometry: Pharmacokinetic study of naproxen alone and associated with esomeprazole.

Naproxen is a widely used non-steroidal anti-inflammatory drug for the control of postoperative inflammatory signs and symptoms in dentistry. Its association with esomeprazole has been widely studied and has yielded good results for the control of acute pain, even with the delayed absorption of naproxen owing to the presence of esomeprazole. To further understand the absorption, distribution, and metabolism of this drug alone and in combination with esomeprazole, we will analyze the pharmacokinetic parameters of naproxen and its major metabolite, 6-O-desmethylnaproxen, in saliva samples. A rapid, sensitive, and selective liquid chromatography-tandem mass spectrometric method for the simultaneous determination of naproxen and 6-O-desmethylnaproxen in saliva will be developed and validated. Sequential saliva samples from six patients will be analyzed before and 0.25, 0.5, 0.75, 1, 1.5, 2, 3, 4, 5, 6 8, 11, 24, 48, 72, and 96 h after the ingestion of one naproxen tablet (500 mg) and esomeprazole-associated naproxen tablets (500 + 20 mg), at two different times. After liquid-liquid extraction with ethyl acetate and HCl, the samples will be analyzed using an 8040 Triple Quadrupole Mass Spectrometer (Shimadzu, Kyoto, Japan). Separation of naproxen and its major metabolic products will be performed using a Shim-Pack XR-ODS 75Lx2.0 column and C18 pre-column (Shimadzu, Kyoto, Japan) at 40°C using a mixture of methanol and 10 mM ammonium acetate (70:30, v/v) with an injection flow of 0.3 mL/min. The total analytical run time will be 5 min. The detection and quantification of naproxen and its metabolite will be validated, which elucidate the pharmacokinetics of this drug, thereby contributing to its proper prescription for the medical and dental interventions that cause acute pain.

Preparation of poly(4-vinylpyridine)-functionalized magnetic Al-MOF for the removal of naproxen from aqueous solution.

In this work, a novel poly(4-vinylpyridine)-functionalized magnetic Al-MOF (Al-MOF-Fe3O4@P4VP) was synthesized successfully as an adsorbent for the adsorption of naproxen from aqueous solution. The resulting adsorbent was characterized with scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, vibrating sample magnetometer (VSM), BET surface area and X-ray photoelectron spectroscopy (XPS). Al-MOF-Fe3O4@P4VP had high surface area (123.68 m2/g), porous structure, rough surface and magnetic property. The maximum adsorption capacity of Al-MOF-Fe3O4@P4VP for naproxen could reach up to 31.67 mg/g and the adsorption process was well described by the Freundlich isotherm. The adsorption rate of naproxen on Al-MOF-Fe3O4@P4VP was very fast and the kinetics could be well modeled by the pseudo-second-order model. The adsorbent exhibited good adsorption ability even after ten adsorption-desorption cycles. Al-MOF-Fe3O4@P4VP had the characteristics of high removal efficiency, fast adsorption speed, good reusability and easy separation, making it a novel environment-friendly and effective magnetic nanomaterial in adsorbing naproxen from wastewater.

Kinetic resolution of racemic naproxen methyl ester by magnetic and non-magnetic cross-linked lipase aggregates.

In this study, the non-magnetic and the magnetic cross-linked enzyme aggregates (CLEAs) from Candida rugosa lipase were synthesized to catalyze the kinetic resolution reaction of naproxen methyl ester (NME). Magnetic iron oxide nanoparticles (MIONPs) were produced through co-precipitation method and their surfaces were modified by silanization reaction. The MIONPs were used as a platform to synthesize the magnetic CLEAs (M-CLEAs). The biocatalysts and MIONPs synthesized were characterized by FTIR spectroscopy and SEM analysis. The kinetic resolution of racemic NME was studied in aqueous buffer solution/isooctane biphasic system to compare the performance of M-CLEAs and CLEAs. The effects of reaction parameters such as temperature, pH, stirring rate on the enantiomeric excess of the substrate (ees%) were investigated in a batch reactor system. The activity recovery of CRL enzyme in CLEAs was higher than M-CLEAs. Compared with M-CLEAs, CLEAs biocatalysts had previously reached ees% values. Although both biocatalysts showed similar cavity structure from SEM analysis, the lower performance of M-CLEAs may be due to the different microenvironments of M-CLEAs from CLEAs. However, the reusability performance of M-CLEAs was higher than that of CLEAs. The optimal reaction conditions for M-CLEAs and CLEAs were found to be 37 °C, pH 7.5, and 300 rpm.

Electrospun NiFe layered double hydroxide/Nylon 6 composite nanofibers as a sorbent for micro solid phase extraction by packed sorbent of non-steroidal anti-inflammatory drugs in human blood.

In the present work, NiFe layered double hydroxide (LDH)/Nylon 6 composite nanofibers were prepared by electrospinning method and used as a new sorbent for the extraction and measurement of non-steroidal anti-inflammatory drugs (naproxen, mefenamic acid, and diclofenac) in whole blood samples. The method is based on micro solid phase extraction (µSPE) by packed sorbent followed by HPLC-UV analysis. Effective parameters on the extraction efficiency were optimized using a central composite design (CCD). In order to characterize the sorbent, Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), field emission scanning electron microscopy (FESEM), energy dispersive X-ray analysis (EDX) and elemental mapping were applied. The method was fully validated based on linearity, limits of detection (LOD) and quantification (LOQ), precision, and recovery. Under the optimal conditions, LOD values were found to be 25 ng mL-1 for naproxen and diclofenac and 15 ng mL-1 for mefenamic acid. A seven-point calibration curve was obtained in the range of 75-2000 ng mL-1 for naproxen and diclofenac and 50-2000 for mefenamic acid. The method showed good linearity with coefficients of determination, r2> 0.9962, for the three drugs. In the entire analytical range, the relative standard deviations (RSD%) were less than 8.1%. Finally, the efficiency of the method was investigated for the analysis of the target analytes in human blood samples, and the recoveries were obtained in the range of 90.7-109.8%.

Synthesis of N-doped TiO2/SiO2/Fe3O4 magnetic nanocomposites as a novel purple LED illumination-driven photocatalyst for photocatalytic and photoelectrocatalytic degradation of naproxen: optimization and different scavenger agents study.

N-doped TiO2/SiO2/Fe3O4 as a new magnetic photocatalyst that is active in visible light has been prepared by simple sol-gel method. The prepared samples were characterized by XRD, FESEM, EDX, TEM, BET, BJH, VSM, XPS, FT-IR, and DRS-UV/Vis analysis. The photocatalytic effect of synthesized samples on naproxen degradation was studied. The operational parameters were optimized through central composite design to achieve maximum efficiency. The optimum values for maximum efficiency were obtained at pH of 4.29, catalyst mass of 0.06 g, naproxen concentration of 9.33 mg L-1, and irradiation time of 217.06 min. At these optimum conditions, the maximum photocatalytic degradation percentages of naproxen were found to be 96.32% at desirability function value of 1.0. Coupling the electrical current with the photocatalytic process proved that the electrical current was considerably efficient in decreasing the degradation time of removing the naproxen from aqueous solutions. The photocatalytic activity of the nanoparticles was also studied under sunlight. Considering the results provided by UV-Vis spectrophotometry and total organic carbon, it was found that the prepared samples are extraordinarily efficient to degrade naproxen under both purple LED and solar lights. Furthermore, the effect of different scavenger agents on naproxen degradation has been studied.

Efficient degradation of refractory organic contaminants by zero-valent copper/hydroxylamine/peroxymonosulfate process.

Degradation of naproxen, bisphenol S and ibuprofen in a hydroxylamine enhanced zero-valent copper (Cu0) catalyzed peroxymonosulfate system was investigated for the first time. We found that hydroxylamine addition accelerated the reduction of Cu2+ to Cu+ as well as the corrosion of Cu0, and environmental friendly gas nitrogen was the main product of hydroxylamine. Additionally, hydroxyl radical and sulfate radical were identified to be the dominant reaction species by competitive experiments. The degradation of naproxen, bisphenol S and ibuprofen kept highly efficient in the pH range of 3.0-7.0 in Cu0/hydroxylamine/peroxymonosulfate process, with their degradation products identified by HPLC-MS, which showed that Cu0/hydroxylamine/peroxymonosulfate system could be an alternative to remove non-steroidal antiinflammatory drugs or plasticizers in wastewater. Furthermore, the effects of Cu0, hydroxylamine and peroxymonosulfate dosage were studied and optimized by a BBD based response surface model. This study provided a method to solve the disadvantages of Cu0/peroxymonosulfate systems, and gave a promising method to enhance the efficiencies of ZVMs activated system such as iron, cobalt and copper.

A nanohybrid composed of polyoxotungstate and graphene oxide for dispersive micro solid-phase extraction of non-steroidal anti-inflammatory drugs prior to their quantitation by HPLC.

A nanohybrid was prepared from polyoxotungstate anion and graphene oxide (POT/GO) and characterized in terms of porosity by applying Fourier transform infrared and transmission electron microscopy. The nanohybrid was applied as a sorbent for the dispersive micro solid-phase extraction of the non-steroidal anti-inflammatory drugs (NSAIDs) ibuprofen, diclofenac, and naproxen. Different types of sorbents were compared, and the POT/GO nanohybrid was found to have the best adsorption affinity. The NSAIDs were quantified via HPLC with UV detection. Under the optimum conditions, the limits of detection (at an S/N ratio of 3) range between 0.02-0.03 ng.mL-1, and the linear response ranges extend from 0.08-200 ng.mL-1, respectively. The relative standard deviations (RSDs) for five replicates at three concentration levels (0.1, 5 and 100 ng.mL-1) of NSAIDs ranged from 4.1 to 6.1%. The applicability of the method was confirmed by analyzing spiked real water samples, and satisfactory results were obtained, with recoveries between 95.6 and 99.6%. Graphical abstract Schematic representation of the polyoxotungstate/graphene oxide nanohybrid preparation.

Competitive Protein Binding Assay of Naproxen by Human Serum Albumin Functionalized Silicon Dioxide Nanoparticles.

We have developed a new competitive protein binding assay (CPBA) based on human serum albumin functionalized silicon dioxide nanoparticles (nano-SiO2-HSA) that can be used for naproxen determination in urine. Compared with a conventional multi-well reaction plate, nano-SiO2 with a high surface-area-to-volume ratio could be introduced as a stationary phase, markedly improving the analytical performance. Nano-SiO2-HSA and horseradish peroxidase-labeled-naproxen (HRP-naproxen) were prepared for the present CPBA method. In this study, a direct competitive binding to nano-SiO2-HSAwas performed between the free naproxen in the sample and HRP-naproxen. Thus, the catalytic color reactions were investigated on an HRP/3,3'5,5'-tetramethylbenzidine (TMB)/H2O2 system by the HRP-naproxen/nano-SiO2-HSA composite for quantitative measurement via an ultraviolet spectrophotometer. A series of validation experiments indicated that our proposed methods can be applied satisfactorily to the determination of naproxen in urine samples. As a proof of principle, the newly developed nano-CPBA method for the quantification of naproxen in urine can be expected to have the advantages of low costs, fast speed, high accuracy, and relatively simple instrument requirements. Our method could be capable of expanding the analytical applications of nanomaterials and of determining other small-molecule compounds from various biological samples.

Dispersive Liquid-Liquid Microextraction Based on Solidification of Floating Organic Drop with Central Composite Design for the Spectrofluorometric Determination of Naproxen.

A quick, simple and efficient method for extraction, preconcentration, and determination of naproxen in water and plasma specimens with acceptable recovery by dispersive liquid-liquid microextraction based on solidified floating organic drop with spectrofluorimetry is presented. Various parameters affecting the extraction efficiency are optimized by the Central Composite Design. Moreover, under optimal conditions (120 µL 1-Undecanol with 1 mL Ethanol, pH = 3.5, 2 mL KCl 10% solution), the calibration curve was linear in the range 10.0-120.0 ng/mL. Finally, for naproxen, the detection limit was 2.4 ng/mL.

Ionisable emerging pharmaceutical adsorption onto microwave functionalised biochar derived from novel lignocellulosic waste biomass.

Functionalised biochar (WpOH) was prepared from wild plum kernels using simultaneous pyrolysis and microwave potassium hydroxide (KOH) functionalisation. This was then applied to the removal (from water) of an ionisable pharmaceutical - naproxen (NPX). Characterization of the WpOH was carried out using pHpzc, SEM/EDX, BET, FTIR, XRD, and the principle adsorption mechanisms were thoroughly studied. A pseudo-second order kinetic model best described the reaction kinetic behaviour, and the Langmuir isotherm provided the best fit to the results. The maximum adsorptive interaction (73.14 mg/g) occurred between pH 5 and 7 through electrostatic attraction (the main interaction mechanism) between the negatively charged NPX and the positively charged WpOH functional groups. In addition, hydrogen-bonding and electron-donor-acceptor (EDA) interactions were important. In a competitive study, using NPX and carbamazepine (a basic/amphoteric drug), the different nature/structure of the two compounds resulted in slight competitive adsorption. The results demonstrate the potential for wild plum kernel biochar to be used in the efficient removal of emerging contaminants such as pharmaceuticals from water.

Chitosan tailor-made membranes as biopolymeric support for electromembrane extraction.

A chitosan membrane composed by 60% (w/w) chitosan and 40% (w/w) Aliquat®336 has been proposed as a new biopolymeric support for electromembrane extraction. The new support has been characterized by Scanning Electron Microscopy, resulting a 30-35 µm thickness. Amoxicillin, nicotinic acid, hippuric acid, salicylic acid, anthranilic acid, ketoprofen, naproxen and ibuprofen have been successfully extracted using the proposed support. Better enrichment factors were obtained for the acidic polar analytes than for the non-steroidal anti-inflammatory compounds (ranging from 118 for hippuric acid and 20 for ibuprofen). Electromembrane extraction was developed applying a DC voltage of 100 V, 1-octanol as supported liquid membrane and 20 min of extraction. The target analytes have also been satisfactorily extracted from human urine samples, providing high extraction efficiencies. The chitosan membrane is presented as a promising alternative for supporting liquid membrane compared to commonly used materials for this purpose.

Residual detection of naproxen, methyltestosterone and 17α-hydroxyprogesterone caproate in aquatic products by simple liquid-liquid extraction method coupled with liquid chromatography-tandem mass spectrometry.

In the present study, we aimed to develop a reliable screening method based on liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS) for the detection and quantification of naproxen, methyltestosterone and 17α-hydroxyprogesterone caproate residues. The target analytes were extracted from samples of eel, flatfish and shrimp using acetonitrile with 1% acetic acid, followed by liquid-liquid purification with n-hexane. Chromatographic separation was achieved on a reversed-phase analytical column using 0.1% formic acid containing 10 mm ammonium formate in distilled water (A) and methanol (B) as mobile phases. All the matrix-matched calibration curves were linear (R2 ≥ 0.99) over the concentration range of the tested analytes. Recovery at three spiking levels (0.005, 0.01 and 0.02 mg/kg) ranged from 68 to 117% with intra- and inter-day precisions <10%. Five market samples for each matrix (eel, flatfish and shrimp) were collected and tested for method application. In summary, the proposed method is feasible to screen and quantify the analytes with high selectivity in aquatic food products meant for human consumption.

Physical-chemical interactions between pharmaceuticals and biochar in synthetic and real urine.

This research advances the knowledge of the pharmaceutical removal interactions by biochar in synthetic and real urine through the use of reference adsorbents and adsorbate probes. Earlier work has combined biochar and urine for pharmaceutical removal, however, the interactions that influence adsorption are unknown. In this study, bamboo biochar and softwood biochar were chosen as the representative materials and the model pharmaceuticals were naproxen and paracetamol. To further investigate the physical-chemical interactions, two nonpolar adsorbates, para-xylene and dimethylnaphthalene, were tested. Graphite and anion exchange resin, were used to isolate van der Waals and electrostatic interactions, respectively. Experimental kinetic and equilibrium data were fit to multiple adsorption models where the pseudo-second order and Freundlich exhibited the best fit, respectively. The Freundlich and Langmuir parameters had similar trends showing that softwood had the highest adsorption capacity. The model parameters indicated higher selectivity for nonpolar para-xylene and dimethylnaphthalene by graphite and polar paracetamol and naproxen by softwood biochar. The decreasing trend of importance of key interactions for pharmaceutical sorption to biochar are: van der Waals > hydrogen bonding > electrostatic interactions. No statistically significant difference was found between urine age (fresh vs. hydrolyzed) and pharmaceutical removal; however, the urine matrix (synthetic vs. synthetic with metabolites vs. real urine) did show a statistically significant difference on pharmaceutical removal where synthetic urine had comparatively greater adsorption. As constituents (i.e., metabolites) were added to urine matrices, reduced adsorption of pharmaceuticals was observed, indicating that adsorption processes should be tested in real urine for accuracy.

Solid-phase extraction of drugs with cuttlefish bone powder as a sorbent.

We investigated cuttlefish bone powder for the solid-phase extraction of naproxen, ibuprofen, and carbamazepine. The basic principles controlling the extraction are presented to aid in the choice of the nature and quantity of the extracting phase according to the sample matrix and the solute properties, based on the mechanisms of phase retention. Their retention mechanism is based on hydrogen bonding and electrostatic interactions. The results show a significant recovery rate for the three drugs, selectivity, and low cost. The method has successfully reduced the amount of tested pharmaceuticals with recoveries >87% at pH 4.

[Chlorination of Naproxen: Removal, Transformation and Risk Assessment].

The by-products produced during chlorination of pharmaceutically active compounds (PhACs) have created widespread public concern. Chlorination of a typical PhAC, naproxen (NAP), was studied. NAP chlorination parameters, intermediates identification, chlorination mechanism, and risk assessment during chlorination process have also been discussed. The results showed that NAP chlorination could fit well with the fist-order kinetics. The rate of removal and rate constants of NAP chlorination decreased with increasing initial NAP concentration and ammonium dosage, while these values increased with increasing initial free chlorine concentration. Acidic condition of the solution could significantly promote NAP chlorination. Five intermediates were identified by HPLC-MS/MS, and the mechanism of NAP chlorination was also put forward. Vibrio fischeri toxicity analysis and ESCOAR prediction indicated that higher toxicity intermediates were produced during NAP chlorination, which pose a potential threat to drinking water safety.

Use of Polymer Inclusion Membranes (PIMs) as support for electromembrane extraction of non-steroidal anti-inflammatory drugs and highly polar acidic drugs.

The use of polymer inclusion membranes (PIMs) as support of 1-octanol liquid membrane in electromembrane extraction (EME) procedure is proposed. Synthesis of PIMs were optimized to a composition of 29% (w/w) of cellulose triacetate as base polymer and 71% (w/w) of Aliquat®336 as cationic carrier. Flat PIMs of 25µm thickness and 6mm diameter were used. EME protocol was implemented for the simultaneous extraction of four non-steroidal anti-inflammatory drugs (NSAIDs) (salicylic acid, ketoprofen, naproxen and ibuprofen) and four highly polar acidic drugs (anthranilic acid, nicotinic acid, amoxicillin and hippuric acid). Posterior HPLC separation of the extracted analytes was developed with diode array detection. Recoveries in the 81-34% range were obtained. EME procedure was applied to human urine samples.

A review on chiral separation by counter-current chromatography: Development, applications and future outlook.

Chiral separation has been a remarkably active area of research over the past long time and it still stays that way. Over the last few decades, counter-current chromatography (CCC) was successfully applied to the field of chiral separation. It provides an attractive approach to obtain pure enantiomer, particularly in preparative application because of its unique advantages of high load capacity, low solvent consumption and easy scale-up. The last several years great strides have been made in chiral separation by CCC, ranging from novel elution modes such as recycling elution mode and multiple dual mode elution to more specialized approaches such as pH-zone-refining and biphasic chiral recognition technologies. These developments have greatly improved the resolution of enantiomers and promoted the application of CCC in the field of chiral separation. Although not as popular as its application to the field of separation of natural product, the development of chiral separation by CCC should not be underrated. In this review article, we refer to the development, applications and future outlook of chiral separation by CCC, with emphasis on topics of its history, mechanism, advantages, limitations, current development and challenges. Meanwhile, its orientation of continued evolution and future outlook also have been discussed. While some scientific and technological problems have not yet been solved thoroughly, chiral separation by CCC has demonstrated potential advantages and prospects in this field and has good chance at preparative enantioseparation.

Volumetric absorptive microsampling combined with impact-assisted extraction for hematocrit effect free assays.

AIM: Volumetric absorptive microsampling (VAMS) is a recent technology available for sampling and analyzing low blood volume. The present work describes the utilization of VAMS for the quantitation of naproxen and ritonavir in human blood using a novel bead-based impact-assisted extraction (IAE) procedure. RESULTS: Sampling volume accuracy of the VAMS device was independent of the blood hematocrit (HCT) level, however analyte recovery decreased with increasing HCT when extracted using ultrasonication. In contrast, IAE was unaffected by HCT, resulting in quantitative recovery for all levels evaluated. Precision and accuracy batches, as well as matrix effect evaluation, met acceptance criteria. CONCLUSION: The IAE procedure coupled with VAMS is immune to HCT biases affecting sampling volume and recovery.