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In current paper, a new advanced modification of fabric phase sorptive extraction is introduced for the first time. This advantageous configuration that integrates the stirring and extraction mechanism into a single sample preparation device was originated by equally considering the beneficial role of the increase of extraction kinetics and more specifically of diffusion on the extraction efficiency of the equilibrium based microextraction techniques and the need for integrating and unite processes for better promotion and implementation of the principles of Green Analytical Chemistry. The resulted magnet integrated fabric phase sorptive extraction (MI-FPSE) device was the spearhead to develop a new analytical methodology for the determination of selected very common endocrine disrupting chemicals as model analytes in human urine by high-performance liquid chromatography-photodiode array analysis. More specifically, the sol-gel Carbowax 20 M coated on hydrophilic cellulose fabric substrate, MI-FPSE device was efficiently employed for the establishment of a new extraction protocol before the chromatographic determination. The sample preparation workflow was methodically optimized in terms of the elution solvent mixture, the volume of the sample, the extraction and the elution time, the stirring speed during the extraction, the ionic strength, and the pH of the sample matrix. The chromatographic separation was performed on a Spherisorb C18 column and a gradient elution program within 14 minutes. Mobile phase consisted of 0.05 ammonium acetate aqueous solution and acetonitrile. The method was validated towards linearity, sensitivity, selectivity, precision, accuracy, and stability. LOD and LOQ ranged between 1.05-1.80 and 3.5-6.0 ng/mL, while %RSD values were found lower than 9.0% in all cases. The method was efficiently applied to the bioanalysis of real samples. All the chosen EDCs were measured at high detection levels. The new MI-FPSE device has demonstrated its performance superiority as a magnet integrated stand-alone extraction device and could be considered as a significant improvement in the field of analytical/bioanalytical sample preparation., Competing Interests: Declaration of Competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

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.

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., (Copyright © 2019 Elsevier B.V. All rights reserved.)

In this report, a polytetrahydrofuran-coated polyester fabric phase sorptive extraction (FPSE) for the determination of doxycycline in human urine was described. The sol-gel polytetrahydrofuran sorbent proved to be superior against other sol-gel coated cellulose and polyester membranes tested. The effect of the extraction parameters including membrane surface area, sample pH and volume, salt concentration, extraction time, stirring rate, etc., on the extraction efficiency of the analyte was studied using the "one-factor-at-a-time" (OFAT) and Box–Behnken design approaches. The analytical method proposed was validated in compliance with FDA guidelines for bioanalytical procedures. The method was linear in the determination range of 100–5000 ng/mL with the determination coefficient of 0.9953. The limit of detection (LOD) and the lower limit of quantification for doxycycline was 17 and 100 ng/mL, respectively. The relative recoveries for intra-day and inter-day studies ranged from 98.5–112.2% and 89.6–96.8%, respectively. The relative standard deviation was lower than 14.7% in all cases, exhibiting good precision. The sol-gel polytetrahydrofuran-modified FPSE membranes were reusable for at least 30 times. The greenness of the developed method was evaluated using Sample Preparation Metric of Sustainability (SPMS) and Blue Applicability Grade Index (BAGI) metric tools. Finally, the analytical scheme was successfully employed for the quantitation of urinary doxycycline collected at various time points following the administration of doxycycline-containing tablets. [ABSTRACT FROM AUTHOR]

A sol–gel Carbowax 20 M/3-[(3-Cholamidopropyl) dimethyl ammonio]-1-propanesulfonate composite sorbent-based capsule phase microextraction device has been fabricated and characterized for the determination of four statins (pravastatin, rosuvastatin, pitavastatin, and atorvastatin) in human urine. The presence of ionizable carboxyl functional groups in statins requires pH adjustment of the sample matrix to ensure that the target molecules are in their protonated form (pH should be 2 units below their pKa values) which not only is cumbersome but also risks unintended contamination of the sample. This challenge was addressed by introducing zwitterionic ionic liquid in addition to neutral, polar Carbowax 20 M polymer in the sol–gel-derived composite sorbent. As such, the composite zwitterionic multi-modal sorbent can simultaneously extract neutral, cationic, and anionic species. This particular attribute of the composite sorbent eliminates the necessity of the matrix pH adjustment and consequently simplifies the overall sample preparation workflow. Various experimental parameters such as the sample amount, extraction time, salt addition, stirring rate, and elution solvent type that may affect the extraction performance of the statins were investigated using a central composite design and the one-parameter-at-a-time approach. The analytes and the internal standard were separated on a C18 column with gradient elution using phosphate buffer (20 mM, pH 3) and acetonitrile as mobile phase. The analytes were detected at 237 nm. The method was validated, and linearity was observed in the range 0.10–2.0 μg mL−1 for all compounds. The method precision was better 9.9% and 10.4% for intra-day and inter-day, respectively, while the relative recoveries were acceptable, ranging between 83.4 and 116% in all cases. Method greenness was assessed using the ComplexGAPI index. Finally, the method's applicability was demonstrated in the determination of the statins in authentic human urine after oral administration of pitavastatin and rosuvastatin-containing tablets. [ABSTRACT FROM AUTHOR]

In this work, a method for the simultaneous determination of four resin monomers: Bisphenol A, bisphenol A methacrylate glycidate, triethyleneglycol-dimethacrylate, and urethane dimethacrylate, from human urine using magnet integrated fabric phase sorptive extraction (MI-FPSE), followed by high performance liquid chromatography (HPLC) diode array detection (HPLC-DAD), is presented. MI-FPSE is a novel configuration of FPSE that incorporates the stirring and extraction mechanism into one device, resulting in an improved extraction kinetic factor. FPSE is a green sample preparation technique that uses a flexible surface, such as cellulose, coated with a polymeric material using sol–gel technology. Poly(tetrahydrofuran) (PTHF) material was selected, due to its higher efficiency in terms of recovery rate among the studied MI-FPSE membranes. Optimization of the extraction process was performed based on several extraction and elution parameters. The method was validated for its linearity, selectivity, accuracy, precision, and stability of the samples. For the four compounds, the LOD and LOQ were 0.170 ng/μL and 0.050 ng/μL, respectively. The relative standard deviation of the method was less than 9.8% and 11.9%, for the within-day and between-day precision, respectively. The relative recoveries were between 85.6 and 105.2% in all cases, showing a good accuracy. The effectiveness of the proposed method was confirmed through successful application to the bioanalysis of real urine samples. [ABSTRACT FROM AUTHOR]

Herein, a fabric phase sorptive extraction-based scheme was reported for the determination of amphotericin B in human urine. The developed method allowed the direct extraction of the analyte from the biological matrix with improved selectivity, repeatability and recovery. Due to the membrane's engineered affinity towards the analyte, extraction equilibrium was achieved in 30 min. Moreover, no additional sample pretreatment was required due to the high permeability of the FPSE membrane and the small volume of eluting solvent required for quantitative back-extraction of the analytes. The hydrophobic sol–gel polydimethylphenylsiloxane (sol–gel PDMDPheS) coated membrane provided the optimum extraction performance. Important parameters that affect the extraction efficiency (such as sample volume, extraction time, membrane size, stirring rate, ion strength, elution solvent and time) were thoroughly investigated. The analyte was separated from the internal standard (nimesulide) and endogenous compounds of the human urine using a gradient elution program. The proposed assay was linear within the range of 0.10–10.0 μg mL−1 while the relative standard deviation of the repeatability (sr) and within-laboratory reproducibility (sR) were less than 12.7% in all cases. The method exhibited good accuracy which varied between 88.1 to 110.3%. The developed method was successfully applied for the monitoring of amphotericin B concentration in human urine. [ABSTRACT FROM AUTHOR]

Fabric phase sorptive extraction (FPSE) has become a popular sorptive-based microextraction technique for the rapid analysis of a wide variety of analytes in complex matrices. The present study describes a simple and green analytical protocol based on in-matrix methyl chloroformate (MCF) derivatization of non-steroidal anti-inflammatory (NSAID) drugs in urine samples followed by FPSE and gas chromatography-mass spectrometry (GC-MS) analysis. Use of MCF as derivatizing reagent saves substantial amounts of time, reagent and energy, and can be directly performed in aqueous samples without any sample pre-treatment. The derivatized analytes were extracted using sol–gel Carbowax 20M coated FPSE membrane and eluted in 0.5 mL of MeOH for GC-MS analysis. A chemometric design of experiment-based approach was utilized comprising a Placket–Burman design (PBD) and central composite design (CCD) for screening and optimization of significant variables of derivatization and FPSE protocol, respectively. Under optimized conditions, the proposed FPSE-GC-MS method exhibited good linearity in the range of 0.1–10 µg mL−1 with coefficients of determination (R2) in the range of 0.998–0.999. The intra-day and inter-day precisions for the proposed method were lower than <7% and <10%, respectively. The developed method has been successfully applied to the determination of NSAIDs in urine samples of patients under their medication. Finally, the green character of the proposed method was evaluated using ComplexGAPI tool. The proposed method will pave the way for simper analysis of polar drugs by FPSE-GC-MS. [ABSTRACT FROM AUTHOR]

An improved fabric‐phase sorptive extraction (FPSE) protocol has been developed and validated herein for the simple, fast, sensitive and green determination of seven parabens—methyl paraben, ethyl paraben, propyl paraben, butyl paraben, isopropyl paraben, isobutyl paraben and benzyl paraben—in human urine samples by HPLC–DAD. The mobile phase consisted of ammonium acetate (0.05 m) and acetonitrile, while total analysis time was 13.2 min. Sol–gel poly (tetrahydrofuran) coated FPSE membrane resulted in optimum extraction sensitivity for the seven parabens. The novel FPSE medium as well as the improved and faster sample preparation procedure resulted in lower limit of detection and quantitation values in comparison with previously reported methods. The separation was carried out using an RP‐HPLC method with a Spherisorb C18 column and a flow rate of 1.4 ml/min. The validation of the analytical method was carried out by means of linearity, precision, accuracy, selectivity, sensitivity and robustness. For all seven parabens, the limits of detection and quantitation were 0.003 and 0.01 μg/ml, respectively. Relative recovery rates were between 86.3 and 104%, while RSD values were <12.6 and 19.3% for within‐ and between‐day repeatability, respectively. The method was subsequently applied to real human urine samples. [ABSTRACT FROM AUTHOR]

An innovative fabric phase sorptive extraction-high performance liquid chromatography-diode array detection (FPSE-HPLC-DAD) method is developed and validated herein for the simultaneous extraction and analysis of five common antidepressants (venlafaxine, paroxetine, fluoxetine, amitriptyline, clomipramine) in human urine samples. Separation was obtained using a reverse phase column LiChroCART-LiChrospher®100 RP-8e (5 μm, 250 × 4 mm) with diode array detection monitoring at 235 nm. Gradient elution was applied at a flow rate of 1.2 mL/min with a mobile phase that consisted of acetonitrile and ammonium acetate (0.05 M). Fabric Phase Sorptive Extraction was evaluated for the first time with regards to the extraction of the examined antidepressants from human urine and proved to be a rapid, simple, environmentally friendly, efficient, and selective sample preparation approach. Sol-gel graphene sorbent, coated on cellulose FPSE media, were the most efficient among other with different polarities. The absolute recovery values were 25.5% for venlafaxine, 33.9% for paroxetine, 67.0% for fluoxetine, 43.0% for amitriptyline and 29.0% for clomipramine, while relative recoveries were higher than 90%. The developed method provides satisfactory limit of detection 0.15 ng/μL. • Innovative Fabric phase sorptive extraction is applied in biosamples. • Isolation of five antidepressants from urine is achieved. • Fast and simple sorptive extraction method is developed herein. • Green analytical principles are satisfied by proposed method. [ABSTRACT FROM AUTHOR]

This paper reports a novel fabric phase sorptive extraction-high performance liquid chromatography-photodiode array detection (FPSE-HPLC-PDA) method for the simultaneous extraction and analysis of three drug residues (ciprofloxacin, sulfasalazine, and cortisone) in human whole blood, plasma, and urine samples, generally administered in human patients to treat inflammatory bowel disease (IBD). The drugs of interest were well resolved using a Luna C 18 column (250 mm × 4.6 mm; 5 μm particle size) in gradient elution mode within 20 min. The analytical method was optimized and validated in the range 0.05–10 μg/mL for whole blood, 0.25–10 μg/mL for human plasma, and 0.10–10 μg/mL for human urine. Blank human whole blood, plasma, and urine were used as the sample matrix for the method development and validation; while methyl- p -hydroxybenzoate was used as the internal standard (IS). Weighted-matrix matched standard calibration curves showed a good linearity up to a concentration of 10 μg/mL. The intra- and inter-day accuracy values (precision and trueness) were found in the range from −10.9% to 12.3%, and the performances of the validated FPSE-HPLC-PDA were further tested on real IBD patient samples. This is the first FPSE procedure applied simultaneously to whole blood, plasma, and urine samples for the determination of residual IBD drugs, which possess a wide range of polarity (logP values ranging from 2.30 for Ciprofloxacin, to 1.66 for Cortisone, and 2.92 for Sulfasalazine). The new approach exhibits high potential for immediate adoptation as a rapid, robust and green analytical tool for future clinical and pharmaceutical applications. [ABSTRACT FROM AUTHOR]

[Display omitted] • The proposed CPME scheme can be easily used in bioanalysis. • Monolithic sol–gel polyethylene glycol was used as sorbent in microextraction capsule. • Accuracy profiles were utilized for method validation. Herein, a monolithic sol–gel polyethylene glycol-based sorbent (PEG) has been in situ synthesized within two conjoined porous polypropylene microextraction capsules and subsequently applied for the microextraction of triazoles and benzimidazoles drugs from human urine. A cylindrical bar magnet was incorporated into the device, offering the ability of spinning when it is placed in a magnetic field resulting in a stand-alone "all-in-one" extraction device. Among other sorbent tested, the sol–gel PEG 300 coated microextraction capsules were found to be beneficial for the extraction of the target analytes. The analysis of the drugs was performed using high-performance liquid chromatography and photodiode array detection (HPLC-PDA). Detailed investigation of the main parameters that affect the extraction performance (i.e., dimensions of the microextraction capsules, sample volume, extraction time, ionic strength, stirring rate, elution time, type of eluent, volume of eluent) was conducted to find the optimum conditions for the extraction procedure. The method was thoroughly validated using the total-error concept. The β -expectation tolerance intervals did not exceed the acceptance criteria of ± 15% meaning that 95% of future results will be included in the defined bias limits. The lower limits of quantitation (LLOQs) of the method were adequate, corresponding to 0.1 and 0.25 μg mL−1 for triazoles and benzimidazoles, respectively. The mean analytical bias in the spiking levels was satisfactory, ranging between ─ 3.8 to + 6.7 % while the relative standard deviation (RSD) was lower than 5.6 %. Finally, the sol–gel PEG 300 encapsulated microextraction capsules were found to be reusable for at least 15 extraction cycles. The developed approach was successfully applied in the analysis of the selected drugs in urine samples. [ABSTRACT FROM AUTHOR]

[Display omitted] • A FPSE was developed for the isolation of adamantine analogues. • Fast and direct extraction of the biological matrices in less than 20 min. • Sensitive determination of the analytes in biological samples using UHPLC-MS/MS. Herein, fabric phase sorptive extraction – a member of sorbent-based microextraction family – is utilized for the rapid isolation of selected antiviral drugs namely amantadine, memantine and rimantadine from human urine prior to their analysis with UHPLC-MS/MS. Fabric phase sorptive extraction membrane coated with sol–gel sorbent coated poly(propylene glycol)-poly(ethylene glycol)-poly(propylene glycol) sorbent was identified as the optimum extraction membrane for the target analytes. Due to the engineered affinity of the fabric phase sorptive extraction towards the analytes, the extraction proceeds in relatively short time (20 min) while its high permeability permits the extraction of biological samples without any other pretreatment. Following selection of the appropriate membrane, significant parameters including extraction time, sample volume, membrane size, elution solvent, etc were optimized. The drugs were analyzed under positive electrospray ionization using multi-reaction monitoring mode. The method was linear in the range of 5 – 100 ng mL−1 by constructing weighted matrix-matched calibration curves. The intra-day and inter-day accuracy were ranged between – 18.7 to + 18.1% and – 18.3 to + 16.1%, respectively. The precision of the method (intra-day, inter-day) were less than 18.5 % in all cases. The method limits of detection were in the range of 0.2 – 0.8 ng mL−1 while the lower limit of quantitation was set at 5 ng mL−1 for all analytes. The developed analytical scheme was efficiently applied to the analysis of the target drugs in human urine and could be adopted as a rapid and robust green analytical tool for clinical applications. [ABSTRACT FROM AUTHOR]

[Display omitted] • The proposed CPME scheme can be easily used in routine bioanalysis. • CPME is an interesting alternative to traditional preparation approaches. • Accuracy profiles were implemented for method validation. • A sol–gel polytetrahydrofuran sorbent was used for the extraction of ibuprofen. Undoubtedly, the exploration of new sample preparation techniques is in the forefront of research in bioanalysis. Capsule phase microextraction (CPME) is a recently introduced extraction technique based on the sol–gel sorbents which are incorporated into a porous tubular polymeric membrane. Herein, we exploited the advantageous features of CPME in biological matrices by utilizing sol–gel poly(tetrahydrofuran) (sol–gel PTHF) sorbent in CPME device for the extraction of ibuprofen (model compound) from urine samples. In CPME, both filtration and stirring mechanisms are merged into a unified extraction device allowing the direct extraction of the analytes from biological matrix without any pretreatment process. The main parameters (sample pH and volume, adsorption and elution time, volume of elution volume etc.) affecting the extraction efficiency of the CPME method were systematically investigated and optimized. The determination of ibuprofen was performed using UHPLC-PDA. The reported method was validated in terms of linearity, selectivity, accuracy, and precision, limit of detection and limit of quantification using the total error concept. Employing the accuracy profiles – as a graphical decision-making tool – the β -expectation tolerance intervals did not exceed the acceptance criteria of ± 15% meaning that 95% of future results will be included in the defined bias limits. The limit of detection (LOD) of the method was adequate, corresponding to 14 ng mL−1. The relative bias in the spiking levels was acceptable being in the range of −4.1 and +3.9% while the relative standard deviation (RSD) was lower than 4.6%. Moreover, the sol–gel sorbent integrated microextraction capsules were found to be reusable for at least 20 extraction cycles. The CPME protocol was successfully employed for the analysis of real urine samples obtained by a healthy volunteer. Finally, the developed CPME method was characterized by absence of matrix-effect and thus its application can be potentially expanded to other types of biological matrices. [ABSTRACT FROM AUTHOR]

• Ti-based fabric phase membranes were used in FPSE of LEV and LTG drugs for fist times. • The application of methods was shown in model solutions and urine samples. • Sensitive analysis of target molecules was achieved at trace levels with the proposed method. • The used materials successively passed the applied tests for reusability and recovery. 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. [ABSTRACT FROM AUTHOR]

This paper reports a novel fabric phase sorptive extraction-high performance liquid chromatography-photodiode array detection (FPSE-HPLC-PDA) method for the simultaneous extraction and analysis of six benzophenone derivative UV filters including benzophenone (BZ); 5-benzoyl-4-hydroxy-methoxybenzenesulfonic acid (BP-4); bis(4-hydroxyphenyl)methanone (4-DHB); bis(2,4-dihydroxyphenyl)methanone (BP-2); (2,4-dihydroxybenzophenone) (BP-1) and 2,2′-dihydroxy-4-methoxybenzophenone (DHMB) in human whole blood, plasma and urine samples. Chromatographic separation method was conducted using a Spherisorb ODS 1 (C 18) column in isocratic elution mode with a run time <25 min. The FPSE-HPLC-PDA method was validated in the range from 0.1 to 10 μg/mL for all the UV filter compounds. Propyl 4-hydroxybenzoate (also known as propyl paraben) was used as the internal standard (IS). The limit of quantification was found to be 0.1 μg/mL and the weighted-matrix matched standard calibration curves of six UV filters showed a good linearity up to a concentration of 10 μg/mL. This new approach exhibits high potential for direct adaptation as a rapid, robust and green analytical tool for several applications, e.g. in the current sample preparation practices used in many bioanalytical fields including pharmacokinetics (PK), pharmacodynamics (PD), therapeutic drug monitoring (TDM), clinical and forensic toxicology, disease diagnosis and drug discovery. Additionally, in the present work was highlighted that applying innovative extraction and clean up procedures before instrumental analysis by means of a well-known, rugged, cheap, and diffused configurations (e.g. HPLC-PDA), could be possible to validate methods that shows analytical performances comparable to more expensive and complex instrumentations (e.g. LC-MS/MS) that require trained personnel, high maintenance costs and a deep knowledge of analytical problems that could be encountered. • FPSE-HPLC-PDA analysis of six benzophenone derivative UV filters • Direct analysis in human whole blood, plasma and urine • First method for the direct analysis in human whole blood without pretreatment • Validated method for clinical, diagnostic, and pharmaceutical applications [ABSTRACT FROM AUTHOR]

[Display omitted] • An FPSE protocol was proposed for the extraction of antihistamine drugs. • Direct extraction from the urine matrices. • Determination of the analytes in urine after oral administration of finished products. Herein, a poly(tetrahydrofuran)-based fabric phase sorptive extraction (FPSE) membrane was utilized for the isolation and determination of three antihistamine drugs (carbinoxamine, chlorpheniramine, and diphenhydramine) in human urine followed by HPLC-UV analysis. Among other membranes tested, the sol–gel poly(tetrahydrofuran) sorbent coated FPSE membrane was found to be more suitable for extracting the selected drugs. Based on their engineered affinity, the fabricated membranes are highly permeable that allows the extraction of biological samples with no previous pretreatment. The experimental parameters were systematically investigated and optimized using a central composite design of experiment and one-factor-at-a-time approaches. The proposed analytical scheme was validated in terms of linearity (0.10 – 5.0 μg mL−1), selectivity, limit of detection (0.03 μg mL−1), limit of quantitation (0.10 μg mL−1), precision (<12.7 % in all circumstances), and accuracy (% relative recovery: 88.1 – 113.7%). The membranes were reusable for at least 15 extractions with a set criterion of a 10% deviation of the initial performance. The final protocol was efficiently applied for the determination of selected antihistamines in authentic human urine after oral administration of chlorpheniramine and diphenhydramine-containing tablet and syrup, respectively. [ABSTRACT FROM AUTHOR]

The present work describes a fast, sensitive and selective procedure for the analyses of aromatase inhibitors including anastrozole, letrozole and exemestane used in the treatment of metastatic breast cancer by high performance liquid chromatography (HPLC) in human whole blood, plasma, and urine samples succeeding an extraction by innovative fabric phase sorptive extraction (FPSE). These drugs were successfully determined using a Luna C 18 column at 25 °C using acetonitrile and phosphate buffer. The analytical method was validated, using weighted-matrix matched standard calibration curves. The intra- and inter-day accuracy values (precision and trueness) fulfill the criteria of International Guidelines on Bioanalytical Methods Validation. The analytical performances were further tested on real human biological samples. To the best of our knowledge, this is the first FPSE procedure applied to human whole blood, plasma, and urine samples for the concurrent analysis of aromatase inhibitors possessing a wide range of polarity index values and could be easily adopted as a rapid and green analytical protocol for clinical and pharmaceutical applications. The proposed HPLC method is very innovative since in the literature there are only methods dealing with a single antitumoral drug, and no process has been described so far for these three antitumoral drugs together directly from the whole blood. [ABSTRACT FROM AUTHOR]

Androgens and progestogens are two important groups of endocrine disrupting compounds (EDCs) which are implicated to produce severe detrimental impact over aquatic biota, even at very low concentrations of ng L −1 . For this reason, one of the major challenges to analytical chemists is the development of sensitive and selective extraction processes which allow the rapid and green determination of these emerging pollutants at low concentrations in environmental samples. Fabric phase sorptive extraction is a new, highly sensitive, efficient and solvent minimized technique which combine the advantages of sol–gel derived microextraction sorbents and the rich surface chemistry of cellulose fabric substrate. This process has several advantages such as minimum usage of organic solvents, short extraction times, small sample volumes and high analyte preconcentration factors. In this study, an extraction method based on sorptive fabric phase coupled to ultra-high-performance liquid chromatography tandem mass spectrometry detection (FPSE-UHPLC–MS/MS) has been developed for the determination of four progestogens and six androgens in environmental and biological samples. All the parameters involved in the extraction, such as sample volume, extraction and desorption times, desorption solvent volume and sample pH values have been optimized. The developed method provides satisfactory limits of detection (between 1.7 and 264 ng L −1 ), good recoveries and low relative standard deviations (below 10% in tap and osmosis water and below 20% in wastewater and urine). Subsequently, the method was used to analyse tap water, wastewater treated with different processing technologies and urine samples. The concentrations of the detected hormones ranged from 28.3 to 227.3 ng L −1 in water samples and from 1.1 to 3.7 μg L −1 in urine samples. [ABSTRACT FROM AUTHOR]