Search

Headspace solid-phase microextraction (HSSPME) of volatile organic compounds (VOCs) from aqueous samples under vacuum conditions (Vac-HSSPME) allows increasing extraction rates and decreasing detection limits compared to HSSPME under atmospheric pressure. The positive effect of the vacuum on HSSPME of an analyte can be quickly estimated using its Henry's law constant (HLC). According to the two-layer model of evaporation, substantial positive effect of the vacuum can be expected for analytes with HLC lower than 1.6·10−4 atm m3 mol−1 (0.0065 at 25 °C), but the model does not consider possible effects of other important extraction parameters. This research was aimed at the evaluation of the possible effect of vacuum on the equilibration time and extracted amounts of analytes with various HLC and fiber coating-headspace distribution constants (Kfh) using the computational model recently developed in COMSOL Multiphysics® software. It has been proven that HSSPME under vacuum provides faster equilibration of VOCs with all studied Kfh and HLC. The largest vacuum effect on the extracted analyte amount was 3.9–4.0 times at logKfh = 6 and HLC = 10−6–10−3. The substantial (≥1.5 times) vacuum impact should not be expected for analytes with logKfh < 5 for 15-min extraction and logKfh < 5.5 for 30-min extraction. The vacuum impact should be more pronounced when using fiber coatings with a stronger affinity to analytes. The obtained results will be useful for the development of new methods based on Vac-HSSPME and evaluation whether HSSPME is reasonable to conduct under vacuum conditions for faster equilibration and/or lower detection limits.

In this study, a novel methodology has been developed for the rapid and sensitive analysis of bongkrekic acid (BA), a highly toxic bacterial metabolite, using a molecularly imprinted polymer-coated wooden-tip coupled with electrospray ionization mass spectrometry (MIPWT-ESI-MS). A MIPWT solid phase microextraction (SPME) probe specifically tailored for BA was fabricated, by employing dummy template molecules/functional monomers in the imprinting coating modification. This approach exhibits an enrichment factor (EF) of 683 ± 53 for efficient extraction of BA from aqueous matrices, demonstrating the utility of dummy templates in enhancing the selectivity and sensitivity of the MIPWT-ESI-MS method. The analytical performance of the MIPWT-ESI-MS method was evaluated, demonstrating a desirable linear correlation (r = 0.9988), along with remarkable sensitivity by a limit of detection (LOD) and limit of quantitation (LOQ) at 0.05 μg/L and 0.16 μg/L in pure water, respectively. Additionally, the method demonstrated high repeatability with a relative standard deviation (RSD) < 3.9 % (n = 6) and reproducibility with an RSD < 13.4 %. The practical application of the method was confirmed through the successful analysis of real-world samples, including tap water, wastewater from a food processing factory, and the aqueous extracts of food samples, with BA detected at 0.296 µg/L in Tremella. Spiking experiments further validated the accuracy of the method, with recoveries ranging from 81 % to 97 %. This study integrates MIP with ambient mass spectrometry, offering a robust, selective, and sensitive tool for the monitoring of trace BA levels in complex food and environmental samples, contributing significantly to public health safety and food quality control.

Assessing the greenness of sample preparation techniques is essential due to the use of various solvents, chemicals, reagents, sorbents, pH adjustments, and energetic inputs. Solid-Phase Microextraction (SPME) is preferred over traditional flavor extraction methods such as Simultaneous Distillation Extraction (SDE) and Solvent-Assisted Flavor Evaporation (SAFE) because of its sensitivity, efficiency, speed, versatility, and economy. SPME fibers coated with stationary phases can extract volatile and semi-volatile flavor compounds from food samples, which are then desorbed and analyzed by Gas Chromatography-Mass Spectrometry (GC–MS). This article provides an assessment of the greenness of 50 SPME techniques for flavor analysis using the AGREE Prep and Sample Preparation Metric of Sustainability (SPMS) tools. This evaluation offers valuable insights into the environmental impact and sustainability of SPME as sample preparation techniques for flavour analysis. As per AGREE Prep, method 34 was found to be environmental friendly with score of 0.66, attributed to safe solvents, minimized waste, high sample throughput, and low energy consumption where as method 7 with SPMS scores of 7.05 is more sustainable due to miniaturization, fewer steps, and low energy use.

In this work, four metal-organic frameworks (MOFs) including DUT-4, DUT-8, IRMOF-8, and MIL-140B were synthesized using 2,6-naphthalene dicarboxylic acid as organic ligand and Al3+, Co2+, Zn2+, and Zr4+as metal centers, then coated on stainless steel wires as solid-phase microextraction (SPME) fiber coatings. Five aldehyde biomarkers (hexanal, heptanal, octanal, decanal, and nonanal) in exhaled breath of lung cancer patients were used as the target analytes, and extracted using four MOFs fiber coatings, followed by thermal desorption and quantitative analysis using GC–MS. The DUT-4 was found to be the most appropriate sorbent. The developed SPME-GC–MS method has large enrichment factors (877–1711), wide linear ranges (0.5–1000 μg L−1), and low detection limits (0.056–0.138 μg L−1). The relative standard deviation for six replicate cycles using one DUT-4 coated fiber were 2.0–7.7 % (intra-day) and 2.2–4.6 % (inter-day), respectively. The fiber-to-fiber reproducibility for three parallel prepared fibers was in the range of 3.7–13.7 % (RSD). The fabricated DUT-4 coated fiber can withstand at least 100 cycles of extraction/desorption/conditioning without significant loss of extraction efficiency and precision. The high enrichment factors of the DUT-4 coatings are attributed to the high specific surface area, unique porous structure, and abundant aluminum coordinated unsaturated metal sites of the DUT-4 material. Moreover, the 2,6-naphthalene dicarboxylic acid has two benzene rings with a 180° orientation, which not only increases the hydrophobicity of the MOFs material to avoid water molecules occupying adsorption sites and helps to form a rigid skeleton structure with a large number of functional adsorption sites on the surface, thereby improving the enrichment factor of target analytes. Ultimately, the developed DUT-4 coated SPME fibers was sucessfully used for the analysis of exhaled breath samples, and the recoveries for the spiked analytes were in the range of 89–105 %.

The primary objective of this contribution is to offer insights into fundamentals associated with typical sample preparation, facilitating rational design of new analytical technologies and effective optimization of existing techniques. Sample preparation stands a pivotal stage in the analytical process. Unfortunately, the optimization of associated parameters often relies on trial and error rather than systematic scientific methodologies. If an extraction method provides good recovery of spikes of standards, it is assumed that it works well and no further consideration is given to the underlying principles driving its performance. In the realm of sample preparation, the fundamentals of method optimization are not accorded the same significance as in other technologies, such as chromatography or mass spectrometry. Consequently, the fundamentals of sample preparation are typically overlooked in analytical chemistry curricula.A notable impediment to progress in the sample preparation area is underdeveloped understanding of the fundamentals of extraction, particularly when dealing with natural, often complex samples, where native analyte-matrix interaction is different compared to spikes. This stands in contrast to the physiochemically simpler systems employed in separation and quantification steps, such as chromatography and mass spectrometry.A careful consideration of the underlying principles of sampling and sample preparation can lead to the creation of more efficient and environmentally friendly technologies. Embracing these principles aligns with global shift towards more sustainable future, challenging the perception that sample preparation is solely an artistic endeavour and highlighting its potential as a scientifically grounded discipline.

In vivo lung perfusion (IVLP) is a novel isolated lung technique developed to enable the local, in situ administration of high-dose chemotherapy to treat metastatic lung cancer. Combination therapy using folinic acid (FOL), 5-fluorouracil (F), and oxaliplatin (OX) (FOLFOX) is routinely employed to treat several types of solid tumours in various tissues. However, F is characterized by large interpatient variability with respect to plasma concentration, which necessitates close monitoring during treatments using of this compound. Since plasma drug concentrations often do not reflect tissue drug concentrations, it is essential to utilize sample-preparation methods specifically suited to monitoring drug levels in target organs. In this work, in vivo solid-phase microextraction (in vivo SPME) is proposed as an effective tool for quantitative therapeutic drug monitoring of FOLFOX in porcine lungs during pre-clinical IVLP and intravenous (IV) trials. The concomitant extraction of other endogenous and exogenous small molecules from the lung and their detection via liquid chromatography coupled to high resolution mass spectrometry (LC-HRMS) enabled an assessment of FOLFOX's impact on the metabolomic profile of the lung and revealed the metabolic pathways associated with the route of administration (IVLP vs. IV) and the therapy itself. This study also shows that the immediate instrumental analysis of metabolomic samples is ideal, as long-term storage at −80 °C results in changes in the metabolite content in the sample extracts.

The endocannabinoid system (ECS), particularly its signaling pathways and ligands, has garnered considerable interest in recent years. Along with clinical work investigating the ECS’ functions, including its role in the development of neurological and inflammatory conditions, much research has focused on developing analytical protocols enabling the precise monitoring of the levels and metabolism of the most potent ECS ligands: exogenous phytocannabinoids (PCs) and endogenous cannabinoids (endocannabinoids, ECs). Solid-phase microextraction (SPME) is an advanced, non-exhaustive sample-preparation technique that facilitates the precise and efficient isolation of trace amounts of analytes, thus making it appealing for the analysis of PCs and ECs in complex matrices of plant and animal/human origin. In this paper, we review recent forensic medicine and toxicological studies wherein SPME has been applied to monitor levels of PCs and ECs in complex matrices, determine their effects on organism physiology, and assess their role in the development of several diseases.

The effect of ultrasonic pre-treatment on moisture removal characteristics of ginger in a convective dryer was investigated. The slabs were dried by practicing sonication durations of 0, 15 and 30 min at different levels of the air temperature and velocity. Following increasing the sonication duration and air temperature, required time and energy to dehydrate the samples were decreased. The pre-treatment played important role in improving rehydration capability and surface color retention in the dried gingers. Content of the main volatile component (α-Zingiberene) was not influenced by the sonication. Mean values for the phenolic contents and antioxidant activity at sonication duration of 0, 15 and 30 min were determined to be 18.93, 18.15 and 17.49 GAE/g dry matter and 83.57, 78.33 and 74.58 %, respectively. The desired values for the temperature, velocity and sonication duration were revealed to be about 66 °C, 3 m/s and 20 min, respectively.

The development of preferably simple, fast, sensitive, selective and relatively inexpensive methods for the determination of pesticide residues in food and environmental samples is essential. The design of methods with the above attributes can pose challenges, especially for complex food and environmental matrices. In this sense, isolation and pre-concentration of pesticides in such matrices are required, and are considered an important step towards the determination of low levels of these analytes. Another characteristic of an analytical approach that is gaining increasing focus is the ''greenness'' of the overall method, most notably in the avoidance of the use of potentially harmful organic solvents. In this vein, scientists are looking for environmentally friendlier alternatives to organic solvents. Ionic liquids (ILs) suitable for use in extraction or sample preparation procedures represent one such alternative. A better understanding of the nature of the IL-based extractions and their impact on pesticide analysis is important for their successful applicability. Due to their unique properties such as polarity, adjustable viscosity, miscibility and surface tension, and their interactions thereof (with respect to sample matrices and analytes) ILs have gained widespread attention and popularity in many areas of analytical chemistry, including modern sample preparation technologies. This mini-review critically discusses recent and/or interesting applications of ILs in the microextraction of pesticides. The topics covered include a brief overview of ILs, their structures and interactions, and their applications as extractants in liquid-phase microextraction and solid-phase microextraction.

In this study, for the first time, multiple monolithic fiber solid-phase microextractions (MMF-SPME) combining with high-performance liquid chromatography was established for the determination of residuals of 39 types of antibiotics, including 12 quinolones, 9 tetracyclines and 18 sulfonamides in meat products (chicken, poultry, beef and mutton) and dairy products (milk, yogurt, cheese and butter) in Khuzestan province. To prepare MMF, we fabricated using metal-organic framework deep eutectic solvents, molecularly imprinted polymers (DES@UMCM-1MOF/MIP) and then used it to get a single thin fiber. Subsequently, five thin fibers were bound together to obtain the MMF-SPME. Optimization of the parameters affecting the desorption of antibiotics was performed using Box–Behnken design. Under optimized conditions, calibration graphs for total antibiotics were linear in a concentration range of 5.0–1400 µg L−1 with correlation coefficients of more than 0.995. Limits of detection and quantification were in the ranges of 1.1- 2.3 µg L−1 and 3.3-7.6 µg L−1, respectively. The relative mean recoveries in different samples ranged from 95.1% to 100.0%.

The direct coupling of solid-phase microextraction (SPME) to mass spectrometry (MS) (SPME-MS) has proven to be an effective method for the fast screening and quantitative analysis of compounds in complex matrices such as blood and plasma. In recent years, our lab has developed three novel SPME-MS techniques: SPME-microfluidic open interface-MS (SPME-MOI-MS), coated blade spray-MS (CBS-MS), and SPME-probe electrospray ionization-MS (SPME-PESI-MS). The fast and high-throughput nature of these SPME-MS technologies makes them attractive options for point-of-care analysis and anti-doping testing. However, all these three techniques utilize different SPME geometries and were tested with different MS instruments. Lack of comparative data makes it difficult to determine which of these methodologies is the best option for any given application. This work fills this gap by making a comprehensive comparison of these three technologies with different SPME devices including SPME fibers, CBS blades, and SPME-PESI probes and SPME-liquid chromatography-MS (SPME-LC-MS) for the analysis of drugs of abuse using the same MS instrument. Furthermore, for the first time, we developed different desorption chambers for MOI-MS for coupling with SPME fibers, CBS blades, and SPME-PESI probes, thus illustrating the universality of this approach. In total, eight analytical methods were developed, with the experimental data showing that all the SPME-based methods provided good analytical performance with R2 of linearities larger than 0.9925, accuracies between 81% and 118%, and good precision with an RSD% ≤ 13%.

Improved analytical methods for the metabolomic profiling of tissue samples are constantly needed. Currently, conventional sample preparation methods often involve tissue biopsy and/or homogenization, which disrupts the endogenous metabolome. In this study, solid-phase microextraction (SPME) fibers were used to monitor changes in endogenous compounds in homogenized and intact ovine lung tissue. Following SPME, a Biocrates AbsoluteIDQ assay was applied to make a downstream targeted metabolomics analysis and confirm the advantages of in vivo SPME metabolomics. The AbsoluteIDQ kit enabled the targeted analysis of over 100 metabolites via solid-liquid extraction and SPME. Statistical analysis revealed significant differences between conventional liquid extractions from homogenized tissue and SPME results for both homogenized and intact tissue samples. In addition, principal component analysis revealed separated clustering among all the three sample groups, indicating changes in the metabolome due to tissue homogenization and the chosen sample preparation method. Furthermore, clear differences in free metabolites were observed when extractions were performed on the intact and homogenized tissue using identical SPME procedures. Specifically, a direct comparison showed that 47 statistically distinct metabolites were detected between the homogenized and intact lung tissue samples (P

For identifying and quantifying prohibited substances, solid-phase microextraction (SPME) continues to arouse interest as a sample preparation method. However, the practical implementation of this method in routine laboratory testing is currently hindered by the limited number of coatings compatible with the ubiquitous high-performance liquid chromatography (HPLC) systems. Only octadecyl (C18) and polydimethylsiloxane/divinylbenzene ligands are currently marketed for this purpose. To address this situation, the present study evaluated 12 HPLC-compatible coatings, including several chemistries not currently used in this application. The stationary phases of SPME devices in the geometry of thin film-coated blades were prepared by applying silica particles bonded with various functional ligands (C18, octyl, phenyl-hexyl, 3-cyanopropyl, benzenesulfonic acid, and selected combinations of these), as well as unbonded silica, to a metal support. Most of these chemistries have not been previously used as microextraction coatings. The 48 most commonly misused substances were selected to assess the extraction efficacy of each coating, and eight desorption solvent compositions were used to optimize the desorption conditions. All samples were analyzed using an HPLC system coupled with triple quadrupole tandem mass spectrometry. This evaluation enables selection of the best-performing coatings for quantifying prohibited substances and investigates the relationship between extraction efficacy and the physicochemical characteristics of the analytes. Ultimately, using the most suitable coatings is essential for trace-level analysis of chemically diverse prohibited substances.

The solid-phase microextraction technique quantifies analytes without considerably affecting the sample composition. Herein, a proof-of-concept study was conducted to demonstrate the use of coated probe electrospray ionization (coated-PESI) and coated blade spray (CBS) as ambient mass spectrometry approaches for monitoring drug biotransformation. The ability of these methods was investigated for monitoring the dephosphorylation of a prodrug, combretastatin A4 phosphate (CA4P), into its active form, combretastatin A4 (CA4), in a cell culture medium supplemented with fetal bovine serum. The CBS spot analysis was modified to achieve the same extraction efficiency as protein precipitation and obtained results in 7 min. Because coated-PESI performs extraction without consuming any samples, it is the preferred technique in the case of a limited sample volume. Although coated-PESI only extracts small quantities of analytes, it uses the desorption solvent volume of 5–10 pL, resulting in high sensitivity, thus allowing the detection of compounds after only 1 min of extraction. The biotransformation of CA4P into CA4 via phosphatases occurs within the simple matrix, and the proposed sample preparation techniques are suitable for monitoring the biotransformation.

Assessment and control of emerging organic pollutants in food have become critical for global food safety and health. The European Union has set standards for certain emerging organic pollutants, such as phthalic acid esters (PAEs) in food. Because of being endocrine disruptors, PAEs are toxic and carcinogenic to humans. Release of PAEs from packaging materials poses a potential risk to human health and causes environmental pollution. In this study, a highly sensitive analytical method for the detection of PAE contents in tea beverages was established using hydroxyl-functionalized covalent organic frameworks (COFs) as solid-phase microextraction (SPME) coating. Results indicate that functionalization with hydroxyl groups enhances the adsorption of PAEs. The proposed method exhibits a wide linear range (1-20,000 ng L -1 ), low limits of detection (> 0.048 ng L -1 ), and satisfactory recovery (72.8 %-127.3 %). To investigate the PAE contamination in beverages, contamination levels of six typical PAEs and their health impacts were surveyed across various brands/types/packaging materials of tea beverages sold in China. Results of the hazard quotient and hazard index approaches suggest no or extremely low health concerns regarding PAE levels. We observe that hydroxyl groups functionalized on COFs enhance the adsorption of PAEs. Moreover, an important outcome of this study is development of an efficient and sensitive direct detection method for PAEs in complex tea matrices, providing a reliable approach for the assessment of PAEs in other complex matrices., 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 © 2024. Published by Elsevier B.V.)

A carboxyl functionalized organic-inorganic hybrid monolithic column (TMOS-co-CES) was applied as in-tube solid-phase microextraction (SPME) sorbent combining with ultra-performance liquid chromatography-triple quadrupole/linear ion trap mass spectrometer for separation and analyzation of seven typical amphetamine-type stimulants (ATSs), including amphetamine (AM), methamphetamine (MAM), cathinone, methcathinone, 3,4-methylenedioxyamphetamine, 3,4-methylenedioxymethamphetamine and 3,4-methylenedioxyethylamphetamine. The application potential of TMOS-co-CES material to ATSs was preliminarily confirmed by computational simulation by using cathinone as a representative. The influences of various SPME parameters and analytical performance were investigated systematically. As matched with the results of computational simulation, TMOS-co-CES column could capture ATSs under milder near neutral pH condition with high extraction efficiency basing on the adsorption mechanism explained as a mixed mode of electrostatic and hydrophobic interactions. Seven target trace ATSs in spiked sewage, pond water and urine could be rapidly and conveniently separated and enriched by the proposed TMOS-co-CES in-tube SPME method under the optimized conditions with good accuracy, repeatability and resistance to matrix interference. Moreover, AM and MAM had been successfully detected in real urines of suspected drug abusers by TMOS-co-CES in-tube SPME method, which indicated that the proposed method had good application feasibility for drug monitoring. The mild extraction condition and ideal method performance further made the TMOS-co-CES in-tube SPME method more potential in applications for forensic analysis and drug abuse., 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 © 2024 Elsevier B.V. All rights reserved.)

Phytohormones are a class of endogenous substances that separately or synergistically regulate the growth, development, and differentiation of plants. Accurately and efficiently detecting and monitoring the concentration of plant hormones in living plants is of significant importance. Herein, a novel mesoporous carbon hollow spheres (MCHS)-based in vivo solid phase microextraction (SPME) probe was designed for in vivo sampling of plant hormones. The designed MCHS features the advantages of high surface area, porous shells, and large hollow spaces, facilitating the dynamic adsorption and enrichment of target phytohormone. In addition, a cationic polyelectrolyte, (poly (diallyl dimethyl ammonium chloride) (PDDA), was further modified onto the MCHS to expedite the extraction process by electrostatic interaction. Utilizing the MCHS@PDDA probe in combination with HPLC-MS/MS facilitated the continuous monitoring of three plant hormones (abscisic acid (ABA), indole-3-acetic acid (IAA), and gibberellin (GA3)) in Chinese aloe. The detection limit of this method was 0.016-0.090 μg/L, the linear range was 10-1000 μg/L, and both the RSD of the single probe (n = 6) and probe-to-probe test (n = 6) were less than 7.2 %. This method had excellent accuracy and good reproducibility comparable to the traditional sample pretreatment method. Ultimately, this established in-vivo SPME method was successfully adopted to quantify three selected plant hormones in living Chinese Aloes, providing a new method for the long-term monitoring of endogenous active substances in living system., 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 © 2024 Elsevier B.V. All rights reserved.)

Covalent organic frameworks (COFs), when utilized as solid-phase microextraction (SPME) coating materials, exhibit remarkable abilities to concentrate phenols by thousands-fold owing to their vast surface area and exceptional stability. However, the prevalent micropores inherent in COFs can impede rapid mass transfer of target molecules, prolonging SPME extraction times. To addresses this limitation, this work introduces a novel approach by integrating hierarchical porous structures into COFs, leveraging polystyrene microspheres as hard templates during the in situ growth process of the SPME coating. Due to the presence of a hierarchical porous structure derived from the template, the resulting hierarchical porous TpBD coating, termed HP-TpBD, demonstrated enhanced extraction efficiency, accelerated extraction kinetics, and notably shortened extraction times for phenolic compounds. Coupled with gas chromatography-mass spectrometry, a highly sensitive method featuring a low limit of detection (0.20-0.28 ng L -1 ), a broad linear range (1.0∼1.0 × 10 4 ng L -1 ), and excellent precision (RSD < 8.5 %) was established. This methodology enables accurate quantitative analysis of phenols in water and soil samples. This work provides valuable insights into developing COF-based SPME coatings for the efficient extraction of volatile contaminants, paving the way for more efficient and sensitive analytical procedures., 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 © 2024 Elsevier B.V. All rights reserved.)

A layer-by-layer chemical bonding strategy was developed for fast in situ growth of bifunctional mesoporous covalent organic framework submicrospheres (COF SMSs) on the nickel-chromium alloy (Ni-Cr) fiber substrate via the ultrasound-assisted Schiff-base reaction for the first time. COF SMSs showed well-defined morphology, extraordinary high surface area (1211 m 2 ·g -1 ) and narrow mesopore (2.50 nm) as well as excellent stability. Furthermore, the resulting Ni-Cr fiber presented outstanding adsorption capability and improved selectivity for bisphenols (BPs). Consequently, an attractive SPME-HPLC-UV approach with the Ni-Cr@Ni-Cr LDHs NSs@COF SMSs fiber was proposed for rapid preconcentration and sensitive determination of BPs. By optimizing adsorption parameters, the SPME-HPLC-UV method presented good linearity for five BPs in the ranges of 0.02-200 ng·mL -1 with coefficients of determination (R 2 ) higher than 0.999. Limits of detection and limits of quantitation were obtained from 0.003 ng·mL -1 to 0.006 ng·mL -1 and from 0.010 to 0.019 ng·mL -1 , respectively. Moreover, the intra-day and inter-day precision expressed as relative standard deviations (RSDs) was 1.57-3.52 % and 2.65-4.38 % for the proposed method with a single fiber, respectively. RSDs of the proposed method with different duplicate fibers were 3.25-6.72 %. The proposed SPME-HPLC-UV method was available for efficient preconcentration and sensitive detection of five BPs from real water and milk samples. The relative recoveries at three spiking levels of BPs were achieved in the range of 80.00-118.8 % with RSDs below 7.81 %. In addition, the prepared fiber still exhibited satisfactory adsorption performance after 120 adsorption-desorption cycles., 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 © 2024 Elsevier B.V. All rights reserved.)

Nitrated polycyclic aromatic hydrocarbons (nitro-PAHs) are pervasive contaminants in aquatic environments. They are characterized by persistence, toxicity, bioaccumulation, and long-range transport, significantly threatening human health. The development of sensitive methods for nitro-PAH analysis in environmental samples is in great need. This study developed a novel carbonaceous SPME coating derived from metal-organic framework (MOF), namely a spherical assembly consisting of carbon nanorods with hierarchical porosity (HP-MOF-C), for the extraction and determination of nitro-PAHs in waters. The HP-MOF-C coated fiber demonstrated superior nitro-PAH extraction efficiencies, with enrichment factors 2∼70 times higher than commercial fibers. This enhancement was due to the strong hydrophobic, π-π electron coupling/stacking, and π-π electron donor-acceptor interactions between the carbonaceous framework of HP-MOF-C and the nitro-PAHs. Moreover, the unique hierarchical porous structure of HP-MOF-C accelerated the diffusion of nitro-PAHs, further facilitating their enrichment. The fiber also exhibited good thermal stability, remarkable chemical stabilities against common acid, base, and polar/non-polar solvents, and long service life (> 150 SPME cycles). The nitro-PAH determination method based on HP-MOF-C coating yielded wide linear ranges, low detection limits (0.4∼5.0 ng L -1 ), satisfactory repeatability and reproducibility, and good recoveries in real water samples. The proposed method was considered to be green according to the Analytical GREEnness assessment. The present study not only offers an efficient SPME coating for the enrichment of nitro-PAHs, but also provides insights into the design of porous coating materials., 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 © 2024 Elsevier B.V. All rights reserved.)

Nitroaromatic compounds (NACs), as a kind of important chemical intermediates, are widely used in industrial productions. However, NACs have carcinogenic effect and their residues may pose harm to human health. Therefore, there is necessity to set up effective analytical method to monitor them in some environmental samples. However, because of their low concentrations in real samples, they need to be enriched by an effective adsorbent before the subsequent instrumental detection. In this work, a three-dimensional nitrogen-rich conjugated microporous polymer (DCT-Try-CMP) was synthesized with 3,6-dichloro-1,2,4,5-tetrazine and triptycene as monomers via Friedel-Crafts reaction. It presented a good adsorption capability for the NACs. After optimization, a solid-phase microextraction with DCT-Try-CMP fiber combined with gas chromatography-flame ionization detection for the quantitation of trace NACs in environmental water and soil samples was developed. The limits of detection of the method (S/N = 3) for environmental water and soil samples were 0.08-0.30 μg L -1 and 1.00-5.00 ng g -1 , and the limits of quantification (S/N = 9) were 0.27-0.90 μg L -1 and 3.00-15.0 ng g -1 , respectively. The linear quantification response ranges for the analytes were 0.27-200 μg L -1 and 3.00-1000 ng g -1 for water and soil samples, respectively. For water samples at the analytes concentrations of 5.00, 50.0 and 100 μg L -1 , the method recoveries ranged from 82.2 % to 120 % and for soil samples at the concentrations of 15.0, 200 and 400 ng g -1 , the method recoveries fell in the range from 80.2 % to 120 %. The method provides a sensitive and effective approach for monitoring trace NACs in environmental water and soil samples., 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 © 2024 Elsevier B.V. All rights reserved.)

Sunitinib, N-desmethyl imatinib, dasatinib, imatinib, and bosutinib are tyrosine kinase inhibitors (TKIs) that are commonly employed in the treatment of a multitude of cancers. However, the inappropriate concentrations of TKIs can result in ineffective treatment or the emergence of multiple adverse effects. Consequently, the development of a rapid and sensitive analytical method for TKIs is of paramount importance for the safe administration of drugs. In this work, solid-phase microextraction (SPME) probe combined with an electrospray ionization mass spectrometry (ESI-MS) coupling platform was constructed for rapid and sensitive determination of TKIs. The covalent organic frameworks (COFs) coated SPME probe was made of 2,4,6-tris(4-aminophenyl)-1,3,5-triazine (TAPT) and 2,5-dibutoxyterephthalaldehyde (DBTA) by in-situ layer-by-layer chemical bonding synthesis strategy. The TAPT-DBTA-SPME probe exhibited several advantageous properties which rendered it suitable for the enrichment of TKIs. Under the optimal conditions, the developed analytical method demonstrated a broad linear range (0.05-500.00 µg/L), a low limit of detection (0.02 µg/L) and a high enrichment factor (51-203) for TKIs. The developed analytical method was successfully applied to a pharmacokinetic study of TKIs in mouse plasma and tissue matrix, demonstrating that the proposed analytical method has promise for clinical applications and metabolic monitoring., 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 © 2024 Elsevier B.V. All rights reserved.)

Solid phase microextraction (SPME) in combination with high-resolution mass spectrometry was employed for the determination of metabolomic profile of mouse melanoma growth within in vitro 2D, in vitro 3D, and in vivo models. Such multi-model approach had never been investigated before. Due to the low-invasiveness of SPME, it was possible to perform time-course analysis, which allowed building time profile of biochemical reactions in the studied material. Such approach does not require the multiplication of samples as subsequent analyses are performed from the very same cell culture or from the same individual. SPME already reduces the number of animals required for experiment; therefore, it is with good concordance with the 3Rs rule (replacement, reduction, and refinement). Among tested models, the largest number of compounds was found within the in vitro 2D cell culture model, while in vivo and in vitro 3D models had the lowest number of detected compounds. These results may be connected with a higher metabolic rate, as well as lower integrity of the in vitro 2D model compared to the in vitro 3D model resulting in a lower number of compounds released into medium in the latter model. In terms of in vitro-in vivo extrapolation, the in vitro 2D model performed more similar to in vivo model compared to in vitro 3D model; however, it might have been due to the fact that only compounds secreted to medium were investigated. Thus, in further experiments to obtain full metabolome information, the intraspheroidal assessment or spheroid dissociation would be necessary.

With the growing requirements for the monitoring of heavy metals at an ultra-trace level in the environment and the real-time detection of toxic elements and their compounds for environmental pollution accidents, researchers devoted significant efforts to seeking atomic spectrometric methods that can be used for the simple, low cost, rapid, and field usable detection of targeted elements and their pollutants. Although conventional atomic spectrometric methods can easily realize the routine analysis of toxic elements in various samples in the laboratory, their bulky instruments and the complex sample matrix of environmental samples limit their further applications in field environmental analysis and complex sample analysis. Solid-phase microextraction (SPME) is an environmentally-friendly sample pre-treatment technique, which can significantly simplify sample pretreatment, increase sensitivity, and reduce the interference from the sample matrix, thus being one of the most ideal sampling techniques for the detection of ultra-trace toxic elements and their compounds by atomic spectrometry (AS) with high sensitivity and good selectivity. During the past decades, significant developments of SPME-AS including novel coating nanomaterials, desorption mode, miniaturized spectrometer, and its use for field elemental analysis have been made to improve the analytical performance in the detection of toxic elements and their pollutants. Herein, we present a short review concerning recent advances in elemental analysis by SPME-AS. Particularly, we highlight their application in the field of environmental analysis based on combing SPME with the available microplasma-based atomic spectrometer. The conclusion section addresses the current challenges and gives an outlook on potential future trends in the field of elemental analysis and elemental speciation analysis.

Ambient ionization allows desorption of molecules and formation of ions directly from samples in native environment. Compared with traditional ionization techniques, it has unique features of simplicity and convenience, thus has attracted considerable interest for the development of promising analytical methods. The concept of green analytical chemistry has raised concern about the safety of experimental process, and microextraction techniques can greatly reduce the use of organic solvents. The simple and fast operation of microextraction coincides with the advantages of ambient ionization mass spectrometry (AIMS) to perform high-throughput analysis. The combination of microextraction and AIMS significantly reduces the matrix effect and thus improves the analytical sensitivity and specificity in comparison with AIMS analysis alone. This review summarizes some typical combinations of microextraction and AIMS and their applications in forensic chemistry, food safety, and environmental monitoring.

This research was aimed at the development of the COMSOL Multiphysics® (CMP) model for simulating the headspace (HS) solid-phase microextraction (SPME) of volatile organic compounds (VOCs) from water using Carboxen/polydimethylsiloxane coating at 25 °C. The developed model is mainly based on existing theory and previous research on the numerical modeling of SPME. Fuller method was used to estimate diffusion coefficients in air as well as pores and voids of the coating. Coating-headspace distribution constants were estimated using linear solvation energy relationship (LSER) model and multiple regression obtained by Prikryl and Sevcik. Headspace-water constants were estimated using vapor pressures and activity coefficients were determined using UNIFAC model. Wilke and Chang method was chosen for estimating diffusion coefficients in water without stirring. Liss and Slater, and Southworth approaches were tested for estimating mass transfer coefficients at the headspace-water boundary under stirring. Southworth approach allowed obtaining benzene, toluene, ethylbenzene and o-xylene (BTEX) extraction profiles from water, which were closest to experimental profiles compared to other approaches. When using Southworth approach, root mean square deviation (RMSD) between experimental and simulated values for BTEX were 8.7–10% indicating the high accuracy of the model. The developed model was successfully applied for computational optimization of extraction parameters (stirring speed, fiber insertion depth, pressure, sample volume and the concentration of added salt). After minor modification, the model was also applied for optimization of preincubation time. It can be recommended for optimization of HSSPME-based analytical methods for VOCs quantification in water.

Solid-phase microextraction (SPME) has become a powerful sample preparation technique which allows to efficiently isolate and enrich analytes from complex matrixes. One of the most widespread SPME modes, consists of the extraction directly from the headspace (HS) which is equilibrated with the sample. In this sense, HS-SPME provides one of the best platforms for sample preparation, especially for the analysis of volatile and semi-volatile organic compounds. Furthermore, this technique has demonstrated to be versatile, sensitive, robust, and environmentally friendly when applied to samples coming from a diverse variety of fields such as bioanalysis, environmental sciences, food and cultural heritage. Moreover, during last years, the implementation of HS-SPME has dramatically grown along with the need to monitor complex systems over time using in situ and in vivo approaches, taking advantage of its noninvasive nature. In this review article, the authors present the fundamentals of this technique aiming to critically understand its advantages and limitations, highlighting the recent advances published in the last ten years. To this aim, special sections dealing with extractive phase development, technological advances and relevant applications in different fields have been carefully designed. Finally, some thoughts and perspectives about the future of the technique are also discussed.

Organophosphorus pesticides (OPPs) present in tea infusions pose a serious threat to human health. In this study, a sensitive method for the determination of OPPs was developed based on a direct-immersion solid-phase microextraction (DI-SPME) probe. By fine adjustment of the ratio and one-step polymerization of dihydroxy-functionalized zirconium-based metal-organic framework UiO-66-(OH) 2 and divinylbenzene-N-vinyl pyrrolidone (DVB-NVP) microspheres, the DVB-NVP@ UiO-66-(OH) 2 (D-N@U) composite with an optimal hydrophilic-lipophilic balance (HLB) was achieved. Furthermore, D-N@U was adhesively bonded to stainless-steel wires to fabricate a DI-SPME probe. OPPs, especially those with nonpolar properties characterized by a high octanol-water partition coefficient (log K OW ), were selectively and efficiently enriched on the D-N@U-coated DI-SPME probe from tea infusions. Coupled with a gas chromatography-flame photometric detector, the as-fabricated D-N@U-coated DI-SPME probe achieved good performance for OPPs analysis with a wide linear dynamic range of 0.10-500.00 μg/L and low detection limits of 1.96-6.69 ng/L. Moreover, in spiked samples, the recoveries and relative standard deviations were in the ranges of 73.12%-101.20 % and 1.03%-6.56 %, respectively. Owing to its simple operation, high extraction efficiency, and high sensitivity, this approach has great potential for the rapid determination of multiple pesticide trace-level residues in food., 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 © 2024 Elsevier B.V. All rights reserved.)

Analysis of heavy metals and their species in complex samples such as environment, biology and medicine is be of paramount importance due to their toxicity, persistence, and bioaccumulation. Considering the complexity of the sample matrix and the low concentration of heavy metals, sample preparation step should be exerted before analysis. Microextraction techniques have received extensive attention due to its miniaturization, quickness, low cost, environmental friendliness, and satisfactory extraction performance. So far, various formats based on microextraction techniques have been developed and applied to entrap heavy metals and related species. This review mainly concentrates on the recent development and applications of microextraction techniques including solvent-based liquid-phase microextraction and sorbent-based solid-phase microextraction for the detection and speciation of heavy metals in water, food, sediment, soil, hair, urine, and serum samples.

Large quantity of the antiviral drug arbidol is used for resisting virus infection like the Corona Virus Disease 2019 and influenza, resulting in unanticipated environmental pollution. Herein, to investigate the environmental risks of the unanticipated arbidol contamination, a novel in vivo sampling probe was developed based on a bromo-substituted porous organic polymer (Br-POP) and then adopted for tracking the bio-accumulation and bio-transformation of arbidol in living plants by coupling with a nano-electrospray ionization fourier-transform ion cyclotron resonance mass spectrometry (Nano-ESI-FT-ICR-MS) method. The established method showed good extraction performance towards arbidol with limit of detection (LOD) of 0.48 ng g -1 , and relative standard deviation (RSD) of single-and multiple- probe of 2.2 and 14 %. Owing to the interactions between the Br-POP and the target analytes, as well as the fast analysis process of Nano-ESI-FT-ICR-MS, <6 min was cost for total sampling and analysis duration, achieving hourly tracking of arbidol and its metabolites in this work. During 21-d in vivo tracking, the concentration of arbidol in living plant stems increased rapidly within 6 h and peaked at 413.93 ± 47.09 ng g -1 . Meanwhile, it was found that dissolved organic matters (DOM) had significant effect on arbidol behaviors in living plants, resulting in a decrease of the maximum concentration of arbidol in plant stems (152.70 ± 42.44 ng g -1 ) and the change of dominant metabolite of arbidol that the S-oxidation rather than N-demethylation product of arbidol was dominant with DOM participation. Additionally, the plant root secretion was found to be significantly altered by arbidol exposure. To summarized, the combination of in vivo SPME and the FT-ICR-MS analysis provide new and important information regarding arbidol contamination and related alternation of plant root metabolism., Competing Interests: Declaration of competing interest There is no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier B.V.)

Characterization of chemical composition in cigarette smoke is essential for establishing smoke-related exposure estimates. Currently used methods require complex sample preparation with limited capability for obtaining accurate chemical information. We have developed an in situ solid-phase microextraction (SPME) method for online processing of smoke aerosols and directly coupling the SPME probes with confined-space direct analysis in real time (cDART) ion source for high-resolution mass spectrometry (MS) analysis. In a confined space, the substances from SPME probes can be efficiently desorbed and ionized using the DART ion source, and the diffusion and evaporation of volatile species into the open air can be largely avoided. Using SPME-cDART-MS, mainstream smoke (MSS) and side-stream smoke (SSS) can be investigated and the whole analytical protocol can be accomplished in a few min. More than five hundred substances and several classes of compounds were detected and identified. The relative contents of 13 tobacco alkaloids were compared between MSS and SSS. Multivariate data analysis unveiled differences between different types of cigarette smoke and also discovered the characteristic ions. The method is reliable with good reproducibility and repeatability, and has the potential to be quantitative. This study provides a simple and high-efficiency method for smokeomics profiling of complex aerosol samples with in situ online extraction of volatile samples, and direct integration of extracted probes with a modified ambient ionization technique., 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 © 2024 Elsevier B.V. All rights reserved.)

Background: Saussurea costus Falc with synonymous Aucklandia costus, S. lappa, and A. lappa, is an ancient perennial plant native to Himalayan region. Purpose: S. costus possesses an ethnopharmacological background for treating diarrhea, tenesmus, dyspepsia, vomiting, inflammation, and age-related diseases because it contains many chemical compounds with different biological potentials. Study design: In the current study, we investigated the phytochemical constituents of S. costus and its anticancer potential against human colon (HCT116) and hepatic (HepG2) cancer cell lines. Methods: In the current study, we identified 122 different chemical compounds using a gas chromatography-mass spectrometry (GC–MS) method and investigated its extract's in vitro anticancer activity. Results: Dehydrocostus lactone, β-caryophyllene oxide, anethole, costunolide, β-sitosterol, and γ-bisabolene were recognized by GC–MS to have an anticancer potential as stated in published studies. Vanillosmin, santolinatriene and β-Sitosterol were identified for the first time in costus oil. Therefore, in the current study, S. costus extract induced apoptotic and anti-angiogenic effects against HCT116 and HepG2 cancer cell lines using in vitro and chorioallantoic membrane (CAM) models. Furthermore, S. costus extract has successfully potentiated the anticancer effect of doxorubicin (Dox), the common chemotherapeutic agent for different cancer type treatment. Conclusion: We can consider S. costus extract as a promising agent for human colon and hepatic cancers either alone or combined with Dox.

Mixed-mode ion-exchange materials have been implanted in different sorptive extraction techniques as they combine capacity and selectivity in a single material. They are a good option for concentrating ionic (or ionisable) compounds from complex samples using an appropriate washing step that simplifies the sample matrix. Research into the development of in-house mixed-mode ion-exchange materials is therefore a field of scientific interest. These materials are developed with the aim to improve the features of both the core and the ionic moieties attached. The study of the optimal extraction protocol to exploit the ionic interactions between the material and the target compounds is a key point in method development.This review is an overview of the preparation, characterisation, evaluation and application of in-house mixed-mode ion-exchange materials. It mainly covers the technique of solid-phase extraction; however, the latest advances in solid-phase microextraction, stir bar sorptive extraction and other emerging microextraction techniques are also presented. Examples of different applications that cover the extraction of different compounds in several types of samples are also illustrated.

Carbon fibers (CFs) were modified with carbon nanoparticles (CNPs) by a facile and fast flame preparation method. CNPs-CFs were observed by scanning electron microscope, and the nano-scaled granular structure on the surface was found. This material was also characterized by Raman microscope and X-ray photoelectron spectroscope. It was placed into a polyetheretherketone tube to get an extraction tube, which was connected with high performance liquid chromatography for online analysis. The tube displayed the effective extraction to several polycyclic aromatic hydrocarbons (PAHs), based on the possible hydrophobic and π stacking mechanism. Under the optimized conditions (60 mL of sample volume, 2.00 mL min−1 of sample rate, 0.5% of methanol in sample, 2.0 min of desorption time), an analytical method towards these PAH targets was established. The low limits of detection (0.001–0.005 μg L−1), satisfactory linear ranges (0.003–5.0 μg L−1, 0.003–10.0 μg L−1) and efficient enrichment factors (1012–3164) were presented. The method was applied to detect trace targets in several water samples and satisfactory results were obtained. The method provided some superiorities over other analytical methods, like online test, shorter time and better sensitivity.

In this work, covalent organic frameworks (COF) derived porous carbon was prepared through employing TpPa-1 as self-sacrificed template and used as solid phase microextraction (SPME) fiber coating. Owing to the high specific surface area and uniform pore size distribution, the resulting porous carbon exhibited excellent extraction ability toward PAHs. Coupled with gas-chromatography mass spectrometry (GC–MS), direct immersion SPME based on the resulting porous carbon was applied for analyzing eight polycyclic aromatic hydrocarbons (PAHs). Under the optimal conditions, the developed method exhibited a wide linear range for PAHs (30–30,000 μg kg−1) along with low limits of detection (LODs, 3.12–8.55 μg kg−1) and limits of quantification (LOQs, 10.4–28.5 μg kg−1). Moreover, the proposed method exhibited high reliability in its application on the determination of PAHs in soil samples, highlighting the application potential of COF derived porous carbons in monitoring aromatic pollutants in the environmental samples.

In this study, a metal-organic gels (MOGs)-coated solid-phase microextraction (SPME) fiber was developed and coupled with gas chromatography-mass spectrometer (GC–MS) for highly sensitive detection of pesticide residues in fruit samples. The MOGs-coated fiber was prepared using a simple in situ hydrothermal growth method, and the influencing factors in preparation process were investigated in detail. The prepared fiber showed high extraction efficiency, and excellent acid and alkali resistance. Under the optimized conditions, the developed SPME-GC–MS method showed wide linearity in the range of 0.01–10.00 ng mL−1 for eleven pesticides. The limits of detection (LODs, S/N=3) and quantification (LOQs, S/N = 10) were in the range of 0.001–0.052 ng mL−1 and 0.005 -0.094 ng mL−1, respectively. The relative standard deviations (RSDs, n = 5) of single steel wire and steel wire to steel wire were all below 10.7%. The method was successfully applied to determine pesticide residues in fruit samples with satisfactory recovery of 79.3% -117.7% and RSDs varying from 2.9% to 9.6%. The MOGs-coated fiber stayed stable after 100 times extractions without significant changes in extraction capacity. The results indicated that the MOGs provided a promising coating for SPME of pesticide residues in complicated matrix.

Pesticides are common pollutants that cause detriment to the ecological environmental safety and health of human due to their toxicity, volatility and bioaccumulation. In this work, an ultra-thin polymetallic layered double hydroxide (FeCoNi-LDH) with hollow nanoflower structure composite was synthesized using ZIF-67 as a self-sacrificial template, which was used as solid-phase microextraction (SPME) coating for the targeted capture pesticides, which could be combined with high-performance liquid chromatography (HPLC) to sensitive inspection pesticides in real water samples. Orthogonal experimental design (OAD) was applied to ensure the best SPME condition. Additionally, the adsorption properties were evaluated by chemical thermodynamics and kinetics. Under the optimized conditions, high adsorption capacity was obtained (117.0-21.5 mg g -1 ). A wide linear range (0.020-1000.0 μg L -1 ), low detection limit (0.008-0.172 μg L -1 ) and excellent reproducibility were obtained under the established method. This research provided a new strategy for designing hollow materials with multiple cations for the adsorption of anion or organic pollutants., Competing Interests: Declaration of competing interest We declare that we do not have any commercial or associative interest that represents a conflict of interest in connection with the work submitted. The work described has not been published before; it is not under consideration for publication anywhere else; and publication has been approved by all co-authors and the responsible authorities at the institute where the work has been carried out., (Copyright © 2024 Elsevier B.V. All rights reserved.)

This study was designed to develop a rapid and sensitive method for quantifying legacy and emerging per- and polyfluoroalkyl substances (PFASs) in environmental samples with solid-phase microextraction (SPME) coupled with mass spectrometry (MS). An innovative SPME probe was fabricated via in situ polymerization, and the probe coating was optimized with response surface methodology to maximize the fluorine-fluorine interactions and electrostatic properties and ensure high selectivity for the target PFASs with enrichment factors of 48-491. The coupled SPME and MS provided a rapid and sensitive method for analyses of PFASs, with excellent linearity (r ≥ 0.9962) over the concentration range 0.001-1 μg/L and remarkably low detection limits of 0.1-13.0 ng/L. This method was used to analyze trace PFASs in tap water, river water, and wastewater samples and proved to be a simple and efficient analytical method for selective enrichment and detection of contaminants in the environment., 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 © 2024 Elsevier B.V. All rights reserved.)

The improvement of the stability and adsorption properties of materials on targets in sample pre-treatment has long been an objective. Extensive efforts have been made to achieve this goal. In this work, metal-organic framework Ni-MOF precursors were first synthesized by solvothermal method using polyvinylpyrrolidone (PVP) as an ideal templating agent, stabiliser and nanoparticle dispersant. After carbonization and acid washing, the nanoporous carbon microspheres material (Ni@C-acid) was obtained. Compared with the material without acid treatment (Ni@C), the specific surface area, pore volume, adsorption performance of Ni@C-acid were increased. Thanks to its excellent characteristics (high stability, abundant benzene rings), Ni@C-acid was used as fiber coatings in headspace solid-phase microextraction (HS-SPME) technology for extraction and preconcentration of polycyclic aromatic hydrocarbons (PAHs) prior to gas chromatography-flame ionization detector (GC-FID) analysis. The experimental parameters of extraction temperature, extraction time, agitation speed, desorption temperature, desorption time and sodium chloride (NaCl) concentration were studied. Under optimal experimental conditions, the wide linear range (0.01-30 ng mL -1 ), the good correlation coefficient (0.9916-0.9984), the low detection limit (0.003-0.011 ng mL -1 ), and the high enrichment factor (5273-13793) were obtained. The established method was successfully used for the detection of trace PAHs in actual tea infusions samples and satisfied recoveries ranging from 80.94-118.62 % were achieved. The present work provides a simple method for the preparation of highly stable and adsorbable porous carbon microsphere materials with potential applications in the extraction of environmental pollutants., 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 © 2024 Elsevier B.V. All rights reserved.)

Simultaneous rapid screening of multiple drugs of abuse in environmental water facilitates effective monitoring and trend assessments. Herein, a novel porphyrin-based metal organic frameworks modified Ti 3 C 2 T x nanosheets (Cu-TCPP/Ti 3 C 2 T x ) composite was prepared and utilized as solid-phase microextraction (SPME) coating for the simultaneous analysis of 21 drugs from water samples. The composite was embedded with matrix-compatible polyacrylonitrile binder to prepare a coated blade with thin and uniform coating layer. Ambient mass spectrometry (MS) technique was used to create a coated blade spray-MS (CBS-MS) method for the quantitative determination of drugs in water samples. High throughput and automated sample preparation were achieved with the use of a Concept 96-well plate system, enabling analysis of 21 drugs of abuse within 1 min per sample, while using only 8 µL of organic solvent for desorption and CBS-MS detection. The developed method showed favorable linearity (R 2 ≥ 0.9983) in the range of 0.05 to 10 ng mL -1 , low limits of detection (1.5-9.0 ng L -1 ), sufficient recovery (67.6-133.2%), as well as satisfactory precision (RSDs≤13.5%). This study not only delivers a novel and efficient SPME coating composite, but also demonstrates the excellent performance of a high-throughput, efficient, and green analytical method for determination of drugs in environmental water., 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 © 2024 Elsevier B.V. All rights reserved.)

In situ measurement of the bioavailability of organic pollutants in soil is crucial for understanding their environmental behavior and assessing health risks. Due to the high heterogeneity of soil, microscale determination is crucial for achieving high accuracy, but few methods are available. In this study, microsized probes coated with polydimethylsiloxane (PDMS) were used to measure the bioavailability of polycyclic aromatic hydrocarbons (PAHs) in soil in situ. The concentrations of PAHs enriched by the PDMS-coated probes correlated well with the results of bioassays using earthworms (R 2  = 0.92-0.99) and ryegrass roots (R 2  = 0.92-0.99). Compared with other chemical extraction methods, such as n-butanol extraction, the proposed method has advantages such as in situ operation, microvolume analysis, and negligible interference to the soil environment. In the soil rhizosphere zone, PAHs bioavailability decreased in the following order: rhizosphere > near-rhizosphere > far-rhizosphere. The bioavailability of PAHs in soil amended with biochar was also successfully characterized by the proposed method. Thus, this study developed an in situ and microscale method to predict the bioavailability of organic pollutants in contaminated soils and provides new insight into migration and transformation processes in rhizosphere soil., 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 © 2024 Elsevier B.V. All rights reserved.)

Background: In vivo solid-phase microextraction (SPME) is a minimally invasive, non-exhaustive sample-preparation technique that facilitates the direct isolation of low molecular weight compounds from biological matrices in living systems. This technique is especially useful for the analysis of phytocannabinoids (PCs) in plant material, both for forensic purposes and for monitoring the PC content in growing Cannabis spp. plants. In contrast to traditional extraction techniques, in vivo SPME enables continuous tracking of the changes in the level of PCs during plant growth without the need for plant material collection. In this study, in vivo SPME utilizing biocompatible C18 probes and liquid-chromatography coupled to quadrupole time-of flight mass spectrometry (LC-Q-TOF-MS) is proposed as a novel strategy for the extraction and analysis of the acidic forms of five PCs in growing medicinal cannabis plants., Results: The SPME method was optimized by testing various parameters, including the extraction phase (coating), extraction and desorption times, and the extraction temperature. The proposed method was validated with satisfactory analytical performance regarding linearity (10-3000 ng/mL), limits of quantification, and precision (relative standard deviations below 5.5 %). The proposed method was then successfully applied for the isolation of five acidic forms of PCs, which are main components of growing medicinal cannabis plants. As a proof-of-concept, SPME probes were statically inserted into the inflorescences of two varieties of Cannabis spp. plants (i.e., CBD-dominant and Δ9-THC-dominant) cultivated under controlled conditions for 30 min extraction of tetrahydrocannabinolic acid (Δ9-THCA), cannabidiolic acid (CBDA), cannabigerolic acid (CBGA), cannabiviarinic acid (CBVA), and tetrahydrocannabivarinic acid (THCVA)., Significance and Novelty: The results confirmed that the developed SPME-LC-Q-TOF-MS method is a precise and efficient tool that enables direct and rapid isolation and analysis of PCs under in vivo conditions. The proposed methodology is highly appealing option for monitoring the metabolic pathways and compositions of multiple PCs in medicinal cannabis at different stages of plant growth., 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 © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

A facile strategy was developed for the fabrication of new nanoparticles-templated carbonaceous coating on a Nitinol (NiTi) fiber substrate. The NiTi fiber was first electrochemically anodized for the growth of nickel-titanium oxide nanoparticles (NiTiONPs). Thereafter, NiTiONPs were used as supporting templates for the derivation of carbonaceous nanoparticles (CNPs) via the hydrothermal reaction of glucose followed by carbonization in nitrogen atmosphere. The adsorption performance of the NiTi@NiTiONPs and the NiTi@NiTiO@CNPs fibers was evaluated using typical aromatic compounds as model analytes coupled to high-performance liquid chromatography with UV detection. The results clearly indicated that the NiTiO@CNPs coating exhibited higher extraction capability for polycyclic aromatic hydrocarbons (PAHs) than UV filters. For this purpose, several parameters of SPME with the NiTi@NiTiO@CNPs fiber were examined for the enrichment of PAHs in water. Under the obtained conditions, the calibration curves were linear over the concentration ranges of 0.05–200 μg·L–1 with correlation coefficients above 0.999. Limits of detection were between 0.012 μg·L–1 and 0.15 μg·L–1. Relative standard deviations (RSDs) of the intra-day and the inter-day analyses with the single fiber varied from 3.03% to 5.34% and from 3.31% to 5.82%, respectively. Moreover, RSDs for the fiber-to-fiber reproducibility with five fibers fabricated in different batches were between 4.89% and 7.10%. Finally, the applicability of the proposed method was validated via determination of target PAHs in real water samples with the relative recoveries of 82.6%–114%. Notably, the superior extraction performance of the fabricated fiber was still maintained even after more than 250 extraction/desorption cycles due to strong adhesion of the CNPs coating to NiTiONPs.

The waters and wastewaters around industrial areas are heavily polluted and have adverse effects on the ecosystems. The present study is mainly focused on the electropolymerization of ortho-phenetidine and co-deposited on a steel wire along with graphene oxide nanosheets as a novel coating for solid-phase microextraction of polycyclic aromatic hydrocarbons (PAHs) from aqueous media prior to gas chromatography-mass spectrometry. PAHs are composed of multiple aromatic rings which have been linked to skin, lung, bladder and liver. Cancer is a primary human health risk of exposure to PAHs. To obtain a firm and stable coating, several empirical factors relevant to the electrochemical process were investigated. Characterization for chemical structure and surface morphology of the synthesized nanocomposite was conducted with FT-IR spectroscopy and FE-SEM, respectively. XRD and TGA were applied to study the other properties of the nanocomposite. Some essential items involved in microextraction process were also checked in details. Under optimized case, validation parameters were assessed. Wide linearity (0.005–5.0 ng mL−1), low detection limits (0.4–4.3 pg mL−1) and good repeatability (3.6–9.5%) and reproducibility (7.6–11.8%) were achieved. The developed method was utilized to analyze contaminated real samples such as wastewater samples from coal processing industries and agricultural water samples collected from the vicinity of the industry in different seasons and high recoveries were obtained, finally.

The residues of polychlorinated naphthalenes (PCNs) produced in multiple industrial production and life processes are continuously entering environmental waters through atmospheric deposition and land drainage, and the water pollution caused by PCNs is continuing public concern due to their potential threat to aquatic ecosystems and public health. Herein, a new chlorine-functionalized covalent organic framework anchored graphene aerogel (COF-GA) was synthesized by covalent modification technology and used as fiber coating of solid-phase microextraction for synergically enhanced extraction of PCNs in environmental water. The extraction efficiency of COF-GA coated fiber was superior to commercial fiber due to the multiple interactions (π-π, hydrophobic interaction, and halogen bonding interaction). The COF-GA coated fiber has good stability, can avoid water vapor interference at 80 °C for a long time (30 -50 min) to maintain adsorption equilibrium, and can be reused at least 96 times. Combined with gas chromatography-tandem mass spectrometry, a sensitive method for the high-efficient enrichment (enrichment factors were 501 -7453 folds) and ultra-sensitive detection (LODs were 0.001 -0.428 pg/mL) of PCNs in environmental water was established. The enrichment factor for PCNs is significantly higher than in previous studies. This proposed method provides new technical support for the daily monitoring and risk assessment of trace PCNs in environmental water., 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 © 2024 Elsevier B.V. All rights reserved.)

Pesticides used in agriculture have low polarity and a tendency to accumulate in fatty tissues, posing potential risks to human health. Effective pre-treatment is crucial due to complex sample matrices and low concentrations of pesticide residues typically encountered in instrument analysis. In this study, polyaniline-coated kapok fiber (PANI-KF) was synthesized successfully using in-situ oxidative polymerization for use as sorbents in in-syringe SPME of pyrethroid pesticides (PYRs) and organochlorine pesticides (OCPs) from aqueous samples. Coating the natural KF with PANI maintained the hollow microtubular structure and fiber morphology while significantly enhancing the extraction efficiency. The extraction process was easily conducted by simply pulling and pushing the syringe plunger. The entire extraction process, utilizing 3 mg of PANI-KF, could be completed in approximately 3 min. Density functional theory results indicated that the adsorption mechanism of PANI-KF towards OCPs and PYRs mainly involved van der Waals interactions, π-π interactions, and weak hydrogen bonding interactions. With the coupling of gas chromatography-mass spectrometry, a quantification method was established that exhibited good linearities (R 2  > 0.990), and relative recoveries (87.2-108.5 %). The limits of detection ranged from 0.4 to 2.0 ng mL -1 and the matrix effects were negligible (-12.3-16.4 %). The validated in-syringe SPME-GC-MS method was successfully applied to determine pesticide residues in fruit juices, oral liquids and herbal extract granules with satisfactory accuracy and precision. PANI-KF exhibits remarkable promise as a sorbent for the extraction and enrichment of pesticide residues in aqueous samples, thereby contributing to the advancement of pesticide residue determination methodologies., 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 © 2024 Elsevier B.V. All rights reserved.)

Transplant centers are currently facing a lack of tools to ensure adequate evaluation of the quality of the available organs, as well as a significant shortage of kidney donors. Therefore, efforts are being made to facilitate the effective use of available organs and expand the donor pool, particularly with expanded criteria donors. Fulfilling a need, we aim to present an innovative analytical method based on solid-phase microextraction (SPME) - chemical biopsy. In order to track changes affecting the organ throughout the entire transplant procedure, porcine kidneys were subjected to multiple samplings at various time points. The application of small-diameter SPME probes assured the minimal invasiveness of the procedure. Porcine model kidney autotransplantation was executed for the purpose of simulating two types of donor scenarios: donors with a beating heart (HBD) and donors after cardiac death (DCD). All renal grafts were exposed to continuous normothermic ex vivo perfusion. Following metabolomic and lipidomic profiling using high-performance liquid chromatography coupled to a mass spectrometer, we observed differences in the profiles of HBD and DCD kidneys. The alterations were predominantly related to energy and glucose metabolism, and differences in the levels of essential amino acids, purine nucleosides, lysophosphocholines, phosphoethanolamines, and triacylglycerols were noticed. Our results indicate the potential of implementing chemical biopsy in the evaluation of graft quality and monitoring of renal function during perfusion., Competing Interests: Declaration of Competing Interest The authors declare no competing interests., (Copyright © 2023 Elsevier Inc. All rights reserved.)

Background: Polycyclic aromatic hydrocarbons (PAHs) are an important class of potentially toxic persistent organic pollutants in environmental water. Their concentrations are usually too low to allow for direct determination with analytical instruments, and the preconcentration is required prior to instrumental analysis. Solid phase microextraction (SPME) is considered as a high-performance green sample preparation technique for volatile and non-volatile organic compounds due to its high enrichment factor. In fact, the nature of SPME coatings governs the adsorption performance. Therefore, more efforts have devoted to the controlled construction of novel long-life SPME fibers with enhanced adsorption performance and improved adsorption selectivity., Results: 2D hierarchical core-shell ZnO/MnO 2 nanosheets (NSs) were constructed on a Nitinol (NiTi) fiber substrate by layer-by-layer assembly for enhanced and selective SPME of PAHs. Firstly, hexagonal ZnO NSs were electrodeposited on the NiTi substrate. Subsequently smaller secondary MnO 2 NSs were uniformly grown on the surface of ZnO NSs by a facile hydrothermal oxidation process. ZnO NSs were well protected by the chemically stable MnO 2 shell, making the coating highly durable and efficient for SPME application. Meanwhile, the ZnO/MnO 2 NSs coating demonstrated superior adsorption performance for PAHs. After the optimization of SPME conditions, the proposed SPME-HPLC-UV method exhibited good analytical performance for preconcentrating and determining trace PAHs with wide linear ranges (0.03-200 μg L -1 ) and low LODs (0.005-0.112 μg L -1 ) as well as good repeatability (1.4%-6.9%) and fiber-to-fiber reproducibility (5.3%-7.1%). Moreover, the proposed method showed good precision and recovery in the preconcentration and determination of target PAHs in real water samples., Significance: As compared with representative commercially available fibers, the NiTi@ZnO/MnO 2 NSs fiber showed enhanced adsorption efficiency and improved adsorption selectivity for PAHs. The constructed fiber can be used as an alternative to commercial fibers for the adsorption and preconcentration of target PAHs in the environmental water samples. Moreover, the preparation strategy is expected to provide new insights into the precisely controlled construction of the efficient and stable core-shell bimetallic oxide nanostructures on the superielastic NiTi-based fibers., 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 © 2024 Elsevier B.V. All rights reserved.)

Estrogens and bisphenols are typical endocrine disruptors (EDs) that pose a potential hazard to the human body due to their widespread presence in aqueous environments. In this study, a β-cyclodextrin porous crosslinked polymer (β-CD-PCP) was prepared in-situ on a glass fiber surface by a nucleophilic substitution reaction. An effective and sensitive solid phase microextraction method using functionalized glass fiber with β-CD-PCP coating as the adsorbent was established for the detection of 11 EDs in a water environment. The β-CD-PCP was in-situ prepared on a glass fiber surface by a nucleophilic substitution reaction. The β-CD-PCP successfully separated five estrogens (ESTs) and six bisphenols (BPs) through hydrophobic and π-π interactions. The conditions affecting extraction were optimized. Under the optimized conditions, the ESTs obtained a high enrichment effect (1795-2328), low limits of detection (0.047 µg L -1 ) and a good linearity range (0.2-15.0 µg L -1 ). Furthermore, the spiked recoveries of analyte ESTs in aqueous environments were between 82.9-115.7 %. The results indicated that the prepared functionalized glass fibers exhibited good adsorption properties, and the established analytical method was reliable for monitoring trace ESTs and BPs in aqueous environments., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests, (Copyright © 2024 Elsevier B.V. All rights reserved.)