A smartphone-enabled visual platform for detecting aflatoxins in peanut oil using colorimetric analysis coupled with magnetic imprinted solid-phase extraction.

The study aimed to develop a rapid and sensitive colorimetric platform based on the Emerson reaction to visualize and determine total aflatoxins (AFs) in peanut oil. This method offers the advantage of fast screening for AFs (AFB1, AFB2, AFG1, and AFG2), eliminating the need for specific antibodies. The proposed approach combined colorimetric detection with magnetic dummy imprinted solid-phase extraction and purification, enhancing sensitivity and selectivity. The oxidizer aided the colorless AFs in reacting with 4-aminoantipyrine, producing green condensates. Thus, a dual-mode approach was developed for AFs detection, employing both UV-vis colorimetric and smartphone-based colorimetry. Both methods showed a good linear relationship with the concentration of AFs. Notably, the smartphone-based method demonstrated a detection range of 0.5-57 µg/kg, with a detection limit as low as 0.21 µg/kg. The suggested colorimetric methods present a promising potential for onsite detection and fast screening of AFs in actual samples.

Development of a NiFe2O4 covalent organic framework based magnetic solid-phase extraction approach for specific capture of quinolones in animal innards prior to UHPLC-Q-Orbitrap HRMS detection.

This study aimed to present a selective and effective method for analyzing quinolones (QNs) in food matrix. Herein, a NiFe2O4-based magnetic sodium disulfonate covalent organic framework (NiFe2O4/COF) was prepared using a simple solvent-free grinding method, and was adopted as a selective adsorbent for magnetic solid phase extraction of QNs. Coupled with UHPLC-Q-Orbitrap HRMS, an efficient method for simultaneous detection of 18 kinds of QNs was established. The method exhibited good linearity (0.01-100 ng g-1), high sensitivity (LODs ranging from 0.0011 to 0.0652 ng g-1) and precision (RSDs below 9.5%). Successful extraction of QNs from liver and kidney samples was achieved with satisfactory recoveries ranging from 82.2% to 108.4%. The abundant sulfonate functional groups on NiFe2O4/COF facilitated strong affinity to QNs through electrostatic and hydrogen bonding interactions. The proposed method provides a new idea for the extraction of contaminants with target selectivity.

Tuning the planarity of molecularly imprinted covalent organic frameworks for selective extraction of ochratoxin A in alcohol samples.

Here, we report a monomer planarity modulation strategy for room-temperature constructing molecularly imprinted-covalent organic frameworks (MI-COFs) for selective extraction of ochratoxin A (OTA). 2,4,6-triformylphloroglucinol (Tp) was used as basic building block, while three amino monomers with different planarity were employed as modulators to explore the effect of planarity on the selectivity of MI-COFs. The MI-TpTapa constructed from Tp and the lowest planarity of monomer Tapa gave the highest selectivity for OTA, and was further used as the adsorbent for dispersed-solid phase extraction (DSPE) of OTA in alcohol samples. Coupling MI-TpTapa based DSPE with high-performance liquid chromatography allowed the matrix-effect free determination of OTA in alcohol samples with the limit of detection of 0.023 µg kg-1 and the recoveries of 91.4-97.6%. The relative standard deviation (RSD, n = 6) of intra and inter day was <3.2%. This work provides a new way to construct MI-COFs for selective extraction of hazardous targets.

Molecularly imprinted resin modified with ionic liquid for dispersive filter extraction and determination of perfluoroalkyl acids in eggs.

Perfluoroalkyl acids (PFAAs) are emerging pollutants that endangers food safety. Developing methods for the selective determination of trace PFAAs in complex samples remains challenging. Herein, an ionic liquid modified porous imprinted phenolic resin-dispersive filter extraction-liquid chromatography-tandem mass spectrometry (IL-PIPR-DFE-LC-MS/MS) method was developed for the determination of perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) in eggs. The new IL-PIPR adsorbent was prepared at room temperature, which avoids the disorder and instability of the template at high temperatures. The imprinting factor of IL-PIPR for PFOA and PFOS exceeded 7.3. DFE, combined with IL-PIPR (15 mg), was used to extract PFOA and PFOS from eggs within 15 min. The established method exhibits low limits of detection (0.01-0.02 ng/g) and high recoveries (84.7%-104.7%), which surpass those of previously reported methods. This work offers a new approach to explore advanced imprinted adsorbents for PFAAs, efficient sample pretreatment technique, and analytical method for pollutants in foods.

Two-dimensional hydrophilic imprinted resin-graphene oxide composite for selective extraction and rapid determination of gibberellin traces in licorice samples.

This study presents novel methodologies and materials for selectively and sensitively determining gibberellin traces in licorice to address food safety concerns. A novel hydrophilic imprinted resin-graphene oxide composite (HMIR-GO) was developed with fast mass transfer, high adsorption capacity, and exceptional aqueous recognition performance for gibberellin. Leveraging the advantages of molecular imprinting, hydrophilic resin synthesis, and rapid mass transfer characteristics of GO, HMIR-GO was employed as an adsorbent, showing resistance to matrix interference. Coupled with HPLC, a rapid and selective method for determining gibberellin was established. Under optimal conditions, the method exhibited a wide linear range (0.02-5.00 µg g-1, r = 0.9999), low detection limits (3.3 ng g-1), and satisfactory recoveries (92.0-98.4%), enabling the accurate and rapid detection of gibberellin in licorice. This study introduces a pioneering strategy for the selective extraction and determination of trace gibberellin levels, offering insights for similar applications in functional foods.

Magnetic solid-phase extraction of tetracyclines from milk using metal-organic framework MIL-101(Cr)-NH2 functionalised hydrophilic magnetic nanoparticles.

Novel metal-organic framework MIL-101(Cr)-NH2 functionalised hydrophilic polydopamine-modified Fe3O4 magnetic nanoparticles (Fe3O4@PDA@MIL-101(Cr)-NH2) were synthesised and used as magnetic solid-phase extraction (MSPE) adsorbents for extracting tetracyclines (TCs) from milk samples. The integrated Fe3O4@PDA@MIL-101(Cr)-NH2 exhibited convenient magnetic separation and exceptional multi-target binding capabilities. Furthermore, the PDA coating significantly enhanced the hydrophilicity and extraction efficiency of the material, thereby facilitating the extraction of trace TCs. Various factors affecting MSPE, such as adsorbent dosage, extraction time, pH value, and desorption conditions, were optimised. The developed MSPE method coupled with high-performance liquid chromatography demonstrated good linearity (R2 ≥ 0.9989), acceptable accuracy (82.2%-106.1%), good repeatability (intra-day precision of 0.8%-4.7% and inter-day precision of 1.1%-4.5%), low limits of detection (2.18-6.25 µg L-1), and low limits of quantification (6.54-18.75 µg L-1) in TCs detection. The approach was successfully used for the quantification of trace TCs in real milk samples.

NiFe-LDH/nylon 6 composite electrospun on polypropylene membrane: A new extractive device development for porous membrane protected micro-solid-phase extraction of organophosphate pesticides from fresh fruit juice samples coupled with liquid chromatography tandem mass analysis.

A unique strategy for developing porous membrane protected micro-solid phase extraction has been provided. An electrospun composite was fabricated on the sheet of membrane. To this end, NiFe-layered double hydroxide/Nylon 6 composite nanofibers were coated on a polypropylene membrane sheet followed by folding into a pocket shape, which were then utilized as a novel extractive device to extract of organophosphorus pesticides from fresh fruit juice samples prior to liquid chromatography-tandem mass spectrometry (LC-MS/MS) analysis. The fabricated hybrid composites were successfully characterized. The effective parameters on extraction performance were investigated. LODs were 0.020-0.065 ng mL-1. Excellent linearity (R2≥0.996) was observed between 0.05 and 100.0 ng mL-1. RSDs% were in the range of 3.1-5.8% (intra-day, n = 3) and 2.6-5.5% (inter-day, n = 3×3). Satisfactory related recovery values within the acceptable range of 90.7-111.2% with RSDs% below 6.7% were achieved for the analysis of real samples.

Development of a smartphone-integrated microfluidic paper-based optosensing platform coupled with molecular imprinting technique for in-situ determination of histamine in canned tuna.

We reported the development of a smartphone-integrated microfluidic paper-based optosensing platform for in-situ detection and quantification of histamine in canned tuna. Molecularly imprinted polymers were synthesized via precipitation polymerization and utilized as dispersive solid phase extraction sorbent to selectively extract histamine from canned tuna. Carbon quantum dots functioning as a fluorescent probe were synthesized and introduced onto the microzones of the microfluidic paper device. This facilitated a noticeable fluorescence color change from dark red to vivid blue upon the addition of histamine. The change in fluorescence on the paper device was converted into specific RGB values using a portable UV light box combined with a smartphone. This assay achieved the limit of detection of 14.04 mg/kg with the linear range from 20 to 100 mg/kg of histamine in canned tuna. The entire molecular imprinting-microfluidic optosensing test could be completed in 45 min including sample preparation.

Thermosensitive molecularly imprinted polymer coupled with HPLC for selective enrichment and determination of matrine in traditional Chinese medicine.

In this study, a temperature-sensitive molecularly imprinted polymer was prepared by using the bifunctional monomer with the critical phase transition characteristics. Infrared spectrometry, scanning electron microscopy, and specific surface area testing were used to characterize the polymers. Then, the recognizing properties of the polymers were studied. Based on the prepared smart polymers, an SPE-HPLC analytical method for the determination of quinolizidine alkaloids in the extracts of Sophora flavescens was established and verified. Finally, the smart polymers were applied to the enrichment of quinolizidine alkaloids in plant extracts. By changing the temperature and solvents of the solid phase extraction conditions, the extraction process can increase the concentration of quinolizidine alkaloids by 4.3 to 5.2 folds. The extraction process has mild conditions and less time consumption, avoiding the use of a large number of toxic reagents, which indicate that the extraction process are more efficient and environmentally friendly.

The pesticide residue analysis in commodities with high content of chlorophyll based on the quick, easy, cheap, effective, rugged, and safe method: A review.

In multiresidue analysis, the QuEChERS (Quick, Easy, Cheap, Effective, Rugged, and Safe) is one of the most popular techniques routinely used by researchers during pesticide analysis of food and vegetable samples. Originally, the QuEChERS method was developed for analysis of pesticide residues from fruits and vegetables, but rapidly gained popularity in the extraction of analytes from different matrices. This analytical approach shows several advantages over traditional extraction techniques: it requires lower sample and solvent amounts while shortening the time of sample preparation. However, it presents some limitations for complex matrices such as those containing high amounts of chlorophyll. To overcome the problem of strong matrix effect and influence of interferences, different approaches are applied. Most are concerning modifications of the cleanup step, that is, sorbent type and its amount. Optimization of other parameters, such as sample size, hydration level, extraction solvent, and buffering, also has an impact on overall performance. Combining proper sample preparation with modern highly sensitive and selective detection techniques enables receiving desired limits of quantification. This article presents an overview of strategies employed by researchers for analysis of green, high chlorophyll content commodities and results obtained in their studies.

Solid-phase extraction methods for nucleic acid separation. A review.

The separation and purification of biomacromolecules such as nucleic acid is a perpetual topic in separation processes and bioengineering (fine chemicals, biopharmaceutical engineering, diagnostics, and biological characterization). In principle, the solid-phase extraction for nucleic acid exhibits efficient phase separation, low pollution risk, and small sample demand, compared to the conventional liquid-phase extraction. Herein, solid-phase extraction methods are systematically reviewed to outline research progress and explore additional solid-phase sorbents and devices for novel, flexible, and high-efficiency nucleic acid separation processes. The functional materials capture nucleic acid, magnetic and magnetic-free solid-phase extraction methods, separation device design and optimization, and high-throughput automatable applications based on high-performance solid-phase extraction are summarized. Finally, the current challenges and promising topics are discussed.

Dispersive clean-up process based on a magnetic graphene oxide nanocomposite for determination of 2-glycerol monopalmitate in olive oil prior to GC-FID and GC-MS analysis.

BACKGROUND: Recently, methods have been developed for the better quality control, fraud detection and analytical investigation of olive oil. Magnetic graphene oxide (GO) material is known for its reusability, high adsorption capability and stability in food sample preparation. Monopalmitine or 2-glycerol monopalmitate (2-GMP) is one of the main parameters in the quality assay and classification of olive oil, which can be classified as extra virgin ≤ 0.9% and olive pomace ≤ 1.2. Hence, newly synthesized magnetic GO (MGO) and commercial silica-gel were used as a dispersive solid-phase clean-up (d-SPE) sorbent to determine 2-GMP value in olive oil samples prior to gas chromatography (GC) analysis. The d-SPE method is validated with olive oil certified reference material (CRM) with respect to silica-gel and a MGO nanocomposite. RESULTS: The developed d-SPE method was applied for various virgin, refined and pomace olive oil samples to determine the value of 2-GMP%. The presence of 2-GMP in the samples was confirmed by GC-mass spectrometry analysis based on silylation derivatives of the analyte. Finally, the d-SPE-MGO method was determined 2-GMP% as 1.9% for pomace olive oil, 0.6% for refined olive oil, 0.4% for virgin olive oil and 3.1% for CRM. The MGO provided satisfactory clean-up recovery (124%) in the acceptable data range for CRM2018, and silica-gel also provided satisfactory recovery (83%) for CRM2018. The proposed method performed with higher sensitivity and efficiency for screening 2-GMP% in olive oil. CONCLUSION: The MGO based d-SPE method was applied for clean-up purposes to determine 2-GMP%. It proved superior via its advantageous features of super quickness, easy isolation with an external magnet and the highly efficient exclusion of all the coexisting interfering peaks conventionally generated with a standard silica-gel material. These methods based on MGO and silica-gel are reflected in the dispersive mode of extraction and can be used as alternatives to conventional methods. Considering the benefits of the consumption of significantly fewer sorbents and less time required regarding the dispersive methods, the methods can be utilized as alternatives in contrast to conventional techniques. © 2021 Society of Chemical Industry.

Fabrication of a Magnetic Fluorinated Covalent Organic Framework for the Selective Capture of Benzoylurea Insecticide Residue in Beverages.

Efficient capture of benzoylurea insecticide (BU) residue in food is a vital procedure for food safe monitoring. Herein, a core-shell structured magnetic fluorinated covalent organic framework with good magnetic responsiveness and abundant fluorine affinity sites was successfully synthesized, suitable for magnetic solid-phase extraction (MSPE) of BUs. Using a room-temperature synthesis strategy, the magnetic fluorinated covalent organic framework was fabricated by in situ polymerization of 1,3,5-tris(4-aminophenyl) triazine (TAPT) and 2,3,5,6-tetrafluoroterephthaldehyde (TFTA) on the surface of carboxylated Fe3O4 nanoparticles. The competitive adsorption experiment and molecular simulation verified that this magnetic fluorinated covalent organic framework possesses favorable adsorption affinity for BUs. This magnetic fluorinated covalent organic framework could be easily regenerated and reused at least eight times with no reduction of enrichment performance. Combining this magnetic fluorinated covalent organic framework-based MSPE with high-performance liquid chromatography-tandem mass spectrometry, a novel sensitive method for the analysis of BUs was developed. In yellow wine and fruit juice samples, good linear correlations were obtained for BUs in the range of 10-2000 and 20-4000 ng·L-1, respectively. The limit of quantitation of the BUs ranged from 1.4 to 13.3 ng·L-1 in the two beverage matrices. Desirable precision was achieved, with intraday and interday relative standard deviations lower than 11%.

Sampling of Volatiles in Closed Systems: A Controlled Comparison of Three Solventless Volatile Collection Methods.

Complex inter-organismal communication among plants, insects, and microbes in natural and agricultural ecological systems is typically governed by emitted and perceived semiochemicals. To understand and ultimately utilize the role of volatile semiochemicals in these interactions, headspace volatiles are routinely collected and analyzed. Numerous collection systems are available (e.g., static or dynamic; adsorption or absorption) where the choice of technique should be dependent upon the plant, insect, or microbial ecological system studied, the information sought, and the limitations of each method. Within these constraints, it remains necessary that each method detects and provides the accurate in situ, or in vitro, volatile profile of the studied system. Herein, we analyzed and compared the pros and cons of three solventless, thermal desorption systems (SPME, Tenax/cold trap, SPDE) using a synthetic standard blend of compounds mimicking a simple natural blend (benzaldehyde, b-caryophyllene, (Z)-3-hexenol, 6-methyl-5-hepten-2-one, and limonene). Direct splitless injection and Super Q collections of the standard blend were used as controls. The results indicated that related qualitative, as well as quantitative differences, could be correlated with adsorbent sampling capacity and structural bias. The results for Tenax/cold trap and SPDE also were affected by sampled headspace volumes. All solventless techniques exhibited high analytical reproducibility, with SPME and SPDE providing ease of use, low cost, and minimal instrument modifications. The more complex Tenax/cold trap technique provided higher collection efficiency. Using these results, we provide guidance for technique selection for chemical communication applications.

Chitosan-Graphene Oxide Composite Membranes for Solid-Phase Extraction of Pesticides.

Solid-phase extraction (SPE) coupled to LC/MS/MS analysis is a valid approach for the determination of organic micropollutants (OMPs) in liquid samples. To remove the greatest number of OMPs from environmental matrices, the development of innovative sorbent materials is crucial. Recently, much attention has been paid to inorganic nanosystems such as graphite-derived materials. Graphene oxide has been employed in water-purification processes, including the removal of several micropollutants such as dyes, flame retardants, or pharmaceutical products. Polysaccharides have also been widely used as convenient media for the dispersion of sorbent materials, thanks to their unique properties such as biodegradability, biocompatibility, nontoxicity, and low cost. In this work, chitosan-graphene oxide (CS_GO) composite membranes containing different amounts of GO were prepared and used as sorbents for the SPE of pesticides. To improve their dimensional stability in aqueous medium, the CS_GO membranes were surface crosslinked with glutaraldehyde. The composite systems were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, thermogravimetric analysis, swelling degree, contact angle, and mechanical measurements. As the GO content increased, a decrease in surface homogeneity, an improvement of mechanical properties, and a reduction of thermal stability of the CS-based membranes were observed. The increased dimensional stability in water, together with the presence of high GO amounts, made the prepared composite membranes more efficacious than the ones based just on CS in isolating and preconcentrating different hydrophilic/hydrophobic pollutants.

Current Applications of Magnetic Nanomaterials for Extraction of Mycotoxins, Pesticides, and Pharmaceuticals in Food Commodities.

Environmental pollutants, such as mycotoxins, pesticides, and pharmaceuticals, are a group of contaminates that occur naturally, while others are produced from anthropogenic sources. With increased research on the adverse ecological and human health effects of these pollutants, there is an increasing need to regularly monitor their levels in food and the environment in order to ensure food safety and public health. The application of magnetic nanomaterials in the analyses of these pollutants could be promising and offers numerous advantages relative to conventional techniques. Due to their ability for the selective adsorption, and ease of separation as a result of magnetic susceptibility, surface modification, stability, cost-effectiveness, availability, and biodegradability, these unique magnetic nanomaterials exhibit great achievement in the improvement of the extraction of different analytes in food. On the other hand, conventional methods involve longer extraction procedures and utilize large quantities of environmentally unfriendly organic solvents. This review centers its attention on current applications of magnetic nanomaterials and their modifications in the extraction of pollutants in food commodities.

Novel solid-phase extraction filter based on a zirconium meta-organic framework for determination of non-steroidal anti-inflammatory drugs residues.

In this study, a zirconium-based metal-organic framework UiO-66-NH2 modified cotton fiber (CF@UiO-66-NH2) was fabricated for the extraction of five common NSAIDs, namely ketoprofen, naproxen, flurbiprofen, diclofenac sodium, and ibuprofen. UiO-66-NH2 was synthesized and immobilized on the surface of cotton fiber using an environmentally friendly aqueous synthesis method. The prepared CF@UiO-66-NH2 composite of 50 mg was loaded into a 13 mm recessed filter for use as a solid-phase extraction (SPE) adsorbent material. The filter was then used to enrich NSAIDs in fish and shrimp muscle tissues followed by ultra-high performance liquid chromatography (UPLC) detection. Several key parameters were evaluated and optimized, including adsorption flow rate, pH value of sample, desorption flow rate, and the formic acid content of the eluent. Under optimized conditions, linear ranges of ketoprofen, naproxen, flurbiprofen, diclofenac sodium, and ibuprofen were 2.0-300.0 ng/mL, 1.4-280.0 ng/mL, 3.0-400.0 ng/mL, 1.0-500.0 ng/mL, and 14.0-560.0 ng/mL, respectively. The detection limits ranged from 0.12 ng/mL to 3.50 ng/mL with recoveries in the range of 72.95-116.99%, RSDs < 9.90%. The results demonstrated that the homemade filters based on CF@UiO-66-NH2 exhibited good reproducibility, stability and adsorption property for the determination of trace-level NSAIDs in complex matrix.

Recent advances in micro- and nanomaterial-based adsorbents for pipette-tip solid-phase extraction.

There are a lot of review papers of sample pretreatment, but the comprehensive review on pipette-tip solid-phase extraction (PT-SPE) is lacking. This review (133 references) is mainly devoted to the development of different types of micro- and nanosorbent-based PT-SPE, including silica materials, carbon materials, organic polymers, molecularly imprinted polymers, and metal-organic frameworks. Each section mainly introduces and discusses the preparation methods, advantages and limitations of adsorbents, and their applications to environmental, biological, and food samples. This review also demonstrates the advantages of PT-SPE like convenience, speed, less organic solvent, and low cost. Finally, the future application and development trend of PT-SPE are prospected.

High crystalline magnetic covalent organic framework with three-dimensional grapevine structure for ultrasensitive extraction of nitro-polycyclic aromatic hydrocarbons in food and environmental samples.

Developing and establishing an efficient pre-treatment approach for the precise extraction of nitrated-polycyclic aromatic hydrocarbons (N-PAHs) from real-life samples is critical for ensuring their safety. In this study, a novel crystalline magnetic covalent organic framework with a grapevine structure not a single core-shell, Fe3O4@TAPT-DMTA-COF, was fabricated via chemical bonding. Unchanging the reticulated structure and high crystallinity of TAPT-DMTA-COF, the combination made this material possess not only simple operation via magnetic decantation but also remarkable chemical stability. Fe3O4@TAPT-DMTA-COF had a large surface area (1578.45 m2/g), and rich electronegative triazine-groups, which makes it become a superior magnetic enrichment material for trace N-PAHs. For N-PAHs analysis, low limits of detection (LODs) (1.43-17.24 ng/L), excellent relative standard deviations (RSDs ≤ 11.52%), and wide linearity (10-5000 ng/L) were obtained. Real-life applications based on this composite have been successfully explored by capturing the N-PAHs emitted from food and environmental samples.

Development of a surfactant-assisted dispersive solid phase extraction using deep eutectic solvent to extract four tetracycline antibiotics residues in milk samples.

In this study, a new floating dispersive solid phase extraction method based on deep eutectic solvents has been developed in a home-made extraction device for the extraction of four tetracycline antibiotics from milk samples. In this approach, the sorbent (activated carbon) was dispersed in whole parts of solution with the aid of air stream and floated on top of the solution with the aid of the surfactant (lauryl betaine) and air bubbles. After collection of the sorbent, the adsorbed analytes were eluted with tetrabutyl ammonium chloride-propionic acid deep eutectic solvent under sonication. In this method, there was no need of organic dispersive and extraction solvents and the used sorbent was collected on top of the solution and collected without centrifugation. The validation parameters showed that low limits of detection (0.1-0.3 µg/kg) and quantification (0.6-1.0 µg/kg), acceptable enrichment factors (52-60), efficient extraction recoveries (80-91%), and satisfactory relative standard deviations (≤9.8%) were obtained. Eventually, the method was successfully applied on different milk samples and tetracycline was determined in them.