Titania-based fabric phase sorptive extraction approach for the determination of antiepileptic drugs, levetiracetam and lamotrigine in urine samples using high-performance liquid chromatography-photo diode array detection.

A new fabric phase sorptive extraction (FPSE) based separation and enrichment method was developed for sensitive determination of two antiepileptic drug molecules, Levetiracetam (LEV) and Lamotrigine (LTG). The analysis of these drug molecules was performed with high-performance liquid chromatography equipped with photodiode array detector (HPLC-PDA) after FPSE. HPLC analysis was carried out by using phenyl hexyl column, under isocratic conditions with the mobile phase composed of pH 3.0 buffer-acetonitrile (77:23 v: v). All parameters affecting the separation and enrichment process were studied and optimized step by step. The linear working range of the developed method was calculated in the range of 10.0-1000.0 ng mL-1 for both the drug molecules (LEV and LTG). The limits of detection of the method (LODs) were calculated as 2.72 and 3.64 ng mL-1, respectively. The relative standard deviation (%RSD) values of the developed method as an indicator of precision were varied between 4.0 and 7.3. The accuracy of the optimized FPSE method was determined by the recovery tests utilizing spiked samples and results were assessed in the range from 94.6 to 106.3%. This is the first application of sol-gel Titania polycaprolactone-polydimethylsiloxane-polycaprolactone (Ti-PCAP-PDMS-PCAP) based FPSE membrane in the determination of antiepileptic drug molecules.

A facile fabric phase sorptive extraction method for monitoring chloramphenicol residues in milk samples.

Determination of pharmaceutical active molecules in the biological matrices is crucial in various fields of clinical and pharmaceutical chemistry, e.g., in pharmacokinetic studies, developing new drugs, or therapeutic drug monitoring. Chloramphenicol (CP) is used for treating bacterial infections, and it's one of the first antibiotics synthetically manufactured on a large scale. Fabric phase sorptive extraction (FPSE) was used to determine Chloramphenicol antibiotic residues in milk samples by means of validated HPLC-DAD instrumentation. Cellulose fabric phases modified with polyethylene glycol-block-polypropylene glycol-block-polyethylene glycol triblock copolymer was synthesized using sol-gel synthesis approach (Sol-gel PEG-PPG-PEG) and used for batch-type fabric phase extractions. Experimental variables of the FPSE method for antibiotic molecules were investigated and optimized systematically. The HPLC analysis of chloramphenicol was performed using a C18 column, isocratic elution of trifluoroacetic acid (0.1%), methanol, and acetonitrile (17:53:30) with a flow rate of 1.0 mL/min. The linear range for the proposed method for chloramphenicol (r2 > 0.9982) was obtained in the range of 25.0-1000.0 ng/mL. The limit of detections (LOD) is 8.3 ng/mL, while RSDs% are below 4.1%. Finally, the developed method based on FPSE-HPLC-DAD was applied to milk samples to quantitatively determine antibiotic residues.

Use of newly synthetized magnetic Fe3O4 nanoparticles modified with hexadecyl trimethyl ammonium bromide for the sensitive analysis of antidepressant drugs, duloxetine and vilazodone in wastewater and urine samples.

A new enrichment and determination method involving HPLC-DAD analysis following magnetic solid-phase extraction (MSPE) was developed to detect trace amounts of two antidepressant drugs, namely, duloxetine (DUL) and vilazodone (VIL). In this study, a solid-phase sorbent was newly synthesized for use in the MSPE and its characterization was carried out by scanning electron microscopy (SEM), Fourier transform infrared (FTIR) spectroscopy, Raman spectroscopy and X-ray diffraction (XRD) techniques. In this proposed method, DUL and VIL molecules were enriched using newly synthesized magnetic-based nanoparticles in the presence of pH 10.0 buffer and desorbed with acetonitrile to a smaller volume prior to chromatographic determinations. After experimental variables were optimized, the VIL and DUL molecules were analyzed at wavelengths of 228 nm for DUL and 238 nm for VIL with isocratic elution of methanol, trifluoroacetic acid (TFA) (0.1%), and acetonitrile (10 : 60 : 30). The detection limits obtained under optimized conditions were 1.48 ng mL-1 and 1.43 ng mL-1, respectively. The %RSD values were found to be lower than 3.50% with model solutions containing 100 ng mL-1 (N:5). Finally, the developed method was successfully applied to wastewater samples and simulated urine samples, and quantitative results were obtained in the recovery experiments.

Sensitive determination of Fluoxetine and Citalopram antidepressants in urine and wastewater samples by liquid chromatography coupled with photodiode array detector.

A new analyte separation and preconcentration method for the trace determination of antidepressant drugs, Fluoxetine (FLU) and Citalopram (CIT) in urine and wastewaters, was developed based on HPLC-DAD analysis after magnetic solid phase extraction (MSPE). In the proposed method, FLU and CIT were retained on the newly synthetized magnetic sorbent (Fe3O4@PPy-GO) in the presence of buffer (pH 10.0) and then were desorbed into a lower volume of acetonitrile prior to the chromatographic determinations. Before HPLC analysis, all samples were filtered through a 0.45 µm PTFE filter. Experimental parameters such as interaction time, desorption solvent and volume, and pH were studied and optimized in order to establish the detection limit, linearity, enrichment factor and other analytical figures of merit under optimum operation conditions. In the developed method, FLU and CIT were analyzed by diode array detector at the corresponding maximum wavelengths of 227 and 238 nm, respectively, by using an isocratic elution of 60% pH 3.0 buffer, 30% acetonitrile, and 10% methanol. By using the optimum conditions, limit of detections for FLU and CIT were 1.58 and 1.43 ng mL-1, respectively, while the limit of quantifications was 4.82 and 4.71 ng mL-1, respectively. Relative standard deviations (RSD%) for triplicate analyses of model solutions containing 100 ng mL-1 target molecules were found to be less than 5.0 %. Finally, the method was successfully applied to urine (both simulated and real healthy human) and wastewater samples, and quantitative results were obtained in recovery experiments.

Fabric-Phase Sorptive Membrane Array As a Noninvasive In Vivo Sampling Device For Human Exposure To Different Compounds.

This study introduces an innovative device for the noninvasive sampling and chromatographic analysis of different compounds present in exhaled breath aerosol (EBA). The new sampling device, especially in light of the recent COVID-19 pandemic that forced many countries to impose mandatory facemasks, allows an easy monitoring of the subject's exposure to different compounds they may come in contact with, actively or passively. The project combines the advantages of a fabric-phase sorptive membrane (FPSM) as an in vivo sampling device with a validated LC-MS/MS screening procedure able to monitor more than 739 chemicals with an overall analysis time of 18 min. The project involves the noninvasive in vivo sampling of the EBA using an FPSM array inserted inside an FFP2 mask. The study involved 15 healthy volunteers, and no restrictions were imposed during or prior to the sampling process regarding the consumption of drinks, food, or drugs. The FPSM array-LC-MS/MS approach allowed us to effectively exploit the advantages of the two complementary procedures (the convenient sampling by an FPSM array and the rapid analysis by LC-MS/MS), obtaining a powerful and green tool to carry out rapid screening analyses for human exposure to different compounds. The flexible fabric substrate, the sponge-like porous architecture of the high-efficiency sol-gel sorbent coating, the availability of a large cache of sorbent coatings, including polar, nonpolar, mixed mode, and zwitterionic phases, the easy installation into the facemask, and the possibility of sampling without interrupting regular activities provide FPSMs unparalleled advantages over other sampling techniques, and their applications are expected to expand to many other clinical or toxicological studies.

Fabric phase sorptive extraction followed by HPLC-PDA detection for the monitoring of pirimicarb and fenitrothion pesticide residues.

A sensitive and readily deployable analytical method has been reported for the simultaneous analysis of pirimicarb (PRM) and fenitrothion (FEN) pesticide residues in environmental water samples using fabric phase sorptive extraction (FPSE) followed by high-performance liquid chromatography combined with photodiode array (HPLC-PDA) detector. Both pesticides were successfully determined with a Luna omega C18 column under isocratic elution mode by means of acetonitrile and phosphate buffer (pH 3.0) as the mobile phase. The quantitative data for PRM and FEN were obtained at their maximum wavelengths of 310 nm and 268 nm, respectively. The calibration plots were linear in the range 10.00-750.00 ng mL-1 and 10.00-900.00 ng mL-1 with correlation coefficient of 0.9984 and 0.9992 for PRM and FEN, respectively. Major FPSE experimental variables were investigated in detail, such as contact time with the FPSE membrane, pH and electrolyte concentration, and the volume and type of desorption solvent. Under the optimized conditions, the developed method showed satisfactory reproducibility with relative standard deviations less than 2.5% and low limits of detection of 2.98 and 3.02 ng mL-1 for PRM and FEN, respectively. The combined procedure allows for enhancement factors ranging from 88 to 113, with pre-concentration values of 125 for both analytes. The chromatographic resolutions were approx. 12 for FEN (retention factor of 3.52) and PRM (retention factor of 6.09), respectively, with a selectivity factor of 1.73. Finally, the validated method was successfully applied to real environmental water samples for the determination of these pesticides. Graphical abstract.

Novel MIPs-Parabens based SPE Stationary Phases Characterization and Application.

In this work, the synthesis, characterization, and application of novel parabens imprinted polymers as highly selective solid-phase extraction (SPE) sorbents have been reported. The imprinted polymers were created using sol-gel molecular imprinting process. All the seven parabens were considered herein in order to check the phase selectivity. By means of a validated HPLC-photodiode array detector (PDA) method all seven parabens were resolved in a single chromatographic run of 25 min. These SPE sorbents, in-house packed in SPE empty cartridges, were first characterized in terms of extraction capability, breakthrough volume, retention volume, hold-up volume, number of theoretical plates, and retention factor. Finally, the device was applied to a real urine sample to check the method feasibility on a very complex matrix. The new paraben imprinted SPE sorbents, not yet present in the literature, potentially encourage the development of novel molecularly imprinted polymers (MIPs) to enhance the extraction efficiency, and consequently the overall analytical performances, when the trace quantification is required.

FPSE-HPLC-PDA analysis of seven paraben residues in human whole blood, plasma, and urine.

This work describes a new, fast and sensitive method for the simultaneous determination of seven paraben residues including methyl paraben (MPB), ethyl paraben (EPB), propyl paraben (PPB), isopropyl paraben (iPPB), butyl paraben (BPB), isobutyl paraben (iBPB) and benzyl paraben (BzPB) in human whole blood, plasma and urine. The analytes were extracted from the biological matrices by an innovative technique, fabric phase sorptive extraction (FPSE) and subsequently analyzed by high-performance liquid chromatography (HPLC) coupled with photo diode array detector (PDA). The separation was carried out with a Spherisorb C18 column using methanol and phosphate buffer as mobile phases. Ketoprofen was used as the internal standard (IS). The analytical method has been validated according to the International Guidelines in terms of calibration curves for each biological matrix, precision (intra and inter day), trueness, selectivity, LODs, LOQs and ruggedness. Subsequently, the performance of the analytical method was evaluated on real biological samples. The proposed innovative method allows simultaneous analysis of seven paraben residues in three different biological matrices, including whole blood, plasma and urine and therefore it is easily applicable to monitor these substances in different biological samples. Furthermore, extraction technique used in this work is fast, easy to use and in accordance with the modern green analytical chemistry (GAC) principles.

Cloud point extraction and spectrophotometric determination of mercury species at trace levels in environmental samples.

A new micelle-mediated separation and preconcentration method was developed for ultra-trace quantities of mercury ions prior to spectrophotometric determination. The method is based on cloud point extraction (CPE) of Hg(II) ions with polyethylene glycol tert-octylphenyl ether (Triton X-114) in the presence of chelating agents such as 1-(2-pyridylazo)-2-naphthol (PAN) and 4-(2-thiazolylazo) resorcinol (TAR). Hg(II) ions react with both PAN and TAR in a surfactant solution yielding a hydrophobic complex at pH 9.0 and 8.0, respectively. The phase separation was accomplished by centrifugation for 5 min at 3500 rpm. The calibration graphs obtained from Hg(II)-PAN and Hg(II)-TAR complexes were linear in the concentration ranges of 10-1000 µg L(-1) and 50-2500 µg L(-1) with detection limits of 1.65 and 14.5 µg L(-1), respectively. The relative standard deviations (RSDs) were 1.85% and 2.35% in determinations of 25 and 250 µg L(-1) Hg(II), respectively. The interference effect of several ions were studied and seen commonly present ions in water samples had no significantly effect on determination of Hg(II). The developed methods were successfully applied to determine mercury concentrations in environmental water samples. The accuracy and validity of the proposed methods were tested by means of five replicate analyses of the certified standard materials such as QC Metal LL3 (VWR, drinking water) and IAEA W-4 (NIST, simulated fresh water).

Determination of ultra trace arsenic species in water samples by hydride generation atomic absorption spectrometry after cloud point extraction.

Cloud point extraction (CPE) methodology has successfully been employed for the preconcentration of ultra-trace arsenic species in aqueous samples prior to hydride generation atomic absorption spectrometry (HGAAS). As(III) has formed an ion-pairing complex with Pyronine B in presence of sodium dodecyl sulfate (SDS) at pH 10.0 and extracted into the non-ionic surfactant, polyethylene glycol tert-octylphenyl ether (Triton X-114). After phase separation, the surfactant-rich phase was diluted with 2 mL of 1M HCl and 0.5 mL of 3.0% (w/v) Antifoam A. Under the optimized conditions, a preconcentration factor of 60 and a detection limit of 0.008 µg L(-1) with a correlation coefficient of 0.9918 was obtained with a calibration curve in the range of 0.03-4.00 µg L(-1). The proposed preconcentration procedure was successfully applied to the determination of As(III) ions in certified standard water samples (TMDA-53.3 and NIST 1643e, a low level fortified standard for trace elements) and some real samples including natural drinking water and tap water samples.