The sensitive detection of trace endocrine disruptors holds immense practical significance for safeguarding food safety. Herein, a boronic acid-decorated magnetic porous organic polymer (POP-PA@Fe3O4) was synthesized as adsorbent for the extraction and enrichment of several phenolic endocrine disruptors (PEDs). The decoration of boronic acid provides a high density of hydroxyl groups, significantly enhancing its adsorption performance. POP-PA@Fe3O4 exhibited excellent adsorption capability toward PEDs by virtue of H-bonding interactions and π-π stacking. Subsequently, combined with high-performance liquid chromatography/mass spectrometry (HPLC/MS), a sensitive method for the determination of PEDs in milk was established by employing POP-PA@Fe3O4 as a magnetic extraction adsorbent. The method showed low detection limits (S/N = 3) of 0.080-0.40 ng·mL-1. The recoveries of spiked samples spanned 84.6% to 100.0% with RSD ≤ 7.5%. This work presents a feasible approach for the detection of PEDs in milk and further expands the application of functionalized porous organic polymers in food safety monitoring.
A cold-assisted headspace solid-phase microextraction (CA-HS-SPME) method combined with gas chromatography-mass spectrometry (GC-MS) was developed for the determination of eight polychlorinated naphthalene (PCN) congeners in water sample. In the CA-HS-SPME setup, frozen gel served as the refrigerant and copper tube as the thermal conductor to cool the polydimethylsiloxane (PDMS) fiber during extraction, thereby enhancing extraction efficiency. The main experimental variables affecting the extraction performance, including temperature, extraction time, and salt concentration, were systematically optimized. Under the optimized conditions, the method exhibited good linearity over the range of 0.1/0.5/1-500 pg/mL, with the correlation coefficient (r) values ≥ 0.9962. The enrichment factors for the PCNs ranged from 955 to 4299, while the limits of detection and quantification were 0.02-0.28 pg/mL and 0.07-0.92 pg/mL, respectively. The intra-day and inter-day precisions (n = 6), expressed as the relative standard deviations, were 10.8%-16.3% and 12.2%-17.8%, respectively. The recoveries obtained from fortified water samples ranged from 90.7% to 117.8%. The proposed method is sensitive, simple, solvent-free, and provides an effective approach for the determination of trace PCNs in water.
A novel amino-functionalized hyper-crosslinked polymer named as ADCPD/TPA-HCP was prepared with 4amino-3,6-dihydropyridazine (ADCPD) and triphenylamine (TPA) as raw materials. The polymer has a high specific surface area, with a specific surface area of 544 m2 g-1, and it exhibits an excellent adsorption performance for nitroimidazoles (NIIMs). Compared with some commercial adsorbents, it has good adsorption performance and good reusability. With ADCPD/TPA-HCP as the adsorbent, a solid phase extraction-high performance liquid chromatography (SPE-HPLC) method was established for the simultaneous detection of NIIMs in river water, honey and pork. Under the optimized conditions (adsorbent dosage: 30 mg; sample volume: 100 mL; sample loading rate: 4 mL min- 1; elution solvent: methanol-acetonitrile (1:1, V/V)), the linear ranges of the method for the compounds in river water, honey and pork matrix were 0.10-80.0 ng mL-1, 1.00-200 ng mL- 1 and 1.33-200 ng g- 1 respectively, and the coefficients of determination (r2) were no less than 0.9916. The detection limits (S/N = 3) for the NIIMs for the three sample matrices were 0.03-0.06 ng mL- 1, 0.2-0.5 ng mL- 1 and 0.4-1.2 ng g-1, respectively. The spiked method recoveries were 79.9%-118%, and the relative standard deviations (RSDs) were less than 10.9%.
Phenolic endocrine disrupting compounds (EDCs) contamination poses a serious public health and environmental threat, therefore develop sensitive and selective detection method for phenolic EDCs is highly desirable. A porous organic polymer (DT-POP3) was synthesized by azo coupling of 2,4,6-tris(o-hydroxyaryl)-1,3,5-triazines and 4,4''-diamino-p-terphenyl. DT-POP3 exhibited high adsorption capacity and fast adsorption kinetics for phenolic EDCs through the hydrogen bond force and π-π stacking interaction. With DT-POP3 as solid-phase extraction adsorbent, a LC-MS method was established to detect phenolic EDCs in fish. The method exhibited wide linear range (4.00-1000 ng·g-1), low detection limit (S/N = 3) (1.20-6.50 ng·g-1), high spiked recoveries (82.9-118.8%) and low relative standard deviation (1.8-9.6%). The contribution of this study is not merely the proposal of a viable adsorption/detection method for trace phenolic EDCs, but also concurrently establishes a novel paradigm for the development of functional materials aimed at removing organic pollutants.
N-(3,4-dihydroxybenzylidene)-4-hydroxybenzenamine (DHB-AP) was synthesized from 3,4-dihydroxybenzaldehyde (DHB) and p-aminophenol (AP), and then it was reacted with biphenyl-4-dichlorobenzyl alcohol (BCM) to synthesize for the first time the porous organic polymer (DHB-AP/BCM-HCP) targeting at the efficient enrichment of neonicotinoid insecticides (NEONICs). With the DHB-AP/BCM-HCP as solid-phase extraction (SPE) adsorbent, the NEONICs including thiamethoxam, imidacloprid, acetamiprid and thiacloprid were efficiently extracted from tap water, beverages, and lettuce samples. Under optimal SPE conditions, with the help of high-performance liquid chromatography-ultraviolet detection, the NEONICs had a linear response range of 0.06to 80 ng mL-1, 0.18to 80 ng mL-1, and 1.50 to 200 ng g-1 for water, beverage and lettuce samples, respectively, depending on both the compounds and sample matrix. The method recoveries ranged from 80.0 % to 118 %, with the relative standard deviations (RSD) between 3.3 % and 8.9 %. The results demonstrate that the method has an excellent method performance in terms of sensitivity, precision and accuracy, which provides a new approach for accurately determining trace NEONICs in some food samples.
An amino-functionalized pyrazine-based highly conjugated covalent organic framework (NH2-PyCOF) was synthesized via a post-synthetic modification strategy and applied as an adsorbent for the solid-phase extraction (SPE) of four neonicotinoid insecticides (NTIs) in honey, beverage and water samples. NH2-PyCOF combines a highly conjugated pyrazine skeleton with multiple amino sites, which not only enhances its hydrophilicity but also provides multiple interaction sites, including hydrogen-bonding and π-π stacking sites. When NH2-PyCOF-based SPE was coupled with HPLC-MS, the method demonstrated low detection limits (0.025-0.10 ng mL-1 for peach beverage samples, 0.01-0.03 ng mL-1 for water samples and 0.20-0.80 ng g-1 for honey samples) and satisfactory recoveries (86.0%-111%) with relative standard deviations below 8.4%. The NH2-PyCOF-SPE-HPLC-MS method exhibits exceptional sensitivity and reproducibility, providing a reliable and efficient approach for monitoring trace NTI residues in complex matrices.
Background Psoriasis, a chronic inflammatory skin disease, imposes a substantial clinical burden with limited long-term treatment efficacy. Quercitrin (QUE), a natural flavonoid possessing anti-inflammatory and antioxidant properties, exhibits therapeutic potential for psoriasis, yet its precise mechanism of action remains to be fully elucidated. Methods To evaluate the effects of QUE, LPS-stimulated HaCaT cells (modeling keratinocyte immune activation) and IMQ-induced psoriatic mice were employed. Skin pathology was assessed by PASI score and histopathological staining. Inflammatory cytokines and oxidative stress markers were measured both in vitro and in vivo using ELISA and commercial kits. NF-κB pathway expression was analyzed by Western blot (in vitro), IHC, and RT-qPCR (in vivo). Molecular docking predicted the binding of QUE to TLR4/MyD88, and 16S rRNA sequencing was used to analyze changes in gut microbiota composition. Results QUE effectively inhibited LPS-induced NF-κB activation and oxidative stress in HaCaT cells, leading to reduced release of pro-inflammatory cytokines. In IMQ-induced psoriatic mice, QUE treatment not only alleviated skin lesions and reduced splenomegaly, but also restored the structural integrity of dermal collagen and elastic fibers, thereby improving skin barrier function. Furthermore, QUE suppressed cutaneous NF-κB activation while ameliorating both systemic and local oxidative stress. Molecular docking analysis revealed that QUE directly binds to TLR4 and MyD88. Additionally, QUE restored gut microbiota homeostasis and enhanced intestinal barrier integrity. Conclusions QUE alleviates psoriatic inflammation through synergistic regulation of the NF-κB pathway and gut microbiota homeostasis, exhibiting potential as a multi-target therapeutic agent.
Developing an effective method for reliable monitoring of insecticide residues is desirable for public health. This study developed a rapid and sensitive method to determine neonicotinoid insecticides (NEONICs) in water, lemon beverage, wax gourd, and tomato samples. An imidazole-functionalized COF (TPT-DB-COF) featuring a spherical core-shell structure was developed and used as a solid-phase extraction (SPE) adsorbent. The TPT-DB-COF exhibited superior adsorption ability for NEONICs. The TPT-DB-COF-SPE/HPLC-DAD approach for trace analysis of NEONICs had low detection limits (0.02-0.03 ng mL-1 for water samples, 0.07-0.08 ng mL-1 for lemon beverage, 0.6-0.8 ng g-1 for wax gourd samples, and 0.9-1.3 ng g-1 for tomato samples), high trueness (method recoveries of 87.0% - 114%), and acceptable precision (relative standard deviations below 7.9%). Such good performance parameters pave the way for the application of TPT-DB-COF in the analysis of NEONICs.
In this study, a low-cost octaphenylcyclotetrasiloxane (OPS) was used as the structural building block to prepare an organic-inorganic hybrid porous material (OPS-OIHM) via a facile Scholl coupling reaction. The material exhibits high specific surface area, and possesses excellent stability. OPS-OIHM demonstrates strong affinity for phenolic compounds through the synergistic effects of π-π stacking, hydrophobic interactions, and hydrogen bonding. A method involving OPS-OIHM-based solid-phase extraction, followed by HPLC detection, was established to analyze chlorophenols (including 2-chlorophenol, bisphenol A, 2,6-dichlorophenol, 2,4-dichlorophenol, and p‑tert-butylphenol) in various samples such as water, juice, and milk. The method achieved detection limits of 0.02-0.08 ng mL⁻1 in water, 0.10-0.22 ng mL⁻1 in juice, and 0.28-0.60 ng mL⁻1 in milk. Linear responses were observed across the following concentration ranges: 0.06-100 ng mL⁻1, 0.30-100 ng mL⁻1, and 0.84-500 ng mL⁻1. The recoveries of spiked water, juice and milk were 80.0%-120.3%, 82.0%-116.0% and 80.8%-113.6%, respectively. The relative standard deviations were less than 7.43%. This work provides an efficient and reliable approach for the analysis of trace phenolic pollutants in complex samples, showing promising potential for applications in environmental monitoring and food safety.
Nitroimidazoles (NIIMs) residues have posed toxic, carcinogenic, and mutagenic threats to human health. Therefore, developing efficient adsorbents for their enrichment and detection is particularly necessitated. Herein, a novel fluorine and boric acid dual-functionalized hyper crosslinked polymer (HCP-BFA/DCX) was developed for the first time with 4-benzyloxy-3-fluorobenzeneboronic acid (BFA) as monomer and α, α'-dichloro-p-xylene (DCX) as crosslinker. The adsorption mechanism is primarily governed by hydrogen bonding, π-π stacking and electrostatic interactions. HCP-BFA/DCX exhibits strong enrichment capability towards NIIMs and was utilized as adsorbent for extracting five NIIMs from fish and pork samples. The method has a good linearity (1.7–1000 ng g−1 for fish samples and 1.3−1000 ng g−1 for pork samples) with r2> 0.9915, low limits of detection (0.5−1.0 ng g−1 and 0.4−0.8 ng g−1, respectively), high accuracy (method recoveries of 85.6%−105%) with relative standard deviations below 8.9%. HCP-BFA/DCX can work as a promising adsorbent for efficient enrichment of NIIMs and other pollutants.
A benzyl-bis(diphenylphosphine)-based hyper crosslinked polymer (denoted as BPM-HCP) was fabricated with the use of alpha,alpha'-dichloro-p-xylene as cross-linker and bis(diphenylphosphino)methane as monomer. The characterization of the polymer was made and subsequently it was explored as an adsorbent for solid-phase extraction (SPE) of nitroimidazoles (NIIMs). The key experimental parameters that affect the extraction efficiency were investigated and optimized. BPM-HCP demonstrated high capability for the effective extraction of trace NIIMs from water, chicken meat and beef samples. Its superior and selective enrichment capability could be attributed to multiple mechanisms: electrostatic attraction, it-stacking, hydrogen bonding, and hydrophobic interactions. Following SPE, the extract was analyzed by HPLC-UV. After optimization, the method for the determination of NIIMs in environmental water, chicken meat and beef samples produced good linear responses within the concentration ranges of 0.21-120.0 ng mL-1, 3.75-120.0 ng g-1, and 2.43-200.0 ng g-1, respectively, with the correlation coefficients (r) falling in the range of 0.9905-0.9997. The limits of detection ranged from 0.025 to 0.067 ng mL-1 for water, 0.625-1.250 ng g-1 for chicken, and 0.53-0.81 ng g-1 for beef. The quantification limits were 0.08-0.21 ng mL-1 (water), 1.88-3.75 ng g-1 (chicken), and 1.59-2.43 ng g-1 (beef), depending on compounds. The recoveries of the method for all the samples ranged from 80.6% to 119%. The method proves applicable for the quantification of NIIMs in environmental water, chicken meat and beef samples.
Bisphenols (BPs) as widely used endocrine-disrupting chemicals can seriously endanger human health. A covalent organic framework (COF) skeleton functionalized with sulfonic acid groups (DT-BD(0.25)-SO3H(0.75)-COF) was designed and constructed through Schiff base reaction. The DT-BD(0.25)-SO3H(0.75)-COF proved to be a brilliant adsorbent, displaying enhanced BPs extraction capability (bisphenol S, bisphenol A, bisphenol F, and bisphenol B). Coupling DT-BD(0.25)-SO3H(0.75)-COF based solid-phase extraction with high performance liquid chromatography-mass spectrometry, we developed a reliable method for sensitive detection of BPs in low-fat milk, skim milk and whole milk samples, realizing excellent analytical performance with low detection limits of 0.06-0.17 ng mL-1, high spiked recovery of 85.7-104%, and satisfactory relative standard deviation of 3.5-6.4%. This work not only highlights DT-BD(0.25)-SO3H(0.75)-COF as a highly effective adsorbent for effectively enriching BPs, but also introduces a novel strategy for COF functionalization, paving the way for broader applications in pollutant monitor and removal.
To address the challenges of phenolic pollutants (PPs), including high toxicity, poor degradability, and difficulty in trace enrichment, this work developed a hydrazone-linked covalent organic framework (DTB-COF). DTB-COF features abundant NH hydrogen bond donors and CN hydrogen bond acceptors within its pores, enabling synergistic adsorption of PPs through hydrogen bonding, hydrophobic interactions, π-π stacking, and pore filling. Employing DTB-COF as a solid-phase extraction adsorbent combined with high-performance liquid chromatography, we established a quantitative detection method. In juice, milk, and honey, the limits of detection were 0.12-0.22, 0.29-0.58, and 0.53-1.51 ng mL-1, respectively; the spiked recoveries ranged from 87.0%-112.0%, 89.1%-112.9%, and 87.6%-112.9%, respectively, with relative standard deviations below 6.89%. This method demonstrates high accuracy and good reproducibility, effectively addressing the limitations of traditional adsorbents, such as low capacity and poor reproducibility, offers a reliable and efficient strategy for the trace analysis of PPs in food matrices.
A novel amino-functionalized pyrazine-based highly conjugated covalent organic framework (NH2-PyCOF) was synthesized via a post-synthetic modification strategy and applied as an adsorbent for the solid-phase extraction (SPE) of four neonicotinoid insecticides (NTIs) in honey, beverage and environmental water samples. The NH2-PyCOF combines a highly conjugated pyrazine skeleton and multiple-NH2 sits, resulting in enhanced hydrophilicity and multiple interaction sites (H bonding sites as well as π-π stacking sites). When coupled NH2-PyCOF based SPE with high-performance liquid chromatography-mass spectrometry (HPLC-MS), the method demonstrated low detection limits (0.01-0.8 ng mL-1), and satisfactory recoveries (86.0-116%) with relative standard deviations below 9.0%. The NH2-PyCOF-SPE-HPLC/MS method exhibits exceptional sensitivity and reproducibility, providing a reliable and efficient approach for monitoring trace NTIs residues in complex matrices.
Trace residues of neonicotinoid insecticides (NIs) in food may pose great risk to the health of human. In this study, an amino and triazine co-functionalized covalent organic framework (Tp@tr-COF) was fabricated and it exhibited significantly enhanced adsorption performance for NIs. The mechanism investigation revealed that hydrogen bond interactions and π-π stacking were the main adsorption forces. With Tp@tr-COF as solid phase extraction adsorbent, a sensitive high-performance liquid chromatography-mass spectrometry method was established for the determination of NIs in leafy vegetables. The accuracy and precision of the established method were verified, achieving low limits of detection (0.18-0.60 ng·g-1) and satisfactory recoveries (90.9%-110%) with RSD ≤ 7.1%. Furthermore, the extraction recovery of Tp@tr-COF remained essentially unchanged after 24 regeneration cycles. These data indicated that the proposed method holds remarkable prospects for the detection of NIs in leafy vegetables and broadens the horizons for the synthesis of functionalized covalent organic frameworks.
Sulforaphane (SFN), a bioactive compound derived from cruciferous vegetables, exhibits anti-cancer properties, though its role in pancreatic cancer is poorly understood. Network pharmacology and molecular docking (computer-simulated) identified the p53 pathway as a potential SFN target. In vitro experiments demonstrated that SFN suppressed PANC-1 cell proliferation and metastasis, induced G2/M arrest, and promoted apoptosis. Western blot analysis revealed SFN-mediated downregulation of cyclin B1 and CDK1 (linked to cycle arrest), upregulation of E-cadherin, and suppression of MMP-9 (impeding invasion). SFN also modulated apoptosis markers (Caspase-3/9 activation, Bax/Bcl-2 imbalance) and activated the p53 pathway (elevated p-p53, p53, p21, and GADD45A). These results underscore SFN's therapeutic potential against pancreatic cancer via p53 signaling.
Hard carbon materials are considered one of the ideal anode materials for sodium-ion batteries (SIBs). However, the practical application of hard carbon materials is limited by complex microstructures and imprecise preparation techniques. On the one hand, advanced hard carbon materials are widely developed through computational simulations and experimental research. On the other hand, the emerging database of precursors − preparation parameters − microstructures − and electrochemical performance has grown fast as more and more research has been reported. The database is greatly beneficial to reducing the trial-and-error nature of the experiments and verifying the reliability of the computational results. In this review, we summarize the rapid development of high-performance hard carbon materials by combining experimental, computational, and data analysis approaches. Focusing on: 1) summarizing the types of precursors and preparation methods to search the development of highly promising precursors and efficient preparation methods, 2) discussing the evolution rule of microstructure parameters and elucidating the correspondence between microstructures and sodium storage mechanisms, 3) revealing the relationship between microstructure characteristics and electrochemical performance of hard carbon, and 4) summarizing the utility potential of various modification strategies on hard carbon. Finally, we outline the main advances and future perspectives of hard carbon in SIBs.
The presence of psychotropic drugs (PDs) in aquatic ecosystems represents an increasing environmental problem, posing a serious threat to human health and aquatic organisms. Lateral flow immunoassays (LFIA) have been widely used in the detection of PD contaminants. However, maintaining signaling tag reporting activity and achieving LFIA's multi-readout capability remain significant challenges to meeting a range of detection scenarios. Here, a rapid multifunctional LFIA has been developed for detecting diazepam (DAP), an emerging environmental and food safety PD contaminant, in lake water and fish samples. Copper hexacyanoferrate nanoparticles doped with Au and Pt (AuPt@Cu-HCF) were designed and manufactured as a multi-signal reporter with exceptional photothermal conversion efficiency and peroxidase-like enzymatic activity. This study integrates the colorimetric, photothermal, catalytic colorimetric, and catalytic photothermal effects of the AuPt@Cu-HCF nanozyme to form a “four-in-one” multi-readout LFIA. The multifunctional detection approach achieved four different detection signal outputs for DAP, with detection limits of 0.82 ng/mL, 12.82 pg/mL, 12.26 pg/mL, and 4.43 pg/mL for the basic colorimetric, photothermal, catalytic colorimetric, and colorimetric photothermal readout modes, respectively. This quadruplex-functional LFIA offers four different options with varying sensitivities and detection ranges, suitable for various application scenarios. It also allows multiple verifications for a single sample, enhancing detection accuracy.
A green and hydroxyl functionalized hypercrosslinked polymer (Esc/BCMBP1:2-HCP) was synthesized for solid-phase extraction (SPE) of diamide insecticides by using natural esculin as monomer for the first time. It exhibited an excellent adsorption performance for the diamides. The major SPE influencing parameters were investigated, and then, a new analytical approach coupling the Esc/BCMBP1:2-HCP based SPE with HPLC-DAD detection was developed for the analysis of the diamide insecticides. Under optimal conditions, a good linearity was achieved in the analytes concentration range of 0.2-100.0 ng mL-1, 3.0-500.0 ng g-1, and 3.0-500.0 ng g-1 for water, rice and soil samples, respectively, with the coefficients of determination>0.9936. The limits of detection were in the range of 0.06-0.30 ng mL-1, 0.90-1.60 ng g-1 and 0.80-1.80 ng g-1, respectively. The method recoveries for the spiked samples were from 87.0 % to 111 %, with the relative standard deviations < 7.5 %.