Ozonolysis of phospholipids at the air-water interface intervened by polyfluoroalkyl substances.

Perfluoroalkyl substances (PFASs) are ubiquitous in the environment and even accumulate in the human body associated with their excellent stability and persistence. However, the effect and reaction mechanism at the molecular level on the cell phospholipid peroxidation remained unclear. In this work, the interfacial reaction of model phospholipids (POPG) intervened by per- and polyfluoroalkyl substances (PFASs) at the air-water interface of a hanged droplet exposed to ozone (O3) was investigated. Perfluorinated carboxylates and sulfonates were evaluated. Four-carbon PFASs promoted interfacial ozonolysis, but PFASs with longer carbon skeletons impeded this chemistry. A model concerning POPG packing was proposed and it was concluded that the interfacial chemistry was mediated by chain length rather than their functional groups. Four-carbon PFASs could couple into POPG ozonolysis by mainly reacting with aldehyde products along with minor Criegee intermediates, but this was not observed for longer PFASs. This is different from that condensed-phase Criegee intermediates preferred to reacting with per-fluoroalkyl carboxylic acids. These results provide insight into the adverse health of PFASs on cell peroxidation.

One-step online analysis of antibiotics in highly saline seawater by nano-based slug-flow microextraction.

The transition to mass spectrometry (MS) in the analysis of antibiotics in the marine environment is highly desirable, particularly in the enhancement of sensitivity for high-salinity (3.5 wt%) seawater samples. However, the persistence of complex operational procedures poses substantial challenges to this transition. In this study, a rapid method for the online analysis of antibiotics in seawater samples via nano-electrospray ionization (nESI) MS based on slug-flow microextraction (SFME) has been proposed. Comparisons with other methods, complex laboratory setups for sample processing are now seamlessly integrated into a single online step, completing the entire process, including desalination and detection, SFME-nESI-MS provides faster results in less than 2 min while maintaining sensitivity comparable to that of other detection methods. Using SFME-nESI, six antibiotics in high-salinity (3.5 wt%) seawater samples have been determined in both positive and negative ion modes. The proposed method successfully detected clarithromycin, ofloxacin, and sulfadimidine in seawater within a linear range of 1-1000 ng mL-1 and limit of detection (LOD) of 0.23, 0.06, and 0.28 ng mL-1, respectively. The method recovery was from 92.8% to 107.3%, and the relative standard deviation was less than 7.5%. In addition, the response intensity of SFME-nESI-treated high-salinity (3.5 wt%) samples surpassed that of untreated medium-salinity (0.35 wt%) samples by two to five orders of magnitude. This advancement provides an exceptionally simplified protocol for the online rapid, highly sensitive, and quantitative determination of antibiotics in high-salinity (3.5 wt%) seawater.

Efficient Extraction and Analysis of Nanoplastics by Ionic Liquid-Assisted Cloud-Point Extraction Coupled with Electromagnetic Heating Pyrolysis Mass Spectrometry.

Nanoplastics have attracted much attention due to their potential hazards. However, analysis of nanoplastics remains challenging. In this study, ionic liquid-assisted cloud-point extraction (IL-assisted CPE) was developed to enrich nanoplastics in the aqueous environment and further coupled with electromagnetic heating pyrolysis mass spectrometry. The use of trace ILs improves the extraction efficiency of CPE for nanoplastics. The effects of ILs (types, contents), nanoplastic properties (type, size), and environmental factors (aging time, humic acid content) were systematically investigated to evaluate the applicability. The limits of detection of poly(methyl methacrylate) (PMMA) and polystyrene (PS) were determined to be 1.78 and 2.67 µg/L, respectively. Real environmental samples including lake water, rainwater, and influent and effluent from wastewater treatment plant were analyzed with good accuracy (79.58-116.87%) and satisfactory precision (RSD ≤ 11.99%). A possible mechanism for ILs being absorbed into the ordered surfactant micellar and generating larger micelles to synergically enclose hydrophobic nanoplastics was proposed. This work provides a simple and efficient approach to the extraction and analysis of nanoplastics in aqueous environments.

The Role of Catecholamines in the Pathogenesis of Diseases and the Modified Electrodes for Electrochemical Detection of Catecholamines: A Review.

Catecholamines (CAs), which include adrenaline, noradrenaline, and dopamine, are neurotransmitters and hormones that critically regulate the cardiovascular system, metabolism, and stress response in the human body. The abnormal levels of these molecules can lead to the development of various diseases, including pheochromocytoma and paragangliomas, Alzheimer's disease, and Takotsubo cardiomyopathy. Due to their low cost, high sensitivity, flexible detection strategies, ease of integration, and miniaturization, electrochemical techniques have been extensively employed in the detection of CAs, surpassing traditional analytical methods. Electrochemical detection of CAs in real samples is challenging due to the tendency of poisoning electrode. Chemically modified electrodes have been widely used to solve the problems of poor sensitivity and selectivity faced by bare electrodes. There are a few articles that provide an overview of electrochemical detection and efficient enrichment of CAs, but there is a dearth of updates on the role of CAs in the pathogenesis of diseases. Additionally, there is still a lack of systematic synthesis with a focus on modified electrodes for electrochemical detection. Thus, this review provides a summary of the recent clinical pathogenesis of CAs and the modified electrodes for electrochemical detection of CAs published between 2017 and 2022. Moreover, challenges and future perspectives are also highlighted. This work is expected to provide useful guidance to researchers entering this interdisciplinary field, promoting further development of CAs pathogenesis, and developing more novel chemically modified electrodes for the detection of CAs.

Determination of amino acid metabolic diseases from dried blood spots with a rapid extraction method coupled with nanoelectrospray ionization mass spectrometry.

In this work, a rapid extraction method of methanol/water (95:5 v/v) with 0.1% formic acid was developed for extraction of amino acids from dried blood spots (DBS) for inherited metabolic diseases (IMDs). The combination of this extraction procedure with nanoelectrospray ionization mass spectrometry (nESI-MS) was used for the rapid analysis of amino acids. This approach with eliminating the chromatographic separation required only 2 min for the extraction of amino acids from DBS, which simplified the configuration and improved the timeliness. Dependence of the sensitivity on the operating parameters was systematically investigated. The LOD of 91.2-262.5 nmol/L and LOQ of 304-875 nmol/L which were lower than the cut-off values were obtained for amino acids within DBS. The accuracy was determined to be 93.82%-103.07% and the precision was determined to be less than 8.30%. The effectiveness of this method was also compared with the gold standard method (e.g., LC-MS/MS). The desalination mechanism was explored with interference mainly originated from the blood. These findings indicated that the rapid extraction procedure coupled with nESI-MS is capable of screening indicators for IMDs in complex biological samples.

Accurate Clinical Detection of Vitamin D by Mass Spectrometry: A Review.

Vitamin D deficiency is thought to be associated with a wide range of diseases, including diabetes, cancer, depression, neurodegenerative diseases, and cardiovascular and cerebrovascular diseases. This vitamin D deficiency is a global epidemic affecting both developing and developed countries and therefore qualitative and quantitative analysis of vitamin D in a clinical context is essential. Mass spectrometry has played an increasingly important role in the clinical analysis of vitamin D because of its accuracy, sensitivity, specificity, and the ability to detect multiple substances at the same time. Despite their many advantages, mass spectrometry-based methods are not without analytical challenges. Front-end and back-end challenges such as protein precipitation, analyte extraction, derivatization, mass spectrometer functionality, must be carefully considered to provide accurate and robust analysis of vitamin D through a well-designed approach with continuous control by internal and external quality control. Therefore, the aim of this review is to provide a comprehensive overview of the development of mass spectrometry methods for vitamin D accurate analysis, including emphasis on status markers, deleterious effects of biological matrices, derivatization reactions, effects of ionization sources, contribution of epimers, standardization of assays between laboratories.

Nicotiana alkaloids-intervened phospholipid ozonolysis at the air-water interface.

Cigarette nicotiana alkaloids associated with lung and cardiovascular diseases attack enormous attention. However, the mechanism at the molecular level between nicotiana alkaloids and phospholipid ozonolysis remains elusive. Herein, we investigated the interfacial ozonolysis of a hung droplet containing 1-palmitoyl-2-oleoyl-sn-phosphatidylglycerol (POPG) intervened by nicotiana alkaloids (4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone, NNK; rac-N'-nitrosonornicotine, NNN; nicotine; and (R,S)-N-nitrosoanasabine, NAT) and followed by on-line mass spectrometry analysis. NNK and NNN showed an acceleration on the interfacial ozonolysis, while nicotine and NAT inhibited this chemistry. Such acceleration/inhibition on POPG ozonolysis was positively correlated with nicotiana alkaloid concentrations. The reaction rate constants suggested that the ozonolysis of lung phospholipids exposed to cigarette smoke at the air-water interface occurred rapidly. A possible mechanism of the hydrophilic/oleophilic nature of nicotiana alkaloids mediating the packing density of POPG was proposed. NNK and NNN with a hydrophilic nature inserted into the POPG monolayer loosed the packing, but nicotine and NAT with an oleophilic nature let the POPG closely pack and shield the CC double bonds exposed to ozone (O3). These results gain the knowledge of nicotiana alkaloids mediated phospholipid ozonolysis at the molecule level and provide a method for online interfacial reaction studies associated with elevated indoor pollutants on public health.

Mass Spectrometry Analysis for Clinical Applications: A Review.

Mass spectrometry (MS) has become an attractive analytical method in clinical analysis due to its comprehensive advantages of high sensitivity, high specificity and high throughput. Separation techniques coupled MS detection (e.g., LC-MS/MS) have shown unique advantages over immunoassay and have developed as golden criterion for many clinical applications. This review summarizes the characteristics and applications of MS, and emphasizes the high efficiency of MS in clinical research. In addition, this review also put forward further prospects for the future of mass spectrometry technology, including the introduction of miniature MS instruments, point-of-care detection and high-throughput analysis, to achieve better development of MS technology in various fields of clinical application. Moreover, as ambient ionization mass spectrometry (AIMS) requires little or no sample pretreatment and improves the flux of MS, this review also summarizes its potential applications in clinic.

Aqueous microdroplets promote C-C bond formation and sequences in the reverse tricarboxylic acid cycle.

The reverse tricarboxylic acid cycle (rTCA) is a central anabolic network that uses carbon dioxide (CO2) and may have provided complex carbon substrates for life before the advent of RNA or enzymes. However, non-enzymatic promotion of the rTCA cycle, in particular carbon fixation, remains challenging, even with primordial metal catalysis. Here, we report that the fixation of CO2 by reductive carboxylation of succinate and α-ketoglutarate was achieved in aqueous microdroplets under ambient conditions without the use of catalysts. Under identical conditions, the aqueous microdroplets also facilitated the sequences in the rTCA cycle, including reduction, hydration, dehydration and retro-aldol cleavage and linked with the glyoxylate cycle. These reactions of the rTCA cycle were compatible with the aqueous microdroplets, as demonstrated with two-reaction and four-reaction sequences. A higher selectivity giving higher product yields was also observed. Our results suggest that the microdroplets provide an energetically favourable microenvironment and facilitate a non-enzymatic version of the rTCA cycle in prebiotic carbon anabolism.

Recent Advances in Catecholamines Analytical Detection Methods and Their Pretreatment Technologies.

Catecholamines (CAs), including adrenaline, noradrenaline, and dopamine, are neurotransmitters and hormones that play a critical role in regulating the cardiovascular system, metabolism, and stress response in the human body. As promising methods for real-time monitoring of catecholamine neurotransmitters, LC-MS detectors have gained widespread acceptance and shown significant progress over the past few years. Other detection methods such as fluorescence detection, colorimetric assays, surface-enhanced Raman spectroscopy, and surface plasmon resonance spectroscopy have also been developed to varying degrees. In addition, efficient pretreatment technology for CAs is flourishing due to the increasing development of many highly selective and recoverable materials. There are a few articles that provide an overview of electrochemical detection and efficient enrichment, but a comprehensive summary focusing on analytical detection technology is lacking. Thus, this review provides a comprehensive summary of recent analytical detection technology research on CAs published between 2017 and 2022. The advantages and limitations of relevant methods including efficient pretreatment technologies for biological matrices and analytical methods used in combination with pretreatment technology have been discussed. Overall, this review article provides a better understanding of the importance of accurate CAs measurement and offers perspectives on the development of novel methods for disease diagnosis and research in this field.

Interfacial Extraction to Trap and Characterize the Criegee Intermediates from Phospholipid Ozonolysis.

Criegee intermediates (CIs) play a significant role in cell membrane peroxidation, but their identification remains elusive at the molecular level. Herein, we combined interfacial extraction and sonic spray ionization mass spectrometry to study the oxidation reaction of 1-palmitoyl-2-oleoyl-sn-glycero-3-phospho-(1'-rac-glycerol) (POPG) mediated by ozone (O3) at/near the surface of a hung water droplet. On-line interfacial extraction and ionization provided a snapshot of the short-lived CIs. Experiments in which the content of water was varied provided evidence for the formation of CIs, which has not been previously observed. Capture experiments using 5,5-dimethyl-pyrroline N-oxide (DMPO) indicated that CIs could be selectively characterized, and the extracted ion current (EICs) of CIs vs DMPO-CI adducts further confirmed the successful observation of CIs. Theoretical calculation suggested that surface ozonolysis of POPG was mainly mediated by anti-CI. These results open a new route for aqueous surface reactive species identification, and benefit toward the understanding of disease development associated with cell oxidative stress mediated by CIs.

Ultrabright silicon nanoparticle fluorescence probe for sensitive detection of cholesterol in human serum.

A highly sensitive fluorescence-based assay for cholesterol detection was developed using water-dispersible green-emitting silicon nanoparticles (SiNPs) as a fluorescence indicator and enzyme-catalyzed oxidation product PPDox (Bandrowski's base) as a quencher. The SiNPs were facilely synthesized via a simple, one-step hydrothermal treatment using 3-[2-(2-aminoethylamino)ethylamino]propyl-trimethoxysilane (AEEA) as the silicon source, which has ultrahigh quantum yield and low phototoxicity. Under the catalysis of cholesterol oxidase (ChOx), hydrogen peroxide (H2O2) was generated as a result of cholesterol oxidation. Utilizing p-phenylenediamine (PPD) as the substrate for horseradish peroxidase (HRP) in the presence of H2O2 led to the production of PPDox. Based upon the inner filter effect (IFE), the established ultrasensitive fluorescent assay could accurately measure cholesterol. The limit of detection (LOD) of the assay was 0.018 µM with a linear range of 0.025-10 µM. The results for the detection of real serum samples by the proposed assay were comparable to those by a commercial reagent kit, demonstrating that our proposed strategy has high application potential in disease diagnosis and other related biological studies.

Extraction of parabens by melamine sponge with determination by high-performance liquid chromatography.

In the present study, we propose a novel method for the extraction of parabens in personal care products. A new, simple adsorptive material was obtained by combining metal-organic frameworks and melamine sponges using the adhesive property of polyvinylidene fluoride. This new material, metal-organic frameworks/melamine sponges, was found to be particularly suitable for solid-phase extraction. The structural characteristics of metal-organic frameworks/melamine sponges were first analyzed by scanning electron microscopy. Subsequently, solid-phase extraction was performed on sample solutions, and the extracted substances were then analyzed by high-performance liquid chromatography. Following optimization of important experimental conditions, excellent recovery rates were obtained. Our novel method was then applied to the extraction of four parabens (methylparahydroxybenzoates, ethylparahydroxybenzoates, propylparahydroxybenzoates, and butylparahydroxybenzoates) from real samples. The results yielded limits of detection of 0.26-0.41 ng/mL. The inter- and intra-day recoveries were 104.0-109.7% and 91.2-98.1%, respectively (relative standard deviation, <13.8%).

A semi-automatic solid phase extraction system based on MIL-101(Cr) foam-filled syringe for detection of triazines in vegetable oils.

In this study, several metal-organic framework-melamine foam columns were first developed and used as a laboratory-made semi-automatic solid phase extraction packed in syringe adsorber for the extraction of six triazine herbicides from vegetable oil samples coupled to high-performance liquid chromatography-tandem mass spectrometry. The metal-organic framework-foam columns were prepared using a simple approach by embedding the solid particles in melamine foam using polyvinylidene difluoride physical encapsulation. The method was applicable to a wide variety of metal-organic framework materials, and the incorporated materials retained their unique properties. Key factors that affect the extraction efficiency, including the MIL-101(Cr) amount, sample flow rate, type and volume of the eluting solvent, and flow rate of eluting solvent, were investigated. Under optimum conditions, the proposed method exhibited low limits of detection (0.017-0.096 ng/mL, S/N = 3) for six triazines. The relative standard deviations calculated for all herbicides ranged from 0.2 to 14.9%. This study demonstrated that the MIL-101(Cr)-foam column can be used as a high-quality adsorption material for the detection of triazines in vegetable oils.

Vortex-assisted solid-phase extraction based on metal-organic framework/chitosan-functionalized hydrophilic sponge column for determination of triazine herbicides in environmental water by liquid chromatography-tandem mass spectrometry.

In the presented work, MIL-101(Cr) and chitosan were directly embedded on the skeleton of melamine sponge material using a simple and environmentally friendly method. Chitosan acts not only as an adhesive during the preparation of functionalized sponges, but also as an adsorption adjuvant in herbicide detection. Unlike other polymers, chitosan has excellent hydrophilicity and contains numerous adsorption sites; thus, it enables the sponge material to be used for determination of contaminants in an aqueous phase. Scanning electron microscopic (SEM) analysis showed that the coating material was uniformly distributed on the skeleton of melamine sponge. The prepared material was used as a sorbent in a vortex-assisted solid-phase extraction and combined with high performance liquid phase tandem mass spectrometry for the extraction and trace determination of six triazines in water samples (Atraton, Desmetryn, Prometon, Ametryn, Prometryn and Dimethametryn). Several parameters that affect the extraction efficiencies were investigated. Under the optimal conditions (MIL-101(Cr) loading, 150 mg; sample pH, 7; salt concentration, 0%; adsorption time, 3 min; desorption solvent, 1.5 mL acetonitrile; desorption time, 4 min), the proposed method was successfully used in the determination of trace triazines in five real water samples (drinking water, tap water, lake waters and river water), satisfactory recoveries were obtained in the range of 78.9%-118.6%. The limits of detection of the proposed method in detecting triazine herbicides in spiked water samples ranged from 0.014 to 0.045 ng mL-1.

One-step fabrication of hydrophilic MIL-68(Al)/Chitosan-coated melamine sponge for vortex-assisted solid-phase extraction of parabens in water samples.

A novel vortex-assisted solid-phase extraction method based on MIL-68(Al)/Chitosan-melamine sponge column (or V-MIL-68(Al)/CS-SC-SPE) is presented in this paper. The MIL-68(Al)/Chitosan-sponge column was prepared by a simple infiltration method and a preparation process that does not consume organic solvents. Scanning electron microscopy was used to characterize the functionalized sponge columns, and the skeleton and pores of the melamine sponge were successfully modified with the coating material (MIL-68(Al) and chitosan). Chitosan was used successfully not only as an adsorption adjuvant material, but also as an adhesive in the preparation of MIL-68(Al)/CS coating sponge materials. The presented method was further combined with high performance liquid chromatography (HPLC) and used in the determination of trace parabens (including methyl-, ethyl-, propyl- and butyl-parabens) in environmental water samples. Several important factors that affect the extraction performance were investigated. Under the optimum conditions, the method was successfully used to detect the four kinds of parabens in different water samples (domestic water, lake water and river water). The limits of detection ranged between 0.21 and 0.50 ng/mL, and the relative standard deviations for all parabens were below 10.8%.

Application of an in-situ formulated magnetic deep eutectic solvent for the determination of triazine herbicides in rice.

In this work, a rapid, convenient, sensitive, and cost-effective in-situ formed magnetic deep eutectic solvent based on a dispersive liquid-liquid extraction method was developed for the determination of triazine herbicides in rice. A novel tetrabutylammonium chloride (TBAC) based magnetic deep eutectic solvent (MDES), [TBAC/ethylene glycol][FeCl4] was generated by means of an simple in-situ reaction of the deep eutectic solvent (DES) with iron chloride in the sample solution. The solvent which has high affinity for target analytes and magnetic ability was successfully employed as an extraction solvent and simplified both the extraction and separation procedure. A series of parameters influencing the extraction efficiency were investigated. Under optimal conditions, calibration curves for the target triazine herbicides were obtained in the ranges of 5-1000 ng g-1, with correlation coefficients greater than 0.9910. The limits of detection (LOD) and quantification (LOQ) were in the range of 1.49-3.10 ng g-1 and 4.96-10.34 ng g-1, respectively. The precision of intra- and inter-day were under 6.2% and 9.6%, respectively, and the precision between laboratories were lower than 7.5%. The accuracy of the method varied from 84.9 to 117.5%. Furthermore, the method showed satisfactory matrix effect and robustness. These results indicate that the technique is suitable for rice sample analysis.

MIL-101(Cr)/MWCNTs-functionalized melamine sponges for solid-phase extraction of triazines from corn samples, and their subsequent determination by HPLC-MS/MS.

In the presented work, we proposed the use of polyvinylidene difluoride (PVDF) as a coupling agent to load MIL-101(Cr) and carboxylated multi-walled carbon nanotubes (MWCNTs) on the skeleton of melamine sponge (MeS) for the preparation of novel extraction media with high-efficiency. The morphology and structure of this composite were characterized by scanning electron microscopy (SEM) analyses. The obtained MIL-101(Cr)/MWCNTs functionalized MeS(MIL/M-MeS) cube was used as a sorbent for the solid-phase extraction (SPE) of six triazines (Atraton, Simetryne, Prometon, Ametryn, Propazine, and Prometryn) spiked corn samples. Several parameters that may affect the extraction efficiencies, including type and volume of extraction solvent, times of ultrasonic extraction, adsorption, and desorption; type and volume of desorption solvent, were optimized. This was followed by elution containing the herbicides, which were quantified using high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). Under optimum conditions, the analytical method for the preparation of MIL/M-MeS cube produced satisfactory recoveries and repeatability. The LODs of the method when applied to spiked corn samples were in the range of 0.01-0.04 ng g-1 (LODs = 3δ/k). The relative intra- and inter-day recoveries ranged from 90.30 to 116.50% and 92.38-116.24%, respectively, and relative standard deviations ranged from 1.08 to 12.32% and 5.36-16.23%, respectively.

Development of a novel acidic task-specific ionic liquid-based effervescence-assisted microextraction method for determination of triazine herbicides in tea beverage.

In this study, a simple, rapid, sensitive and eco-friendly effervescence-assisted microextraction method was established for the determination of triazine herbicides in tea beverage samples. For the first time, acidic task-specific ionic liquid [C4mim][HSO4] was utilized not only as extraction solvent, but also as Brønsted acid to generate carbon dioxide which can enhance mass transfer between extraction solvent and analytes. Extraction parameters, including amounts of ionic liquid and sodium bicarbonate, concentration of salt, pH value of the sample solution and volume of elution solvent, were evaluated. Under the optimal conditions, the developed method had good linearity in the range of 1-200 ng mL-1 or 2-200 ng mL-1 with the correlation coefficients higher than 0.9990. Additionally, minimum detection and quantification limits were 0.08 ng mL-1 and 0.25 ng mL-1, respectively, precision was in the satisfactory range of 0.8%-9.3%, and recovery of the herbicides from the real samples, which was varied from 76.3% to 135.9%, was in the acceptable range. Moreover, stability of the analytes in sample solution and robustness of the experiment were measured and obtained satisfactory results. In addition, the method does not require external energy supplied by an external source or apparatus. These results demonstrate that the method could be applied for determining trace triazine herbicides in beverage samples.

Solid-phase microextraction of triazine herbicides via cellulose paper coated with a metal-organic framework of type MIL-101(Cr), and their quantitation by HPLC-MS.

Cellulose paper was coated with the metal-organic framework MIL-101(Cr) in a chitosan matrix and utilized for thin-film microextraction (TFME). The coated paper possesses excellent extraction efficiency for the triazine herbicides atraton, desmetryn, secbumeton, prometon, ametryn, dipropetryn, and dimethametryn. High-performance liquid chromatography-tandem mass spectrometry was applied to quantify target analytes. The effects of mass ratio of MIL-101(Cr) to chitosan, sample pH value, time of adsorption and desorption, and type and volume of desorption solvent on extraction efficiency were optimized. Under the optimal conditions, the method has limits of detection between 1.5 and 22 ng·L-1. The recoveries of triazines from spiked tap water, drinking water, lake water and river water range from 77.0 to 125.3%, with relative standard deviations of <17.4%. Graphical abstract Cellulose paper was modified with metal-organic framework MIL-101(Cr)/chitosan by using a simple, efficient and environmentally friendly approach. The modified cellulose paper was then used as a novel extraction phase in thin-film microextraction (TFME).