Fabric Phase Sorptive Extraction Research Articles

Exploring the potentialities of a biodegradable polymeric film in sample preparation: An optimized “white” protocol to extract and quantify emerging contaminants in water

BackgroundThe introduction of white analytical chemistry encourages the development of methods characterized by a balance among greenness, productivity/feasibility and analytical performances. In the environmental analysis of emerging contaminants (ECs), for which high sensitivity and specificity are mandatory, the use of green and sustainable sample preparation needs to be coupled to a reliable analytical determination. Herein, an extraction method based on the use of a biodegradable polymeric film (Mater-Bi) and coupled to LC-MS/MS analysis was developed for the sensitive determination of ECs in wastewater. ResultsThe interaction among a range of ECs and the Mater-Bi film (a commercially available patented blend of polybutylene-terephthalate, starch and fatty acids) was investigated by two sequential experimental designs, to simultaneously study several factors and optimize extraction efficiency. The final method, resembling a fabric phase sorptive extraction, involved pH and ionic strength modification of the sample, 1h extraction and desorption in ethanol. Satisfactory recoveries from real wastewater were obtained for sixteen analytes (56–116 %), as well as excellent precision (inter-day relative standard deviations below 10 % for most compounds). Matrix effect was in the range 88–116 % at the lower pre-concentration factor, but also acceptable in most cases at the higher pre-concentration factor. LODs in matrix, from 0.004 to 0.159 μg L−1, were lower than or comparable to those from recent studies employing green extraction procedures. The method demonstrated its applicability to samples from wastewater treatment plants, allowing quantification of pharmaceuticals and UV filters at the μg L−1 and ng L−1 levels, respectively. SignificanceFor the first time, the synthetic biopolymer Mater-Bi, so far unexplored for the use in analytical chemistry, was exploited for a green, simple and extremely cheap extraction protocol. The optimized method is suitable for several ECs, guaranteeing very good accuracy, precision and specificity, also thanks to the LC-MS/MS analysis. The evaluation by green and white analytical chemistry metrics highlighted its superiority to conventional extraction methods.

Fabric phase sorptive extraction increases the accuracy of liquid chromatography-fluorescence detection of zearalenone in food samples

ABSTRACT The accuracy of mycotoxins detection in the food samples has always been controversial and more sensitive methods help better regulatory activities and, therefore, the quality of final products. Zearalenone is a toxic substance from mycotoxins mainly produced by Fusarium fungi that has proven endocrine effects and is potentially carcinogenic. This research aimed to apply the fabric phase sorptive extraction (FPSE) technique to the liquid chromatography- fluorescence detection method to increase the sensitivity and accuracy of zearalenone extraction and determination in food samples. Applying graphene nanoparticles in the sol-gel process modifies the method depending on the amount of nanoparticles, volume and type of the back-extraction solvent, sample pH, ionic strength, and back-extraction time, which are all considered and investigated. At analytical conditions, the limit of quantification (LOQ) 16.57 and detection (LOD) of 4.97 ng/mL were observed. The method’s accuracy was determined by three spiking levels of 100, 150, and 200 ng/mL in the real samples. The mean recovery percentage in wheat were 61.69, 70.56, and 97.95%, and in the rice, 58.13, 66.00, and 102.59, respectively. The average percentages of the relative standard deviation of the instrument for intra-and inter-laboratory repeatability were less than 1.7%. This work provided a superior analytical condition to the conventional detection procedures in food safety laboratories.

New fabric phase sorptive extraction for nondestructive analysis of heritage textile samples

Several types of pesticides used in museum collections over time become dangerous for people who may handle textile articles treated with such substances. In the case of the analysis of ancient, modern, and contemporary textile materials, it is particularly important to keep the artifacts intact, as they cannot be replaced. The need to use micro- or nondestructive techniques led to the development of methods such as solid-phase microextraction (SPME), liquid‒liquid dispersive microextraction (DLLME), and single-droplet microextraction (SDME). In this paper is described an optimized extraction method of three pesticides (malathion, methoxychlor, and permethrin) by creating a non-destructive solid phase extraction system on a textile support, abbreviated FPSE – 100 % cotton fabric coated with a sol-gel solution prepared from a polymer (PEG or PDMS). To obtain a suitable FPSE, the following parameters were evaluated: polymer selection (individual or mixture of polymers), acid catalyst (trifluoroacetic acid, acetic acid and hydrochloride acid), amount of polymer (1.0 g, 2.5 g or 5.0 g), polymerization time (30 min, 120 min and 240 min), ultrasonic bath temperature (40 °C and 70 °C), and type of bath to obtain the sol-gel (ultrasonic bath, water bath with stirring and mechanical stirrer). To complete the FPSE optimization, the influence of pesticide extraction time on FPSE and desorption from FPSE in ethyl acetate was also assessed.The pesticides extraction yields obtained for the laboratory textile samples are in the range of 52.7 %–128.0 %. The technique proposed in the manuscript proved to be effective as a nondestructive tool for evaluating and quantifying the presence of pesticides in textile museum collections. The approach described here reduces heritage object damage due to sampling compared to methods commonly employed and may represent a starting point for future research.

Adapting Fabric Phase Sorptive Extraction as an Innovative Multitool for Sample Transfer and Extraction in Pharmacokinetic Analysis Followed by LC-MS Determination of Levofloxacin in Plasma Samples.

Fabric phase sorptive extraction (FPSE) is a simple microextraction technique that allows analytes to be rescued from matrix components while using a small volume of samples to analyze complex biological systems. This study used FPSE as a microextraction tool and a sample storage and transfer device. Levofloxacin as a model molecule was applied intravenously (IV) to New Zealand male rabbits. The samples were simultaneously extracted by using FPSE and protein precipitation methods. The final solutions were analyzed using LC-MS equipped with an ACE C18 LC Column (150 mm × 4.6 mm, 5 μm) at 25 °C employed in isocratic elution mode using solution A (0.1% formic acid in water)/solution B (0.1% formic acid in acetonitrile) (80:20, v/v). The total analysis time was less than 15 min. The developed method was validated using the ICH M10 bioanalytical method validation and study sample analysis guidelines. The results obtained using FPSE were statistically identical to those obtained using protein precipitation. The plasma samples applied onto FPSE (10 μL onto 1.0 cm × 1.0 cm Biofluid Sampler) were stored in three different temperatures [refrigerator (2-8 °C), at ambient temperature (20 ± 5 °C), and in the stability cabinet (40 °C, 75% humidity)] and three different storage conditions (Eppendorf tubes, plastic containers, and straw paper envelopes). Levofloxacin in plasma samples adsorbed by FPSE biofluid sampler remained stable at 2-8 °C in Eppendorf tubes for at least 1 week. This study showed that FPSE could be used as a sample storage and transfer device for pharmacokinetic applications that need to work with small sample volumes and discard aggressive cold chains to store and transfer the plasma samples.

Fabric phase sorptive extraction: A sustainable approach in analysis of pharmaceutical product

As the pharmaceutical industry continues to evolve, there is an increasing demand for sustainable and efficient analytical techniques in the analysis of pharmaceutical products. This manuscript explores the application of Fabric Phase Sorptive Extraction (FPSE) as a novel and sustainable approach for the extraction and analysis of pharmaceutical compounds. FPSE, a recent advancement in sample preparation, offers a greener alternative by utilizing a fabric-like sorbent material. The environmentally friendly nature of FPSE, with reduced solvent consumption and waste generation, aligns with the principles of green analytical chemistry. Case studies involving the analysis of various pharmaceutical products showcase the versatility and applicability of FPSE in different matrices.

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.

Development of a fabric phase sorptive extraction method using ethylenediamine tetra-acetic acid modifier for quantitative determination and elimination of Pb2+, Cu2+ and Zn2+ cations in real sample solutions

A novel and simple fabric phase sorptive extraction technique based on using ethylenediamine tetra-acetic acid (EDTA-FPSE), was used for selective solid phase extraction of Pb2+, Cu2+ and Zn2+ cations followed by using inductively coupled plasma-optical emission spectrometry (ICP-OES). Then, the synthesized adsorbent was characterized by field emission scanning electron microscopy (FESEM) and energy dispersive X-Ray (EDX) analysis. The effect of some parameters including pH of the sample solution, extraction time, sample solution volume and the type and concentration of desorbent solution was investigated and they were optimized in details. Under the optimum experimental conditions, the limits of detection (LOD) were found to be: 0.062, 0.032 and 0.036 µg/L for Pb2+, Cu2+ and Zn2+cations, respectively and the limits of quantification (LOQ) were equal to 0.18, 0.1 and 0.12 µg/L for Pb2+, Cu2+ and Zn2+cations, correspondingly. Also, the reusability of the synthesized EDTA based on fabric phase sorptive adsorbent, showed that for these metal cations, it could be used for at least 12 adsorption/desorption cycles. Adsorption mechanism was evaluated by different isotherm models and based on the obtained results, the adsorption of Pb2+, Cu2+ and Zn2+ cations is followed by Langmuir isotherm model with a maximum adsorption capacity of 92.60, 75.76 and 101.10 mg g−1 for Pb2+, Cu2+ and Zn2+cations, respectively. Finally, the selective behavior, high recovery percentage (more than 90 %), simple extraction procedure (easily separation of adsorbent from solution), makes the EDTA based on fabric phase sorptive extraction (EDTA-FPSE) technique as an unique technique for solid phase extraction of these heavy metal cations in different real sample solutions.

Development a green analytical methodology for the sensitive determination of antidepressant drugs using fabric phase sorptive extraction as a simple sample pretreatment procedure

A new enrichment and determination method including HPLC-DAD analysis after fabric phase sorptive extraction (FPSE) has been developed to monitor trace amounts of antidepressant drugs including Amitriptyline (AMP), Fluoxetine (FLU), Vilazodone (VLZ), and Duloxetine (DUL). The target antidepressant drug molecules were retained onto the medium-polar sol–gel polytetrahydrofuran (PTHF) coated fabric phase sorptive extraction membrane in the presence of pH 9.0 medium, and back-extracted by desorbing to a smaller volume of acetonitrile (ACN) before chromatographic determinations. Chemical characterization of the used fabric phase sorptive extraction membrane and experimental variables of FPSE were studied step by step and optimized. HPLC analysis of antidepressant drugs were carried out by isocratic elution of 20 % methanol, 50 % trifluoroacetic acid (0.1 %, v:v) (TFA), 30 % acetonitrile (ACN). In the developed method. After enrichment of antidepressant molecules, 20 % Methanol, 50 % trifluoroacetic Acid (0.1 % TFA), and 30 % ACN by using C18 column. The detection limits for target antidepressant drugs under optimized conditions were found lower than 0.38 ng mL−1. The relative standard deviation (% RSD) values were calculated below 4.80 %. The developed method has been successfully applied to synthetic urine, real urine and pharmaceutical tablet samples and quantitative results have been obtained in recovery experiments.

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.

Application of sol‐gel universal sorbent coated fabric phase sorptive extraction membranes in combination with high‐performance liquid chromatography‐ultraviolet detection to monitor endocrine‐disrupting chemicals in milk and environmental water samples

AbstractHere, we deployed sol‐gel universal sorbent‐coated fabric phase sorptive extraction membranes in tandem with high‐performance liquid chromatography equipped with an ultraviolet detector (HPLC‐UV) for the analysis of 10 endocrine‐disrupting chemicals (EDCs). Due to the varying polarities of the studied compounds indicated by their octanol/water partition coefficient ‘log Kow’ (1.47–5.07), the extraction membrane was designed with different functionalities that are capable of simultaneous interaction with compounds of diverse natures including polar, non‐polar, and ionic species via sol‐gel sorbent coating technology. An isocratic mode of HPLC‐UV at 55:45% acetonitrile:water (v/v) on a reverse phase C18 Zorbax column (5 μm, 150 mm, 4.6 mm) was used for the separation and quantitation. Calibration curves were found linear between 25 and 2000 ppb for all compounds except cortisone in the range of 25–1000 ppb which provided an R2 value above 0.9940 in all cases. The intra‐day reproducibility and inter‐day reproducibility were found in the range of 1.2–12.8 and 0.2–14.1 (expressed as percent relative standard deviation), respectively. The validated method was finally deployed for the analysis of environmental water and milk samples with estradiol showing the highest concentrations among the studied compounds.

Development of a universal sol–gel sorbent for fabric phase sorptive extraction and its application in tandem with high performance liquid chromatography-ultraviolet detection for the analysis of phthalates in environmental and drinking water samples

Most sorbent-based sample preparation methods are designed to interact with a class of analytes i.e., a polar sorbent for polar analytes, a non-polar sorbent for non-polar analytes, an ion-exchange sorbent for ionized compounds. A big challenge surfaces when making a choice of an appropriate sorbent when there is a mixture of compounds of varying polarities and ionization states in the complex sample matrices. Hence, the aim of this study was to develop a universal sol–gel sorbent coating for fabric phase sorptive extraction that would effectively and simultaneously extract polar, nonpolar, organic acids and bases via different intermolecular/interionic interactions. The universal sol–gel sorbent coated fabric phase sorptive extraction membrane was created by exploiting sol–gel surface coating technology to implant different functional moieties, ion exchanging ligands and an organic polymer that results in a 3-D organic–inorganic hybrid structure on the fabric substrate with a high level of selectivity/affinity for the target compounds. The preconcentrated extracts containing the isolated phthalates after the fabric phase sorptive extraction procedure were injected into the high-performance liquid chromatography-ultraviolet detection (HPLC-UV) system for the quantification. The FPSE-HPLC-UV method demonstrated a linear range between 50 and 1000 ng/mL for dimethyl phthalate, diethyl phthalate, dipropyl phthalate, diallyl phthalate, benzyl butyl phthalate, 1–10000 ng/mL for di-n-heptyl phthalate, 1–5000 ng/mL for di-n-heptyl phthalate, 10–5000 ng/mL for di-n-ethyl hexyl phthalate and 100–7500 ng/mL di-n-octyl phthalate. The intra-day and inter-day reproducibility (in terms of percentage relative standard deviation, %RSD) did not exceed 13.6. This method proves to be a selective, accurate, reproducible, cheap, and fast analytical approach for the quantitative and qualitative determination of the phthalates which is useful in crafting regulations for phthalates content in beverages and juices as well as in environmental monitoring.

Fabric phase sorptive extraction as a sustainable sample preparation procedure to determine synthetic musks in water

A rapid sample preparation fabric phase sorptive extraction (FPSE) methodology followed by gas chromatography coupled to tandem mass spectrometry is proposed for the first time to determine 12 synthetic musks including nitro-, polycyclic and macrocyclic musk in environmental water and wastewater. An asymmetric screening design of experiments was used to evaluate the influence of nine parameters affecting FPSE in only 16 experiments. The factors included the sol–gel sorbent coating, stirring mode (both extraction and desorption), extraction and desorption time, salting-out effect, sample volume, type of solvent, and desorption solvent volume. The selected conditions imply the use of the sol–gel PDMS sorbent coating, 15 min extraction by ultrasound energy employing 10 mL of sample and 0.5 mL of ethanol as desorption solvent during 5 min. Accuracy and precision were assessed in different real water samples. Matrix effects were evaluated performing recovery studies in several aqueous matrices: river, sea, spring, laundry washing place, and wastewater at different concentration levels (0.1, 2, 10 µg L−1) demonstrating method accuracy (results ranged between 82 and 110%) and good precision (relative standard deviation, RSD < 12% in all cases). Limits of detection (LODs) were below 8 ng L−1 for the analyzed synthetic musks. As extraction was quantitative (exhaustive extraction), calibration was carried out using solvent standards without the need of repeating the extraction step, which is required in most microextraction methods, improving sample throughput, and reducing costs. Finally, the analysis of real contaminated samples revealed the presence of 11 out of the 12 target synthetic musks at concentrations up to 30 µg L−1, three of them banned in cosmetic regulation (musk tibetene, ambrette, and moskene). The developed FPSE based methodology uses low volume (0.5 mL) of a Generally Recognized as Safe (GRAS) solvent (ethanol), as well as minimum energy and time consumption, demonstrating to be a sustainable alternative to detect these microcontaminants in environmental waters and wastewaters.

Design and development of second-generation fabric phase sorptive extraction membranes: Proof-of-concept for the extraction of organophosphorus pesticides from apple juice prior to GC-MS analysis.

In this work, different sol-gel sorbent-coated second-generation fabric phase sorptive extraction (FPSE) membranes were synthesized using titania-based sol-gel precursors. The proposed membranes were tested for their efficiency to extract eleven selected organophosphorus pesticides (OPPs) from apple juice samples. Among the examined materials, sol-gel C18 coated titania-based FPSE membranes showed the highest extraction efficiency. These membranes were used for the optimization and validation of an FPSE method prior to analysis by gas chromatography-mass spectrometry. The detection limits for OPPs ranged between 0.03 and 0.08ngmL-1. Moreover, the relative standard deviation was<8.2% and 8.4% for intra-day and inter-day studies, respectively. The relative recoveries were 91-110% (intra-day study) and 90-106% (inter-day study) for all the target analytes, demonstrating good overall method accuracy. Moreover, the novel membranes were reusable at least 5 times. The titania-based membranes were compared to the conventional silica-based membranes and their utilization resulted in higher extraction recoveries.

Dual sorbent coating based magnet-integrated fabric phase sorptive extraction as a front-end to gas chromatography–mass spectrometry for multi-class pesticide determination in water samples

Magnet-integrated fabric phase sorptive extraction (MI-FPSE) is a sample preparation technique that has proved to be a powerful tool for environmental analysis. The fabrication and application of magnet-integrated dual sorbent-based FPSE membrane prepared by combining two different sol-gel sorbent-coated disks of different polarities together with a magnetic bar inserted between the two membranes to allow the stirring, was examined as novel preparation technique that not required samples pretreatments. The dual sorbent-based sample preparation platforms (made up of poly(tetrahydrofuran) and Carbowax 20M) were used for the extraction of seven classes of pesticides from ambient surface water samples prior to their determination by gas chromatography–mass spectrometry. Initially, different single and dual sol-gel sorbent-based MI-FPSE membranes were evaluated in terms of their extraction efficiency. The MI-FPSE with dual sol-gel sorbents were found to be superior to the single-materials MI-FPSE devices in terms of extraction recovery. The main parameters affecting the MI-FPSE extraction protocol (e.g., adsorption time, sample volume, stirring rate, salt addition, eluent type, desorption time and elution volume) were investigated. The selected extraction protocol enabled detection limits in the range between 0.001 and 0.16 ng mL−1. Furthermore, good relative standard deviation values for the intra-day and inter-day repeatability studies were obtained and were lower than 5.9 and 9.9 %, respectively. The proposed method was successfully used for the multi-class analysis of environmental surface water samples.

Optimization of a Fabric Phase Sorptive Extraction protocol for the isolation of six bisphenols from juice pouches to be analysed by high performance liquid chromatography coupled with diode array detector

Fabric Phase Sorptive Extraction (FPSE) combined with high pressure liquid chromatography using to diode array detection (HPLC-DAD) was applied for the simultaneous determination of bisphenols (BPA, BPB, BPC, BPE, BPF, BPS) in juice pouches. The FPSE procedure was optimized with regards to the critical parameters that affect the performance of the method including the selection of the FPSE membrane type and size, adsorption time, extraction time, solvent volume desorption, magnetic stirring ratio, and salt addition. The FPSE membrane could be reused up to 14 times. The developed FPSE-HPLC-DAD method was validated in terms of linearity, sensitivity, accuracy andprecision. The limits of detection (LODs) were lower than 6.9 ng/mL, while the limits of quantification (LOQs) were lower than 21 ng/mL. The results obtained are satisfactory in terms of precision, accuracy and repeatability, with recoveries above 86% and CV values below 9.5%. The FPSE-HPLC-DAD method was successfully applied in the determination of six bisphenols in juice samples stored in pouches.

Fabric phase sorptive extraction combined with dispersive liquid-liquid extraction for the extraction of some pesticide residues from fruit juices using partially carbonized cotton textile followed by gas chromatography–flame ionization detector

A piece of carbonized cotton textile (denim) was prepared and shown to be a viable sorbent for the fabric phase sorptive extraction of pesticide residues from various fruit juices. The presented sorbent was made by heating the acidified cotton textile in a furnace. The raw material used was readily accessible, green, and natural. The extracted analytes were more enriched using a liquid phase microextraction technique and quantified by gas chromatography equipped with a flame ionization detector. Under the optimum conditions, the limits of detection and quantification were in the ranges of 0.31–0.51 and 1.0–1.5 µg L−1, respectively. Satisfactory linearity for the calibration curves with coefficients of determination ranging from 0.995 to 0.997 was observed. Five replicated analyses were performed during the same day (intra-day precision) and five consecutive days (inter-day precision) and the obtained relative standard deviations for intra- and inter-day precisions were equal to or less than 8%. Relative recoveries of the analytes varied between 91 % and 103 % with relative standard deviations in the range of 3–6 %. The sorbent was reused for up to 12 analyses without significant loss of extraction efficiency and has a potential to be a useful and low–cost alternative to existing sorbents.

Exploiting the potential of fabric phase sorptive extraction for forensic food safety: Analysis of food samples in cases of drug facilitated crimes

Drug-facilitated crimes (DFCs) entail the use of a single drug or a mixture of drugs to render a victim unable. Traditionally, biological samples have been gathered from victims and conducting analysis to establish evidence of drug administration. Nevertheless, the rapid metabolism of various drugs and delays in analysis can impede the identification of such substances. For this, the present article describes a rapid, sustainable, highly efficient and miniaturized protocol for the identification and quantification of three sedative-hypnotic drugs namely diazepam, chlordiazepoxide and ketamine in alcoholic beverages and complex food samples (cream of biscuit, flavoured milk, juice, cake, tea, sweets and chocolate). The methodology involves utilizing fabric phase sorptive extraction (FPSE) to extract diazepam (DZ), chlordiazepoxide (CDP), and ketamine (KET), Subsequently, the extracted sample are subjected to analysis using gas chromatography-mass spectrometry (GC–MS). Several parameters, including type of membrane, pH, agitation time and speed, ionic strength, sample volume, elution volume and time, and type of elution solvent, were screened and thoroughly optimized. Sol-gel Carbowax 20M (CW-20M) has demonstrated most effective extraction efficiency for the target analytes among all evaluated membranes. Under optimal conditions, the method displayed linearity within the range of 0.3–10 µg mL−1 (or µg g−1), exhibiting a coefficient of determination (R2) ranging from 0.996 to 0.999. The limits of detection (LODs) and limits of quantification (LOQs) for liquid samples ranging between 0.020 and 0.069 µg mL−1 and 0.066–0.22 µg mL−1, respectively. Correspondingly, the LODs for solid samples ranged from 0.056 to 0.090 µg g−1, while the LOQs ranged from 0.18 to 0.29 µg g−1. Notably, the method showcased better precision, with repeatability and reproducibility both below 5% and 10%, respectively. Furthermore, the FPSE-GC–MS method proved effective in determining diazepam (DZ) in forensic food samples connected to drug-facilitated crimes (DFCs). Additionally, the proposed method underwent evaluation for its whiteness using the RGB12 algorithm.

Exploring the potential of fabric phase sorptive extraction in postmortem toxicology: Green analysis of pheniramine in a forensic case of its fatal intoxication

Sample preparation is vital in postmortem toxicology to extract and purify analytes from complex matrices. Challenges like interfering substances and limited sample quantity can be overcome with effective preparation, ensuring accurate results. Hence, a simple, sustainable, affordable, and high-throughput method using fabric phase sorptive extraction (FPSE) - gas chromatography - mass spectrometry (GC–MS) was developed for pheniramine (PHN) analysis in postmortem biological samples (blood and liver). FPSE extraction efficiency was optimized by studying factors like membrane type, stirring time and speed, back-extraction solvent, sample pH, and ionic strength. The optimized method was validated following SWGTOX guidelines for linearity, precision, sensitivity, recovery, matrix effect, stability, and other relevant parameters. The method exhibited linearity in the range of 0.1–10 µg mL−1 for blood and 0.1–10 µg g−1 for liver samples under optimal conditions. The limit of quantification (LOQ) was 0.066 µg mL−1 and 0.073 µg g−1 for PHN in blood and liver, respectively. Intra-day and inter-day precision were < 5.8% and < 9.8%, respectively. Recovery and accuracy ranged from 74 to 80% and 95–100%, respectively. Real autopsy samples were analyzed using this method, compared to conventional solid-phase extraction (SPE), demonstrating its effectiveness. Additionally, the environmental impact and sustainability were assessed using ComplexGAPI and Analytical Eco-Scale tools. The FPSE-GC–MS method showed superior performance, marking a notable advancement in postmortem toxicology sample preparation. To the best of our knowledge, this is the first application of FPSE in the analysis of postmortem tissue samples. In conclusion, FPSE-GC–MS method offers a simple, sustainable, and affordable approach to sample preparation for postmortem forensic samples, overcoming challenges such as interfering substances and limited sample quantity. These advantages of FPSE make it a promising alternative to traditional methods, positions it as a significant advancement in the field, poised to shape the future of sample preparation in forensic toxicology.

Poly(tetrahydrofuran)-based fabric phase sorptive extraction combined with HPLC-UV for the determination of antihistamines in human urine

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.

Investigating the applicability of polar fabric phase sorptive extraction for the HPLC quantitation of salivary vitamin B12 following administration of sublingual tablets and oral sprays.

In this study, a simple and rapid fabric phase sorptive extraction (FPSE) protocol combined with high performance liquid chromatography-ultraviolet detection (HPLC-UV) was developed for the monitoring of salivary vitamin B12 levels. Different sol-gel coated cellulose and polyester membranes were evaluated and sol-gel Carbowax 20M coated polyester membranes were chosen for the selective extraction of the target analyte from saliva samples. Face-centered central composite design (FC-CCD) was employed for the investigation and optimization of sample volume, extraction time and stirring rate, while the other experimental factors were investigated using the classical one-factor-at-a- time" (OFAT) method. Validation of the FPSE-HPLC-UV method was conducted according to the FDA guidelines for bioanalytical methodologies. The lower limit of quantification for vitamin B12 was 0.10μgmL-1 and the linear range was 0.10-10.0μgmL-1. The relative recoveries for intra-day and inter-day studies were 87.5-113.8% and 88.2-119.2%, respectively. The relative standard deviation was better than 8.2% in all cases, demonstrating good method precision. The sol-gel Carbowax 20M coated FPSE membranes were found to be reusable for up to 25 times. Finally, the proposed scheme was successfully employed for the quantitation of salivary vitamin B12 at different time points following the administration of sublingual tablets and oral sprays.