Nitrogen-rich based conjugated microporous polymers for highly efficient adsorption and removal of COVID-19 antiviral drug chloroquine phosphate from environmental waters.

Chloroquine phosphate (CQP) has been suggested as an important and effective clinical reliever medication for the 2019 coronavirus (COVID-19). Nevertheless, its excessive use will inevitably cause irreparable damage to the entire ecosystem, thereby posing a considerable environmental safety concern. Hence, the development of highly-efficient methods of removing CQP from water pollution sources, e.g., effluents from hospitals and pharmaceutical factories is significant. This study reported the fabrication of novel C-N bond linked conjugated microporous polymers (CMPs) (BPT-DMB-CMP) with multiple nitrogen-rich anchoring sites for the quick and efficient removal of CQP from aqueous solutions. The irreversible covalent C-N bond linked in the internal framework of BPT-DMB-CMP endowed it with good chemical stability and excellent adsorbent regeneration. With its predesigned functional groups (i.e., rich N-H bonds, triazine rings, and benzene rings) and large area surface (1,019.89 m2·g-1), BPT-DMB-CMP demonstrated rapid adsorption kinetics (25 min) and an extraordinary adsorption capacity (334.70 mg·g-1) for CQP, which is relatively higher than that of other adsorbents. The adsorption behavior of CQP on BPT-DMB-CMP corresponded with Liu model and mixed-order model. Based on the density functional theory (DFT) calculations, X-ray photoelectron spectroscopy (XPS), and adsorption comparisons test, the halogen bonding, and hydrogen bonding cooperates with π - π, C - H···π interactions and size-matching effect in the CQP adsorption system on BPT-DMB-CMP. The excellent practicability for the removal of CQP from real wastewater samples verified the prospect of practical application of BPT-DMB-CMP. BPT-DMB-CMP exhibited the application potentials for the adsorption of other antiviral drugs. This work opens up an efficient, simple, and high adsorption capacity way for removal CQP.

Discovery and Functional Analysis of Secondary Hair Follicle miRNAs during Annual Cashmere Growth.

Secondary hair follicles (SHFs) produce the thermoregulatory cashmere of goats. MicroRNAs (miRNAs) play indispensable roles in hair follicle formation and growth. However, most studies examining miRNAs related to cashmere have been performed on goat skin. It remains unclear which miRNAs are highly expressed in SHFs or how miRNAs affect cashmere growth. In the present study, we isolated the SHFs under a dissecting microscope and analyzed the miRNA signatures during annual cashmere growth. Small-RNA sequencing followed by genome-wide expression analysis revealed that early anagen is a crucial phase for miRNA regulation of the cashmere growth, as revealed by two predominant groups of miRNAs. Although they exhibited opposite expression patterns, both groups demonstrated sharp changes of expression when in transit from early anagen to mid-anagen. In addition, we identified 96 miRNA signatures that were differentially expressed between different phases among 376 miRNAs. Functional analysis of the predicted target genes of highly expressed or differentially expressed miRNAs indicated that these miRNAs were involved in signal pathways associated with SHF development, regeneration, and regression. Furthermore, miR-143-3p was preferentially expressed in SHFs and Itga6 was identified as one of targets. The dual-luciferase and in situ hybridization assay demonstrated that miR-143-3p directly repressed the expression of Itga6, suggesting a possible novel role for miR-143-3p in cashmere growth.

Sulfonic acid-functionalized covalent organic frameworks as the coating for stir bar sorptive extraction of fluoroquinolones in milk samples.

Sulfonic acid-functionalized covalent organic frameworks (COF-SO3) as a coating of stir bar sorptive extraction (SBSE) for capturing three fluoroquinolones from milk have been developed. The COF-SO3 material was characterized by X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, and infrared spectroscopy. Milk without any typical treatments like protein precipitation and defatting was only diluted five times with water for test. Combined with high-performance liquid chromatography (HPLC), a SBSE-HPLC method was established for detecting fluoroquinolones in milk samples. The corresponding wide linear ranges (4.00-500.0 µg L-1), low detection limits (1.20-2.62 µg L-1), good test repeatability (RSD < 5.2%), and acceptable enrichment factors (56.2-61.5) were implemented for three fluoroquinolones. The analytical method was applied to determine trace targets and provided satisfactory results. Furthermore, the research displayed satisfied reproducibility for bar-to-bar (RSD < 6.5%) and batch-to-batch (RSD < 8.6%) tests.

Development and Validation of a Method for Determination of 43 Antimicrobial Drugs in Western-Style Pork Products by UPLC-MS/MS with the Aid of Experimental Design.

Western-style pork products have attracted many modern urban consumers, and these products have rapidly entered the Chinese market. The current hazard analysis of processed meat products mainly focuses on processing hazards (PAHs, microorganisms, and food additives), with less attention to veterinary drug residues. According to the survey results, the residues of antimicrobial drugs (sulfonamides and quinolones) in pork and its products in China are a severe problem, which may cause metabolic reactions, toxic effects, or enhance drug resistance. This study applied a modified QuEChERS method combined with ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MSMS) to develop a rapid and sensitive method for determining antimicrobial drugs in bacon and ham was successfully evaluated methodologically by EU 2002/657/EC. This study used a three-level, three-factor Box-Behnken design (BBD) to optimize the QuEChERS method by response surface methodology. The excellent linearity of the calibration curve was shown in the corresponding concentration range with a coefficient of determination greater than 0.99. The values of decision limit (CCα) and detection capability (CCß) were in the range of 10.9-31.3 µg/kg and 11.8-52.5 µg/kg, respectively. The method successfully detected two trace levels of antimicrobial drugs in commercially available samples, including sulfadiazine and moxifloxacin.

A core-shell structured magnetic covalent organic framework (type Fe3O4@COF) as a sorbent for solid-phase extraction of endocrine-disrupting phenols prior to their quantitation by HPLC.

A magnetic covalent organic framework (Fe3O4@COF) with core-shell structure was fabricated at room temperature and used as an adsorbent for magnetic solid-phase extraction of polar endocrine-disrupting phenols (4-n-nonylphenol, 4-n-octylphenol, bisphenol A and bisphenol AF). The sorbent was characterized by transmission electron microscopy, FTIR, powder X-ray diffraction and other techniques. The main parameters governing the extraction efficiency were optimized. The phenols were quantified by HPLC with fluorometric detection. The method has attractive features such as low limits of detection (0.08-0.21 ng.mL-1), wide linear ranges (0.5-1000 ng.mL-1), and good repeatability (intra-day: 0.39%-4.99%; inter-day: 1.57%-5.21%). Satisfactory results were obtained when the developed method was applied to determine the four target pollutants in real world drink samples with spiked recoveries over the range of 81.3~118.0%. This indicates that the method is a powerful tool for the enrichment and determination of endocrine-disrupting phenols in drink samples. Graphical abstract A magnetite based covalent organic framework (Fe3O4@COFs) was synthesized with TPAB, TPA and Fe3O4. It was used for magnetic solid-phase extraction of endocrine-disrupting phenols from plastic-packaged tea drink samples coupled with liquid chromatography (LC) for determination.

Determination of the Total Phenolic Content in Wine Samples Using Potentiometric Method Based on Permanganate Ion as an Indicator.

A rapid and accurate determination method for total phenolic content is of great importance for controlling the quality of wine samples. A promising potentiometric detection approach, based on permanganate ion fluxes across ion-selective electrode membranes, is fabricated for measuring the total phenolic content of wine. The results show that the presence of phenols, such as gallic acid, leads to a potential increase for the potentiometric sensor. Additionally, the present sensor exhibits a linear potential response with the concentration range from 0.05 to 3.0 g/L with a detection limit of 6.6 mg/L calculated using gallic acid. These sensors also exhibit a fast response time, an acceptable reproducibility and long-term stability. These results indicate that the proposed potentiometric sensor can be a promising and reliable tool for the rapid determination of total phenolic content in wine samples.

Determination of 107 Pesticide Residues in Wolfberry with Acetate-buffered Salt Extraction and Sin-QuEChERS Nano Column Purification Coupled with Ultra Performance Liquid Chromatography Tandem Mass Spectrometry.

A multi-residue method for the determination of 107 pesticide residues in wolfberry has been developed and validated. Similar pretreatment approaches were compared, and the linearity, matrix effect, analysis limits, precision, stability and accuracy were validated, which verifies the satisfactory performance of this new method. The LODs and LOQs were in the range of 0.14-1.91 µg/kg and 0.46-6.37 µg/kg, respectively. The recovery of analytes at three fortification levels (10 µg/kg, 50 µg/kg, 100 µg/kg) ranged from 63.3-123.0%, 72.0-118.6% and 67.0-118.3%, respectively, with relative standard deviations (RSDs) below 15.0%. The proposed method was applied to the analysis of fifty wolfberry samples collected from supermarkets, pharmacies and farmers' markets in different cities of Shandong Province. One hundred percent of the samples analyzed included at least one pesticide, and a total of 26 pesticide residues was detected in fifty samples, which mainly were insecticides and bactericide. Several pesticides with higher detection rates were 96% for acetamiprid, 82% for imidacloprid, 54% for thiophanate-methyl, 50% for blasticidin-S, 42% for carbendazim, 42% for tebuconazole and 36% for difenoconazole in wolfberry samples. This study proved the adaptability of the developed method to the detection of multiple pesticide residues in wolfberry and provided basis for the research on the risks to wolfberry health.

Michael-Addition-Mediated Photonic Crystals Allow Pretreatment-Free and Label-Free Sensoring of Ciprofloxacin in Fish Farming Water.

Abuse of antibiotics results in a large number of antibiotics residues in the environment and even causes the problem of "super bacteria". Therefore, it is crucial to develop a powerful analytic method to monitor antibiotics quickly and simply. Photonic crystal (PC), as a sensing material, has promising application prospects. Herein, we try to use PC to realize pretreatment-free and label-free detection of Ciprofloxacin (CF) through Michael addition reaction. The recognition process is carried out by the Michael addition reaction between the piperazine group of CF and the o-benzoquinone group on the PC. The monodisperse microspheres with o-benzoquinone groups are prepared by polymerization and oxidation and then stacked to form PC. During the detection, the peak intensity of the PC decreases with the increasing CF concentration, and the linear range is from 2 to 512 µg/L. The limit of detection (LOD) is 0.76 µg/L. Furthermore, the PC retains 97% of the initial response after storage in a Petri dish at room temperature for 1 month, which shows that it has good stability. Moreover, CF in fish farming water can be detected directly without any pretreatment and label, and the results are in good accordance with the LC-MS-MS results. This Michael-addition-mediated PC is accurate, easily prepared, cost-efficient, and long-term stable. In addition, it is environmentally friendly, because little organic solvent is needed during both the preparation and the detection.

Magnetic covalent triazine-based frameworks as magnetic solid-phase extraction adsorbents for sensitive determination of perfluorinated compounds in environmental water samples.

Covalent organic frameworks (COFs), which are a new type of carbonaceous polymeric material, have attracted great interest because of their large surface area and high chemical and thermal stability. However, to the best of our knowledge, no work has reported the use of magnetic COFs as adsorbents for magnetic solid-phase extraction (MSPE) to enrich and determine environmental pollutants. This work aims to investigate the feasibility of using covalent triazine-based framework (CTF)/Fe2O3 composites as MSPE adsorbents to enrich and analyze perfluorinated compounds (PFCs) at trace levels in water samples. Under the optimal conditions, the method developed exhibited low limits of detection (0.62-1.39 ng·L-1), a wide linear range (5-4000 ng L-1), good repeatability (1.12-9.71%), and good reproducibility (2.45-7.74%). The new method was successfully used to determine PFCs in actual environmental water samples. MSPE based on CTF/Fe2O3 composites exhibits potential for analysis of PFCs at trace levels in environmental water samples. Graphical abstract Magnetic covalent triazine-based frameworks (CTFs) were used as magnetic solid-phase extraction adsorbents for the sensitive determination of perfluorinated compounds in environmental water samples. PFBA perfluorobutyric acid, PFBS perfluorobutane sulfonate, PFDA perfluorodecanoic acid, PFDoA perfluorododecanoic acid, PFHpA perfluoroheptanoic acid, PFHxA perfluorohexanoic acid, PFHxS perfluorohexane sulfonate, PFNA perfluorononanoic acid, PFOA perfluorooctanoic acid, PFPeA perfluoropentanoic acid, PFUdA Perfluoroundecanoic acid.

A Zr(IV)-based porphyrinic metal-organic framework as a solid-phase sorbent for extraction of sulfonamides prior to their quantitation by LC-MS.

A porphyrinic metal-organic framework (PCN-224) was fabricated and used as an adsorbent for solid-phase extraction of ultratrace levels of polar sulfonamide antibiotics from food and drinking waters. The PCN-224 was characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, and powder X-ray diffraction analyses. Parameters affecting the extraction efficiency were optimized. The sulfonamides were quantified by liquid chromatography-tandem mass spectrometry. Figures of merit include (a) low limits of detection (0.07-0.47 ng·L-1), (b) wide linear ranges (0.5-2000 ng·L-1), and (c) good repeatabilities (2.8%-6.7%) and reproducibilities (1.7%-5.1%). The method was successfully applied to the determination of sulfonamides in food and drinking water samples. Graphical abstract A Zr(IV)-based porphyrinic metal-organic framework (PCN-224) was synthesized from a Zr6 cluster and the H2TCPP ligand. It was used for solid-phase extraction of sulfonamides from food and drinking water samples coupled with liquid chromatography-tandem mass spectrometry (LC-MS/MS) for determination.

Preconcentration and Determination of Perfluoroalkyl Substances (PFASs) in Water Samples by Bamboo Charcoal-Based Solid-Phase Extraction Prior to Liquid Chromatography-Tandem Mass Spectrometry.

In this work, bamboo charcoal was used as solid-phase extraction adsorbent for the enrichment of six perfluoroalkyl acids (PFAAs) in environmental water samples before liquid chromatography-tandem mass spectrometry analysis. The specific porous structure, high specific surface area, high porosity, and stability of bamboo charcoal were characterized. Several experimental parameters which considerably affect extraction efficiency were investigated and optimized in detail. The experimental data exhibited low limits of detection (LODs) (0.01-1.15 ng/L), wide linear range (2-3 orders of magnitude and R ≥ 0.993) within the concentration range of 0.1-1000 ng/L, and good repeatability (2.7-5.0%, n = 5 intraday and 4.8-8.3%, n = 5 interday) and reproducibility (5.3-8.0%, n = 3). Bamboo charcoal was successfully used for the enrichment and determination of PFAAs in real environmental water samples. The bamboo charcoal-based solid-phase extraction coupled with liquid chromatography-tandem mass spectrometry analysis possessed great potential in the determination of trace PFAA levels in environmental water samples.

Poly(styrene-co-N-methacryloyl-l-phenylalanine methyl ester)-functionalized magnetic nanoparticles as sorbents for the analysis of sodium benzoate in beverages.

In this study, poly(styrene-co-N-methacryloyl-l-phenylalanine methyl ester)-functionalized magnetic nanoparticles were constructed and used as magnetic solid-phase extraction sorbents for analysis of food preservatives in beverages. To prepare the poly(amino acid)-based sorbents, N-methacryloyl-l-phenylalanine methyl ester, and styrene served as the functional monomers and modified onto the magnetic nanoparticles via free radical polymerization. Interestingly, compared with propylparaben and potassium sorbate, the proposed poly(amino acid)-based sorbents showed a good selectivity to sodium benzoate. The adsorption capacity of the sorbents to sodium benzoate was 6.08 ± 0.31 mg/g. Moreover, the fast adsorption equilibrium could be reached within 5 min. Further, the resultant poly(amino acid)-based sorbents were applied in the analysis of sodium benzoate in real beverage samples. The results proved that the proposed magnetic solid-phase extraction sorbents have a great potential for the analysis of preservatives in food samples.

Aminosilanized magnetic carbon microspheres for the magnetic solid-phase extraction of bisphenol A, bisphenol AF, and tetrabromobisphenol A from environmental water samples.

Aminosilanized magnetic carbon microspheres as a novel adsorbent were designed and fabricated. The adsorbent was used for the magnetic solid-phase extraction of bisphenols at trace levels from environmental water samples before liquid chromatography with tandem mass spectrometry analysis. The structure, surface, and magnetic behavior of the as-prepared aminosilanized magnetic carbon microspheres were characterized by elemental analysis, scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, powder X-ray diffraction, and vibrating sample magnetometry. The effects of the experimental parameters were investigated by the Plackett-Burman design, and then the parameters that were significant to the extraction efficiencies were optimized through a response surface methodology. The aminosilanized magnetic carbon microspheres exhibited high adsorption efficiency and selectivity for bisphenols. Under optimal conditions, low limits of detection (0.011-2.22 ng/L), and a wide linear range (2-3 orders of magnitude), good repeatability (4.7-7.8%, n = 5), and reproducibility (6.0-8.3%, n = 3) were achieved. The results demonstrate that the novel adsorbent possesses great potentials in the determination of trace levels of bisphenols in environmental water samples.

Metal-Organic Framework@Microporous Organic Network as Adsorbent for Solid-Phase Microextraction.

The practical applications of moisture sensitive metal-organic frameworks (MOFs) in the extraction technique are faced with avoided challenges related to competitive adsorption and hydrostability. The target analytes cannot be effectively extracted under humid conditions because of the competitive moisture adsorption and/or framework structure collapse of MOFs. In this Letter, metal-organic framework (MOF)@microporous organic network (MON) hybrid materials were explored for the first time as fiber coatings for solid-phase microextraction (SPME). Microporous materials with a hydrophobic surface was formed by coating the MOFs (MIL-101 and MOF-5) with MON through a sonogashira coupling reaction. MON acted as a hydrophobic "shield" to hinder the competitive moisture adsorption and improve moisture resistance and stability of the fiber. The sorbent exhibited higher enrichment factors (1215-3805) toward PAHs than other analytes in the water samples. An SPME method using MOF@MON-based fiber was developed to quantitatively determine PAHs. The proposed method was successfully applied to analyze PAHs in environmental water, particulate matter (PM2.5), and food samples. A successful technique is proposed to chemically control MOF for applications in solid-phase sorption-based extraction techniques.

Cadmium(II)-based metal-organic nanotubes as solid-phase microextraction coating for ultratrace-level analysis of polychlorinated biphenyls in seawater samples.

In this study, stable cadmium(II)-based metal-organic nanotubes (Cd-MONTs) were prepared and used as a coating material for solid-phase microextraction (SPME) of polychlorinated biphenyls (PCBs) from environmental water samples. The as-prepared Cd-MONT SPME coating material was characterized by thermal gravimetric analysis, scanning electron microscopy, and X-ray diffraction. The synthesized Cd-MONTs exhibited high thermal stability (385 °C) and excellent extraction performance toward PCBs. The important conditions were optimized systematically by the response surface method. Under the optimal conditions, the new fiber achieved high enrichment factors (938-3417), low limits of detection (1.80-8.73 pg L-1), and wide linearity (10-5000 pg L-1). The method developed was used in ultratrace-level analysis of PCBs in seawater samples, with satisfactory results for each sample.

Enrichment and determination of octylphenol and nonylphenol in environmental water samples by solid-phase microextraction with carboxylated carbon nano-spheres coating prior to gas chromatography-mass spectrometry.

In this paper, a novel and simple method for the sensitive determination of endocrine disrupter compounds octylphenol (OP) and nonylphenol (NP) in environmental water samples has been developed using solid-phase microextraction (SPME) coupled with gas chromatography-mass spectrometry. Carboxylated carbon nano-spheres (CNSs-COOH) are used as a novel SPME coating via physical adhesion. The CNSs-COOH fiber possessed higher adsorption efficiency than 100 µm polydimethysiloxane (PDMS) fiber and was similar to 85 µm polyacrylate (PA) fiber for the two analytes. Important parameters, such as extraction time, pH, agitation speed, ionic strength, and desorption temperature and time, were investigated and optimized in detail. Under the optimal parameters, the developed method achieved low limits of detection of 0.13~0.14 ng·L(-1) and a wide linear range of 1~1000 ng·(-1) for OP and NP. The novel method was validated with several real environmental water samples, and satisfactory results were obtained.

Accelerated solvent extraction combined with dispersive liquid-liquid microextraction before gas chromatography with mass spectrometry for the sensitive determination of phenols in soil samples.

A method combining accelerated solvent extraction with dispersive liquid-liquid microextraction was developed for the first time as a sample pretreatment for the rapid analysis of phenols (including phenol, m-cresol, 2,4-dichlorophenol, and 2,4,6-trichlorophenol) in soil samples. In the accelerated solvent extraction procedure, water was used as an extraction solvent, and phenols were extracted from soil samples into water. The dispersive liquid-liquid microextraction technique was then performed on the obtained aqueous solution. Important accelerated solvent extraction and dispersive liquid-liquid microextraction parameters were investigated and optimized. Under optimized conditions, the new method provided wide linearity (6.1-3080 ng/g), low limits of detection (0.06-1.83 ng/g), and excellent reproducibility (<10%) for phenols. Four real soil samples were analyzed by the proposed method to assess its applicability. Experimental results showed that the soil samples were free of our target compounds, and average recoveries were in the range of 87.9-110%. These findings indicate that accelerated solvent extraction with dispersive liquid-liquid microextraction as a sample pretreatment procedure coupled with gas chromatography and mass spectrometry is an excellent method for the rapid analysis of trace levels of phenols in environmental soil samples.

MiR-22 suppresses the proliferation and invasion of gastric cancer cells by inhibiting CD151.

Gastric cancer (GC) is the second common cause of cancer-related death worldwide. microRNAs (miRNAs) play important roles in the carcinogenesis of GC. Here, we found that miR-22 was significantly decreased in GC tissue samples and cell lines. Ectopic overexpression of miR-22 remarkably suppressed cell proliferation and colony formation of GC cells. Moreover, overexpression of miR-22 significantly suppressed migration and invasion of GC cells. CD151 was found to be a target of miR-22. Furthermore, overexpression of CD151 significantly attenuated the tumor suppressive effect of miR-22. Taken together, miR-22 might suppress GC cells growth and motility partially by inhibiting CD151.

Feasibility of hydrofluoric acid etched sand particles for enrichment and determination of polychlorinated biphenyls at trace levels in environmental water samples.

This study aims to investigate the feasibility of etched sand particles being used as solid-phase extraction adsorbents to enrich polychlorinated biphenyls (PCBs), which are typical persistent organic pollutants in the environment, at trace levels. Gas chromatography-tandem mass spectrometry was selected to detect the compounds. Etched sand particles exhibited excellent merits on the enrichment of PCBs. Related important factors affecting extraction efficiencies were investigated and optimized in detail. Under optimized conditions, low limits of detection (0.42 to 3.69 ng L(-1)), wide linear range (10 to 1,000 ng L(-1)), and high repeatability (1.9 to 8.2%) were achieved. The developed method was validated with several real water samples, and satisfactory results were obtained. All of these findings indicate that etched sand particles would be useful for the enrichment and determination of organic pollutants at trace levels in water samples.

Determination of preservatives in soft drinks by capillary electrophoresis with ionic liquids as the electrolyte additives.

A capillary electrophoresis method for separating preservatives with various ionic liquids as the electrolyte additives has been developed. The performances for separation of the preservatives using five ionic liquids with different anions and different substituted group numbers on imidazole ring were studied. After investigating the influence of the key parameters on the separation (the concentration of ionic liquids, pH, and the concentration of borax), it has been found that the separation efficiency could be improved obviously using the ionic liquids as the electrolyte additives and tested preservatives were baseline separated. The proposed capillary electrophoresis method exhibited favorable quantitative analysis property of the preservatives with good linearity (r(2) = 0.998), repeatability (relative standard deviations ≤ 3.3%) and high recovery (79.4-117.5%). Furthermore, this feasible and efficient capillary electrophoresis method was applied in detecting the preservatives in soft drinks, introducing a new way for assaying the preservatives in food products.