Large-pore covalent organic framework as solid phase extraction absorbentforefficientdetermination of polypeptide antibiotics in animal-derived foods.

The precise determination of polypeptide antibiotics (PPTs) in foods has been always challenging because of the interference of various endogenous peptides in complex matrix. Herin, a novel large-pore covalent organic framework (TABPT-SPDA-COF) with accessible pore size of 7.9 nm was synthesized as a solid phase extraction (SPE) absorbent for efficiently enriching four PPTs existed in foods originating from animals. The parameters of SPE process were systematically optimized. Subsequently, four PPTs were determined by UHPLC-MS/MS. Under the optimal conditions, TABPT-SPDA-COF shows outstanding enrichment capacity for PPTs in contrast to commercial absorbents ascribed to size selectivity and multiple interaction effects. The method exhibits excellent linear range (0.005-100 ng mL-1), satisfactory limits of detection (0.1 pg mL-1) as well as relative recoveries (86.2-116 %). This work offers a practicable platform to monitor trace PPTs from complex animal-derived foodstuffs.

A biosensor method based on surfactant-mediated surface droplet evaporation for the detection of Aflatoxin B1.

Aflatoxin B1 (AFB1) is a common mycotoxin that is of significant global concern due to its impact on food safety. Herein, we innovatively develop a sensing platform to detect AFB1 based on evaporation of surfactant solutions on the hydrophobic surface, resulting in dried patterns with varied sizes. The surfactant CTAB solution produces a relatively large dried pattern due to the surface wetting. However, the reduction in the dried pattern size is found when the mixture of CTAB and AFB1 aptamer is tested, because the formation of CTAB/aptamer complex. Moreover, the dried pattern size of the mixture of CTAB, aptamer, and AFB1 increases due to the specific binding of AFB1 to its aptamer. Using this innovative strategy, the AFB1 detection can be fulfilled with a detection limit of 0.77 pg/mL. As a simple, convenient, inexpensive, and label-free method, the surfactant-mediated surface droplet evaporation-based biosensor is very promising for various potential applications.

Fabrication of caffeoylquinic acid-loaded burdock polysaccharide nanoparticles and their antioxidant activity in hydrogen peroxide-damaged HepaRG cells.

Herein, burdock polysaccharide (BP) and modified burdock polysaccharide (MBP) were prepared, followed by the fabrication of chlorogenic acid (CA)-BP, CA-MBP, isochlorogenic acid A (ICA)-BP, and ICA-MBP nanoparticles. Afterward, the structural characteristics, physical stability, digestive characteristics, and antioxidant activity of hydrogen peroxide (H2O2)-damaged HepaRG cells were evaluated. The result indicated that the loading capacities of CA in BP-CA and MBP-CA were 0.14 and 0.53 µg/mg, respectively. Conversely, the loading capacities of ICA in BP-ICA and MBP-ICA were 0.36 and 0.60 µg/mg, respectively. Four complex nanoparticles exhibited excellent physical stability under different pH values, temperatures, and ionic concentrations, especially MBP-CA and MBP-ICA. Moreover, four complex nanoparticles could protect caffeoylquinic acid from being released in gastric fluid. All six samples exhibited high antioxidant activity in H2O2-induced HepaRG cells, especially BP and MBP-CA. These findings indicated that caffeoylquinic acid-polysaccharide complexes were successfully prepared and highlighted the potential of polysaccharides as natural carriers for hydrophobic bioactive molecules.

Comprehensive Investigation of Ginsenosides in the Steamed Panax quinquefolius with Different Processing Conditions Using LC-MS.

Panax quinquefolius (PQ) has been widely used in traditional Chinese medicine and functional food. Ginsenosides are the important functional components of PQ. The ginsenosides' diversity is deeply affected by the processing conditions. The ginsenosides in the steamed PQ have been not well-characterized yet because of the complexity of their structure. In the study, the comprehensive investigation of ginsenosides was performed on the steamed PQ with different steaming times and temperatures by UPLC-Q-TOF-MS. Based on the molecular weight, retention time and characterized fragment ions, 175 ginsenosides were unambiguously identified or tentatively characterized, including 45 protopanaxatriol type, 49 protopanaxadiol type, 19 octillol type, 6 oleanolic acid type ginsenosides, and 56 other ginsenosides. Ten new ginsenosides and three new aglycones were discovered in the steamed PQ samples through searching the database of CAS SciFindern. Principal component analysis showed the significant influence on the chemical components of PQ through different processing conditions. The steaming temperature was found to promote the transformation of ginsenosides more than the steaming time. The protoginsenosides were found to transform into the rare ginsenosides by elimination reactions. The malonyl ginsenosides were degraded into acetyl ginsenosides, and then degraded into neutral ginsenosides. The sugar chain experienced degradation, with position changes and configuration inversions. Furthermore, 20 (S/R)-ginsenoside Rh1, Rh2, Rg2, and Rh12 were found to transform from the S-configuration to the R-configuration significantly. This study could present a comprehensive ginsenosides profile of PQ with different steaming conditions, and provide technical support for the development and utilization of PQ.

Imprinted covalent organic frameworks solid-phase microextraction fiber for in vivo monitoring of acidic per- and polyfluoroalkyl substances in live aloe.

Per- and polyfluoroalkyl substances (PFASs) can lead to risks associated with animal and human health through the transfer along food chains. It is confirmed that PFASs can be transported to each part of plants after taken up by the roots. To better elucidate the underlying mechanisms for such exposure, it is highly valuable to develop analytical capabilities for in vivo monitoring of PFASs in live plants. In this work, a novel imprinted covalent organic frameworks (CMIP) solid-phase microextraction coupled with ultra-performance liquid chromatography-tandem mass spectrometry was developed with low limits of detection for six acidic PFASs (0.1-0.3 ng g-1) and used for in vivo monitoring in live aloe. The CMIP coating shows good precision (RSD of intra and inter ≤9.6 % and 10.2 %, respectively) and possesses much higher extraction efficiency than the commercial coatings. After cultivating aloe in soil spiked PFASs, the in vivo assays gave a wealth of information, including steady-state concentrations, translocation factors, elimination rate constants, and half-life of PFASs. The in vivo tracing method for live plants can provide much needed and unique information to evaluate the risk of PFASs, which are very important for the safety of agriculture production.

Synthesis of an ordered macroporous metal-organic framework for efficient solid-phase extraction of aflatoxins from milk products.

Aflatoxins (AFs) exhibit hepatotoxicity, immunotoxicity, and carcinogenicity, and their detection in food has attracted widespread concern. An ordered macroporous metal-organic framework (OM-ZIF-8) based on solid-phase extraction (SPE) was used to extract six AFs from milk products. The SPE conditions, including eluting solvent, eluting volume, amounts of OM-ZIF-8, pH of loading solution, loading solvent, ionic strength, loading flow rate, and elution flow rate, were exhaustively optimized. Under optimal parameters, the six AFs were detected by ultra-high-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS). The OM-ZIF-8 exhibited satisfactory AFs extraction performance through ordered macropore structure, π-π interaction, coordination interaction, and electrostatic interaction. Furthermore, linearity in the range of 0.01-100 ng mL-1 with low detection limits of 0.002-0.0150 ng mL-1 was obtained, and the relative recoveries of AFs were 80.3-110 % with relative standard deviation ≤8.7 %. Thus, this research provides a promising platform for the analysis of trace AFs in complex foods.

Mononuclear Non-Heme Manganese-Catalyzed Enantioselective cis-Dihydroxylation of Alkenes Modeling Rieske Dioxygenases.

The practical catalytic enantioselective cis-dihydroxylation of olefins that utilize earth-abundant first-row transition metal catalysts under environmentally friendly conditions is an important yet challenging task. Inspired by the cis-dihydroxylation reactions catalyzed by Rieske dioxygenases and non-heme iron models, we report the biologically inspired cis-dihydroxylation catalysis that employs an inexpensive and readily available mononuclear non-heme manganese complex bearing a tetradentate nitrogen-donor ligand and aqueous hydrogen peroxide (H2O2) and potassium peroxymonosulfate (KHSO5) as terminal oxidants. A wide range of olefins are efficiently oxidized to enantioenriched cis-diols in practically useful yields with excellent cis-dihydroxylation selectivity and enantioselectivity (up to 99% ee). Mechanistic studies, such as isotopically 18O-labeled water experiments, and density functional theory (DFT) calculations support that a manganese(V)-oxo-hydroxo (HO-MnV═O) species, which is formed via the water-assisted heterolytic O-O bond cleavage of putative manganese(III)-hydroperoxide and manganese(III)-peroxysulfate precursors, is the active oxidant that effects the cis-dihydroxylation of olefins; this is reminiscent of the frequently postulated iron(V)-oxo-hydroxo (HO-FeV═O) species in the catalytic arene and alkene cis-dihydroxylation reactions by Rieske dioxygenases and synthetic non-heme iron models. Further, DFT calculations for the mechanism of the HO-MnV═O-mediated enantioselective cis-dihydroxylation of olefins reveal that the first oxo attack step controls the enantioselectivity, which exhibits a high preference for cis-dihydroxylation over epoxidation. In this study, we are able to replicate both the catalytic function and the key chemical principles of Rieske dioxygenases in mononuclear non-heme manganese-catalyzed enantioselective cis-dihydroxylation of olefins.

Research progress of applications for nano-materials in improved QuEChERS method.

The quick, easy, cheap, effective, rugged, and safe (QuEChERS) approach is widely used in sample pretreatment in agricultural products, food, environment, etc. And nano-materials are widely used in QuEChERS method due to its small size and large specific surface area. In this review, we examine the typical applications of several commonly used nano-materials in improved QuEChERS method. These materials include multi-walled carbon nanotubes (MWCNTs) and their derivatives, magnetic nanoparticles (MNPs), metal organic frameworks (MOFs), covalent organic frameworks (COFs), graphene oxide (GO), lipid and protein adsorbent (LPAS), cucurbituril (CBs), and carbon nano-cages (CNCs), and so on. The strengths and weaknesses of each nano-material are presented, as well as the challenging aspects that need to be addressed in future research. By comparing the applications and the current technology development, this review suggests utilizing artificial intelligence (AI) to screen suitable combinations of purification agents and performing virtual simulation experiments to verify the reliability of this methodology. By doing so, we aim to accelerate the development of new products and decrease the cost of innovation. It also recommends designing smarter pretreatment instruments to enhance the convenience and automation of the sample pretreatment process and reduce the margin for human error.

Facile Synthesis of Quinolinecarboxylic Acid-Linked Covalent Organic Framework via One-Pot Reaction for Highly Efficient Removal of Water-Soluble Pollutants.

To efficiently eliminate highly polar organic pollutants from water has always been a difficult issue, especially in the case of ultralow concentrations. Herein, we present the facile synthesis of quinolinecarboxylic acid-linked COF (QCA-COF) via the Doebner multicomponent reaction, possessing multifunction, high specific surface area, robust physicochemical stability, and excellent crystallinity. The marked feature lies in the quinolinyl and carboxyl functions incorporated simultaneously to QCA-COF in one step. The major cis-orientation of carboxyl arms in QCA-COF was speculated by powder X-ray diffraction and total energy analysis. QCA-COF demonstrates excellent adsorption capacity for water-soluble organic pollutants such as rhodamine B (255.7 mg/g), methylene blue (306.1 mg/g), gentamycin (338.1 mg/g), and 2,4-dichlorophenoxyacetic acid (294.1 mg/g) in water. The kinetic adsorptions fit the pseudo-second order model and their adsorption isotherms are Langmuir model. Remarkably, QCA-COF can capture the above four water-soluble organic pollutants from real water samples at ppb level with higher than 95% removal efficiencies and excellent recycling performance.

An Imine-Based Porous 3D Covalent Organic Polymer as a New Sorbent for the Solid-Phase Extraction of Amphenicols from Water Sample.

In this paper, an imine-based porous 3D covalent organic polymer (COP) was synthesized via solvothermal condensation. The structure of the 3D COP was fully characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, and powder X-ray diffractometry, thermogravimetric analysis, and Brunauer-Emmer-Teller (BET) nitrogen adsorption. This porous 3D COP was used as a new sorbent for the solid-phase extraction (SPE) of amphenicol drugs, including chloramphenicol (CAP), thiamphenicol (TAP), and florfenicol (FF) in aqueous solution. Factors were investigated for their effects on the SPE efficiency, including the types and volume of eluent, washing speed, pH, and salinity of water. Under the optimized conditions, this method gave a wide linear range (0.1-200 ng/mL) with a high correlation coefficient value (R2 > 0.99), low limits of detection (LODs, 0.01-0.03 ng/mL), and low limits of quantification (LOQs, 0.04-0.10 ng/mL). The recoveries ranged from 83.98% to 110.7% with RSDs ≤ 7.02%. The good enrichment performance for this porous 3D COP might contribute to the hydrophobic and π-π interactions, the size-matching effect, hydrogen bonding, and the good chemical stability of 3D COP. This 3D COP-SPE method provides a promising approach to selectively extract trace amounts of CAP, TAP, and FF in environmental water samples in ng quantities.

Metabolomics Analysis of Different Tissues of Lonicera japonica Thunb. Based on Liquid Chromatography with Mass Spectrometry.

Lonicera japonica Thunb. (LJT) has been widely used as medicines or food additives in Asian countries for thousands of years. The flower buds are often medicinally used, and the other tissues are ignored. However, flowers, leaves and stems have also been reported to have antimicrobial, anti-inflammatory and antioxidant effects. In the current study, un-targeted metabolomics analysis was performed to investigate the metabolic difference among different tissues (flowers, flower buds, stems and leaves) of LJT based on liquid chromatography with mass spectrometry. A total of 171 metabolites were identified, including 28 flavonoids, 35 phenolic acids, 43 iridoids, 9 amino acids, 6 nucleotides, 16 fatty acids, 22 lipids and 12 others. Four new secondary metabolites were discovered. Some flavonoids and iridoids were not detected in leaves and stems. Principal component analysis showed significant differences among four different tissues. Some 27, 81, 113 differential metabolites were found between flowers/flower buds, leaves/flower buds, stems/flower buds, respectively. Primary metabolites showed a higher content in the flowers and flower buds. For the flavonoids, flavones were mainly accumulated in the leaves, flavonols were mainly accumulated in the flower buds, and acylated flavonol glucosides were mainly accumulated in the flowers. Most phenolic acids showed a higher content in the flowers or flower buds, while phenolic acid-glucosides showed significantly higher content in the flower buds. The most abundant iridoids in the LJT also showed a higher content in the flowers and flower buds. These results can provide new insights into the understanding of the metabolites changes in different tissues, and lay a theoretical foundation for the comprehensive utilization of LJT.

Online solid-phase extraction based on size-controllable spherical covalent organic framework for efficient determination of polybrominated diphenyl ethers in foods.

An analytical method of microspheric brominated covalent organic framework (Br-COF)-online solid-phase extraction integrated with high-performance liquid chromatography (online SPE-HPLC) was proposed for efficiently enriching six polybrominated diphenyl ethers (PBDEs) in foods. The Br-COF microspheres were facilely prepared with uniformity and dispersion by a size-controllable synthesis at the room temperature. Attributed to multiple interactions of the halogen bonding, Van der Waals forces, hydrophobic interaction along with size-matching effect, Br-COF performed satisfactory extraction capacity for PBDEs compared with commercial adsorbents. Five primary influencing factors were optimized, including loading solvent, loading flow rate, elution solvent, elution flow rate and elution volume. Under the optimal parameters, the implement displayed excellent linear ranges (0.5-500 ng mL-1) and low detection limits (0.01-0.05 ng mL-1). The relative recoveries in six spiked food samples ranged from 87.8 to 119.7 % with relative standard deviations below 10 %. This research estabished a promising platform for quantitatively determining trace PBDEs in complex foods.

Preparation of a pyridyl covalent organic framework via Heck cross-coupling for solid-phase microextraction of perfluoropolyether carboxylic acids in food.

The growing detection of emerging perfluoropolyether carboxylic acids (PFECAs) in food has raised considerable concerns about their high persistence, bioaccumulation, and toxicity. In this study, a pyridine-functionalized covalent organic framework (Py-COF) was synthesized by introducing basic pyridyl groups into Br-COF via Heck cross-coupling. According to density functional theory, PFECAs were adsorbed in the pore sites of Py-COF via O-···HN+ interaction, which was the stable and predominant adsorption configuration. After systematic characterization, Py-COF was used as the coating for solid-phase microextraction combined with high-performance liquid chromatography-tandem mass spectrometry (SPME-HPLC-MS/MS) for the efficient determination of PFECAs in food. Under the optimum conditions, the method showed satisfactory linearity (R2 ≥ 0.998), low limits of detection (0.001-0.004 ng g-1), and good relative recoveries (82.5 %-112 %). The established method was satisfactorily used for the analysis of trace PFECAs in food samples.

An amine-functionalized olefin-linked covalent organic framework used for the solid-phase microextraction of legacy and emerging per- and polyfluoroalkyl substances in fish.

Due to the environmental persistence and various health problems associated with per- and polyfluoroalkyl substances (PFASs), they have come under increased public scrutiny. However, the efficient extraction of PFASs from complex media remains challenging. Herein, an olefin-linked covalent organic framework (COF-CN) has been prepared via a Knoevenagel condensation reaction, followed by reduction using LiAlH4 to form an amine-functionalized COF (COF-NH2). The characterization results demonstrated that the crystal structure was maintained during the post-modification step. Isothermal and kinetic adsorption studies showed the higher affinity of COF-NH2 toward PFASs. Based on density functional theory, the adsorption mechanism of the stable six-member-ring structure formed between COF-NH2 and PFASs via hydrogen bonding was tentatively revealed. After optimizing the solid-phase microextraction parameters, legacy and emerging PFASs were efficiently extracted from fish using the COF-NH2 coating, followed by detection using ultra-performance liquid chromatography-tandem mass spectrometry. The method exhibited ideal linearity, low limits of quantification, excellent precision, and high relative recoveries. Finally, the bioconcentration kinetics for goldfish was studied, which can provide a feasible platform for investigating the accumulate ion and toxicity of PFASs.

Online extraction based on ionic covalent organic framework for sensitive determination of trace per- and polyfluorinated alkyl substances in seafoods by UHPLC-MS/MS.

The ionic covalent organic framework (TPB-BFBIm-iCOF) was facilely synthetized by the size-controllable confinement method and chosen as the online solid phase extraction (SPE) adsorbent. This adsorbent showed fast adsorption equilibrium (5 min) and high adsorption capacity (87.7-140.8 mg g-1) for the per- and polyfluorinated alkyl substances (PFASs). The TPB-BFBIm-iCOF microsphere revealed the satisfactory enrichment performance for PFASs by means of the electrostatic interaction, hydrophobic effect and ordered channel structure. After extraction, the loaded TPB-BFBIm-iCOF-online SPE column was eluted and applied to the ultrahigh performance liquid chromatography tandem mass spectrometry analysis. Under the optimum conditions, the method displayed satisfactory linearity (R2 ≥ 0.9910) and low limits of detection (≤0.0017 ng g-1) for five seafoods. The relative recoveries of PFASs were 85.3%-109.4% with the relative standard deviation ≤ 9.9%. The method exhibited potential value in monitoring the toxicokinetics and environmental behaviors of PFASs.

Boronic Acid-Functionalized Scholl-Coupling Mesoporous Polymers for Online Solid-Phase Extraction of Brassinosteroids from Plant-Derived Foodstuffs.

Brassinosteroids (BRs) are natural, nontoxic, non-hazardous, biosafe, and eco-friendly plant hormones, possessing diverse pharmacological activities. However, little is known about the type and content of BRs in frequently consumed plant-derived foodstuffs because of their low abundance and high abundance of interference. In this study, a selective, accurate, and sensitive method based on the online solid-phase extraction using the boronic acid-functionalized Scholl-coupling microporous polymer was developed for the analysis of BRs in plant-derived foodstuffs. Under optimum conditions, an excellent linearity (R2 ≥ 0.9970) and lower limits of detection (0.010-0.070 pg mL-1) were obtained. The high relative recoveries were in the range of 90.33-109.34% with relative standard deviations less than 9.73%. The method was successfully used for the determination of BRs in fifteen plant-derived foodstuffs. The present work offers a valuable tool for exploring BRs from the plant-derived foodstuffs and can provide useful information for developing functional foods.

Molecularly imprinted polymers prepared from a single cross-linking functional monomer for solid-phase microextraction of estrogens from milk.

In this work, a single cross-linking functional monomer, 2,5-divinylterephthalaldehyde, was designed and synthesized to simplify the preparation of molecularly imprinted polymers (MIPs). In the presence of estradiol as a template, MIPs were successfully prepared using 2,5-divinylterephthalaldehyde along with a solvent and initiator. This method reduced most of the complex variables encountered in the traditional synthesis. Characterization of the morphology and structure of the MIPs was performed by scanning electron microscopy, Fourier transform infrared spectroscopy, and Brunauer-Emmett-Teller analysis. Compared with non-imprinted polymers, the MIPs had higher adsorption capacities for five estrogens with imprinting factors above 2.9. The MIPs had high extraction efficiencies, good functional properties, long lifetimes, and good reproducibility, which made them suitable for solid-phase microextraction (SPME). Coupled with ultra-high performance liquid chromatography tandem mass spectrometry, the MIP-based fibers were applied to SPME for the analysis of five estrogens in milk samples. Under the best conditions, the established method had a wide linear range (0.5-10000 ng kg-1), low limits of detection (0.08-0.26 ng kg-1) and quantification (0.26-0.87 ng kg-1), good precision (3.2-8.1%, n = 6), and fiber-to-fiber reproducibility (4.3%-8.8%, n = 3). The MIPs-based fibers can be reused at least 60 times without apparent loss of extraction efficiency. Finally, this method was applied to the determination of target estrogens in milk samples with satisfactory relative recoveries (84.3%-105%, relative standard deviation ≤ 7.8%).

Spherical conjugated microporous polymers for solid phase microextraction of carbamate pesticides from water samples.

Conjugated microporous polymers (CMPs) with uniform morphology have shown fascinating application in the separation science. In this study, metal-free Knoevenagel condensation was adopted to prepare spherical sp2 carbon-conjugated microporous polymers, which used tetrakis(4-formylphenyl)methane and 1,4-phenylenediacetonitrile as monomers. Due to the remarkable extraction capability for carbamate pesticides (CPs), the as-synthesized CMPs were fabricated as the coating for solid-phase microextraction (SPME). After optimized SPME parameters (adsorption time, salt concentration, sample pH, adsorption temperature, desorption time, desorption solvent and desorption volume), ten CPs in water samples were quantified by ultrahigh performance liquid chromatography tandem mass spectrometry (UPLC-MS/MS). Linearity in the range 0.005-100 ng mL-1 with low detection limits of 0.00060-0.017 ng mL-1 was obtained. The intra-day and inter-day precisions expressed as relative standard deviations were 1.5-8.1% and 1.1-8.0%, respectively. Fiber-to-fiber reproducibility was below 7.3%. The CMPs-SPME-UPLC-MS/MS method was applied to detect trace CPs in real water samples with relative recoveries from 91.8% to 108%.

Facile synthesis of trifluoromethyl covalent organic framework for the efficient microextraction of per-and polyfluorinated alkyl substances from milk products.

Trifluoromethyl covalent organic framework (CF3-COF) is facilely synthesized at room temperature using for solid-phase microextraction (SPME). The CF3-COF coating displays an improved extraction performance for per- and polyfluorinated alkyl substances (PFASs) comparing to amorphous polymer coating, non-contained fluorine covalent organic framework coating and commercially available SPME coating. The fluorine affinity of trifluoromethyl in CF3-COF for PFASs is demonstrated using the density functional theory calculation. Following the microextraction with CF3-COF-coated fiber, the targeted PFASs are eluted with 1 mL acetonitrile and quantified by ultrahigh performance liquid chromatography tandem mass spectrometry. The low limits of detection are 0.1-0.7 pg g-1 for milk and 0.2-0.8 pg g-1 for milk powder, suggesting the outstanding sensitivity. The precision for the method ranges between 2.9 and 9.9%. The fiber-to-fiber repeatability is in the range of 4.2-9.5%. Under the optimum conditions, the relative recoveries are 91.0-110% with RSDs ≤ 10% for milk and 89.8-111% with RSDs ≤ 10% for milk powder.