Textural Precursor Compositions Harvested for Independent Signal Generators: Scaling Micron-Sized Flower-Like Metal-Organic Frameworks as Amplifying Units for Dual-Mode Glycoprotein Assay.

In this work, a micron-sized flower-like metal-organic frameworks (MOFs)-based boronate-affinity sandwich-type immunoassay was fabricated for the dual-mode glycoprotein assay. For proof of concept, the flower-like MOFs were synthesized from transition Cu nodes and tetrakis (4-carboxyphenyl) porphyrin (TCPP) ligands by spontaneous standing assembly. In addition, the specificity toward glycoprotein involved the antigen recognition as well as covalent bonding via the boronate-glycan affinity, and the immediate signal responses were initiated by textural decomposition of the flower-like MOFs. Intriguingly, Cu nodes, of which the valence state is dominant by CuI species, can endow the Fenton-like catalytic reaction of the fluorogenic substrate for generating fluorescence signals. For benefits, TCPP ligands, in which each TCPP molecule has four guest donors, can provide multiple valences for the assembly of cyclodextrin-capped gold nanoparticles via host-guest interaction for colorimetry output. Albeit important, the scaling micrometer patterns for the flower-like MOFs carrying numerous Cu nodes and TCPP ligands can also function as amplifying units, signifying the output signal. The detection limit of the dual-mode glycoprotein assay can reach 10.5 nM for the fluorescence mode and 18.7 nM for the colorimetry mode, respectively. Furthermore, the merits of harvesting different signal generators toward the multimodal readout patterns can allow the mutual verification and make the analytical results more reliable. Collectively, our proposed assay may offer a new idea in combining the inherent textural merits from MOFs for dual signal generators, which can also emphasize accurate detection capability for glycoprotein assay.

Highly Active Hydrogen-rich Photothermal Reverse Water Gas Shift Reaction on Ni/LaInO3 Perovskite Catalysts with Near-unity Selectivity.

Photo-assisted reverse water gas shift (RWGS) reaction is regarded green and promising in controlling the reaction gas ratio in Fischer Tropsch synthesis. But it is inclined to produce more byproducts in high H2 concentration condition. Herein, LaInO3 loaded with Ni-nanoparticles (Ni NPs) was designed to obtain an efficient photothermal RWGS reaction rate, where LaInO3 was enriched with oxygen vacancies to roundly adsorbing CO2 and the strong interaction with Ni NPs endowed the catalysts with powerful H2 activity. The optimized catalyst performed a large CO yield rate (1314 mmol gNi -1 h-1 ) and ≈100 % selectivity. In situ characterizations demonstrated a COOH* pathway of the reaction and photoinduced charge transfer process for reducing the RWGS reaction active energy. Our work provides valuable insights on the construction of catalysts concerning products selectivity and photoelectronic activating mechanism on CO2 hydrogenation.

Near 90% Transparent ITO-Based Flexible Electrode with Double-Sided Antireflection Layers for Highly Efficient Flexible Optoelectronic Devices.

As a widely used substrate for flexible electronics, indium-tin oxide-based polymer electrodes (polymer-ITO electrodes) exhibit poorly visible light transmittance of less than 80%. The inferior transmittance for polymer-ITO electrodes severely limits the performance improvement of polymer-ITO based electronics. Here, a conceptually different approach of the double-sided antireflection coatings (DARCs) strategy is proposed to modulate both the air-polymer substrate interface and ITO-air interface refractive index gradient, to synergistically improve the transmittance of polymer-ITO electrodes. On the basis of SiO2 nanoparticles antireflection layer on polymer substrate, a polymer-metal oxide composite antireflection film is fabricated on the ITO side. Resultantly, the transmittance of ITO-based flexible electrodes is successfully improved from 76.8% to 89.8%, which is the highest transmittance among the reported ITO-based flexible electrodes. Furthermore, the photoluminescence emission intensity of luminescent materials enveloped with the DARCs electrodes increases by 74% over that with reference electrodes, demonstrating the DARCs antireflection strategy can efficiently improve the performance of flexible optoelectronic devices. With DARCs electrode, the flexible perovskite solar cells exhibit an enhanced efficiency from 18.80% to 20.85%.

Hydrophilic molecularly imprinted polymers functionalized magnetic carbon nanotubes for selective extraction of cyclic adenosine monophosphate from winter jujube.

In this work, a green strategy was developed to prepare molecularly imprinted polymers functionalized magnetic carbon nanotubes in aqueous phase under mild conditions for cyclic adenosine monophosphate. Thanks to water solubility of chitosan, a natural polysaccharide which is rich in amino and hydroxyl groups, provided the feasibility to synthesize the green molecularly imprinted polymers for water soluble template in aqueous media. Coupled with high-performance liquid chromatography, the method exhibited a short equilibrium time (6 min), high adsorption capacity (22.42 µg/mg), high magnetic susceptibility, and good selectivity to template molecule with the imprinting factor of 2.94. A good linearity in the range of 0.020-3.0 mg/mL for target was obtained with a correlation coefficient of 0.9998. The limit of detection (signal-to-noise ratio = 3) and limit of quantitation (signal-to-noise ratio = 10) of the magnetic solid phase extraction method for cyclic adenosine monophosphate were 5 and 15 ng/mg, respectively. And the practical application of chitosan-based molecularly imprinted polymers as adsorbent to isolate and determine cyclic adenosine monophosphate in real natural samples (winter jujube) was demonstrated.

Molecularly imprinted polymer functionalized magnetic Fe3 O4 for the highly selective extraction of triclosan.

We present a facile strategy to prepare the molecularly imprinted polymers layer on the surface of Fe3 O4 nanoparticles with core-shell structure via sol-gel condensation for recognition and enrichment of triclosan. The Fe3 O4 nanoparticles were first synthesized by a solvothermal method. Then, template triclosan was self-assembled with the functional monomer 3-aminopropyltriethoxysilane on the silica-coated Fe3 O4 nanoparticles in the presence of ethanol and water. Finally, the molecularly imprinted polymers were formed on the surface of silica-coated Fe3 O4 nanoparticles to obtain the product. The morphology, magnetic susceptibility, adsorption, and recognition property of magnetic molecularly imprinted polymers were characterized using transmission electron microscopy, Fourier transform infrared spectroscopy, X-ray diffractometry, vibrating sample magnetometry, and re-binding experiments. The magnetic molecularly imprinted polymers showed binding sites with good accessibility, fast adsorption rate, and high adsorption capacity (218.34 µg/g) to triclosan. The selectivity of magnetic molecularly imprinted polymers was evaluated by the rebinding capability of triclosan and two other structural analogues (phenol and p-chlorophenol) in a mixed solution and good selectivity with an imprinting factor of 2.46 was obtained. The application of triclosan removal in environmental samples was demonstrated.

Revealing the A-Site Effect of Lead-Free A3 Sb2 Br9 Perovskite in Photocatalytic C(sp3 )-H Bond Activation.

The lead-free halide perovskite A3 Sb2 Br9 is utilized as a photocatalyst for the first time for C(sp3 )-H bond activation. A3 Sb2 Br9 nanoparticles (A3 Sb2 Br9 NPs) with different ratios of Cs and CH3 NH3 (MA) show different photocatalytic activities for toluene oxidation and the photocatalytic performance is enhanced when increasing the amount of Cs. The octahedron distortion caused by A-site cations can change the electronic properties of X-site ions and further affect the electron transfer from toluene molecules to Br sites. After the regulation of A-site cations, the photocatalytic activity is higher with A3 Sb2 Br9 NPs than that with classic photocatalysts (TiO2 , WO3 , and CdS). The main active species involved in photocatalytic oxidation of toluene are photogenerated holes (h+ ) and superoxide anions (. O2 - ). The octahedron distortion by A-site cations affecting photocatalytic activity remains unique and is also a step forward for understanding more about halide-perovskite-based photocatalysis. The relationship between octahedron distortion and photocatalysis can also guide the design of new photocatalytic systems involving other halide perovskites.

Single-Particle Enumeration-Based Sensitive Glutathione S-Transferase Assay with Fluorescent Conjugated Polymer Nanoparticle.

Glutathione S-transferase (GST) is a group of multifunctional enzyme and participates in many physiological processes, such as xenobiotic biotransformation, drug metabolism, and degradation of toxic products. Herein, we demonstrate a label-free fluorescent conjugated polymer nanoparticle (FCPNPs)-based single-particle enumeration (SPE) method for the sensitive GST assay. Fluorescence resonance energy transfer (FRET) is formed between the glutathione-modified FCPNPs (FCPNPs-GSH) and polyethylenimine-capped gold nanoparticles (GNPs@PEI). Therefore, the fluorescence of FCPNPs-GSH is quenched remarkably. In the presence of GST, GNPs@PEI stay away from FCPNPs-GSH due to the specific interaction between FCPNPs-GSH and GST, leading to the inhibition of FRET. As a result, the fluorescence emission of FCPNPs-GSH is restored, which is reflected as the increase of the number of fluorescent particles in the microscopic image. By statistically counting the target concentration-dependent fluorescent particle number, accurate quantification of GST is achieved. The linear range from 0.01 to 6 µg/mL is obtained for GST assay and the limit-of-detection (LOD) is 1.03 ng/mL, which is much lower than the ensemble fluorescence spectra measurements in bulk solution. In urine sample assay, satisfactory recoveries in the range of 97.5-106.5.0% are achieved. Because of the high sensitivity and excellent specificity, this method can be extended to the detection of other disease-related biomolecules in the future.

Stable and Highly Efficient Photocatalysis with Lead-Free Double-Perovskite of Cs2 AgBiBr6.

Composition engineering of halide perovskite allows the tunability of the band gap over a wide range so that photons can be effectively harvested, an aspect that is of critical importance for increasing the efficiency of photocatalysis under sunlight. However, the poor stability and the low photocatalytic activity of halide perovskites prevent use of these defect-tolerant materials in wide applications involving photocatalysis. Here, an alcohol-based photocatalytic system for dye degradation demonstrated high stability through the use of double perovskite of Cs2 AgBiBr6 . The reaction rate on Cs2 AgBiBr6 is comparable to that on CdS, a model inorganic semiconductor photocatalyst. The fact of fast reaction between free radicals and dye molecules indicates the unique catalytic properties of the Cs2 AgBiBr6 surface. Deposition of metal clusters onto Cs2 AgBiBr6 effectively enhances the photocatalytic activity. Although the stability (five consecutive photocatalytic cycles without obvious decrease of efficiency) requires further improvements, the results indicate the significant potential of Cs2 AgBiBr6 -based photocatalysis.

Background-Free Imaging of a Viral Capsid Proteins Coated Anisotropic Nanoparticle on a Living Cell Membrane with Dark-Field Optical Microscopy.

Exploring the diffusion dynamics of a viral capsid proteins (VCP)-functionalized nanocarrier on a living cell membrane could provide much kinetic information for the better understanding of their biological functionality. Gold nanoparticles are an excellent core material of nanocarriers because of the good biocompatibility as well as versatile surface chemistry. However, due to the strong scattering background from subcellular organelles, it is a grand challenge to selectively image an individual nanocarrier on a living cell membrane. In this work, we demonstrated a convenient strategy to effectively screen the scattering background from living cells for single-particle imaging with a polarization-resolved dual-channel imaging module. By taking advantage of the polarization of anisotropic gold nanoparticles (gold nanorods, GNRs), the signals from cell components could be counteracted after subtracting the sequential images one by one, while those transiently rotating GNRs on the cell membrane still exist in the processed image. In contrast to the previously reported methods, this method does not require a complicated optical setup alignment and sophisticated digital image analysis process. According to the single-particle imaging results, the majority of VCP-GNRs were anchoring on the cell membrane with confined diffusion. Interestingly, on further inspection of the diffusion trajectories, the particles displayed anomalous confined diffusion with randomly distributed large walking steps during the whole track. Non-Gaussian step distribution was noted, indicating heterogeneous binding and desorption processes on the cell membrane. As a consequence of the robust background screening capability, this approach would find broad applications for single-particle imaging under a noisy environment, e.g., living cells.

Electrospun Fiber Membrane with the Dual Affinity of Chelation and Covalent Interactions for the Efficient Enrichment of Glycoproteins.

As important biomarkers of many diseases, glycoproteins are of great significance to biomedical science. It is essential to develop efficient glycoprotein enrichment platforms and investigate their adsorption mechanism. In this work, a conspicuous enrichment strategy for glycoproteins was developed by using an electrospun fiber membrane wrapped with polydopamine (PDA) and modified with 3-aminophenylboronic acid and nickel ions, named PAN/DA@PDA@APBA/Ni. The enrichment characteristics of PAN/DA@PDA@APBA/Ni toward glycoproteins were explored through adsorption behavior. Thanks to the existence of two sites of interaction (metal ion chelation and boronate affinity), PAN/DA@PDA@APBA/Ni exhibited significant enrichment capacity for glycoproteins, ovalbumin (604.6 mg/g), and human immunoglobulin G (331.0 mg/g). The adsorption kinetic results of glycoprotein ovalbumin on PAN/DA@PDA@APBA/Ni conform to the pseudo-first-order kinetic model in the first adsorption stage, while the second half adsorption stage is more in line with the pseudo-second-order kinetic model. Moreover, the physical characteristics of PAN/DA@PDA@APBA/Ni and subsequent adsorption experiments on electrospun fiber modified with only phenylboronic acid or nickel ions both confirmed two sites of interaction (metal ion chelation and boronate affinity, respectively). Furthermore, a stepwise elution method with dual-affinity interaction was designed and successfully applied to enrich glycoproteins in real biological samples. This work provides an idea for sample pretreatment, especially for the design of dual-affinity materials in glycoproteins enrichment.

A self-calibrating ratiometric fluorescence sensor with photonic crystal-based signal amplification for the detection of tetracycline in food.

A dual-color ratiometric fluorescence sensor based on photonic crystals (PCs) was developed to detect tetracycline (TC) in food. PC was fabricated via self-assembly of carbon dots (CDs)-loaded SiO2 nanoparticles. Gold nanoclusters (AuNCs) and copper ions (Cu2+) were then adsorbed onto the PC for sensor fabrication. The fluorescence of AuNCs was amplified by the PC with an enhancement ratio of 7.6, providing higher sensitivity. The fluorescence of AuNCs was quenched by Cu2+, whereas that of CDs remained unchanged as an internal reference. TC restored the fluorescence of AuNCs owing to its complexation with Cu2+, resulting in a change in the fluorescence intensity ratio. The sensor exhibited a good linear relationship with TC concentrations ranging from 0.1 to 10 µM, with a detection limit of 34 nM. Furthermore, the sensor was applied for TC detection in food with satisfactory recoveries and relative standard deviations, revealing great potential in practical application.

Construction of Stable Magnetic Vinylene-Linked Covalent Organic Frameworks for Efficient Extraction of Benzimidazole Fungicides.

Covalent organic frameworks (COFs) have attracted impressive interest in separation on aqueous media. Herein, we integrated the stable vinylene-linked COFs with magnetic nanosphere via the monomer-mediated in situ growth strategy to construct a crystalline Fe3O4@v-COF composite for enrichment and determination of benzimidazole fungicides (BZDs) from complex sample matrices. The Fe3O4@v-COF has a crystalline assembly, high surface area, porous character together with a well-defined core-shell structure, and serves as progressive pretreatment materials for magnetic solid phase extraction (MSPE) of BZDs. Adsorption mechanism studies revealed that the extended conjugated system and numerous polar cyan groups on v-COF provides abundant π-π and multiple hydrogen bonding sites, which are conducive to interact with BZDs collaboratively. Fe3O4@v-COF also displayed enrichment effects to various polar pollutions with conjugated structures and hydrogen-bonding sites. Fe3O4@v-COF-based MSPE-high-performance liquid chromatography exhibited the low limit of detection, wide linearity, and good precision. Moreover, Fe3O4@v-COF showed better stability, enhanced extraction performance, and more sustainable reusability in comparison with its imine-linked counterpart. This work proposes a feasible strategy on constructing the crystalline stable magnetic vinylene-linked COF composite for the determination of trace contaminants in complex food matrices.

Construction of magnetic covalent organic frameworks functionalized by benzoboroxole for efficient enrichment of glycoproteins in the physiological environment.

To date, the development of highly selective and efficient glycoproteins/peptides enrichment is still a challenge for mass spectrometry-based proteomic analysis. In this work, we reported a novel strategy to prepare a magnetic amide-linked covalent organic framework functionalized by benzoboroxole (denoted as Fe3O4@COF-ABB), which was then used as an adsorbent for the enrichment of glycoproteins. The physical and adsorption properties of Fe3O4@COF-ABB were fully investigated. The Fe3O4@COF-ABB presents a regular core-shell spherical structure, quick magnetic response performance, regular porosity, and multiple binding sites of phenylboronic acid. Taking advantage of these benefits, the synthesized magnetic composites exhibited a superior adsorption capacity (565.8 mg g-1) and high selectivity towards glycoprotein immunoglobulin G (IgG) under physiological state (pH 7.4). Additionally, the adsorbent Fe3O4@COF-ABB could be easily regenerated and reused 5 times with no reduction of enrichment performance. More importantly, the practical applications of Fe3O4@COF-ABB were further demonstrated by the selective adsorption of IgG from human serum. The present work represents a rational design of versatile functionalization of magnetic COFs, which demonstrates an avenue for the selective enrichment and analysis of IgG from real biological sample matrices.

An ultrasensitive label-free biosensor based on aptamer functionalized two-dimensional photonic crystal for kanamycin detection in milk.

A novel photonic crystal aptamer biosensor SiO2-Au-ssDNA two-dimensional photonic crystal (2D PC), allowing label-free and highly sensitive to kanamycin (KANA), is successfully manufactured. This 2D PC biosensor was prepared via a needle tip flow method, using electrostatic adsorption to introduce negatively charged gold nanoparticles (Au NPs) into the 2D PC, combined with sulfhydryl-modified ssDNA for the rapid measurement. Benefiting from the localized surface plasmon resonance effect of Au NPs and optical response capability of PC, the biosensor has an excellent performance on quantitative analysis of KANA ranging from 5 pg∙mL-1 to 5 µg∙mL-1, with a limit of detection of 1.10 pg∙mL-1. The recovery of KANA is between 97 % and 110 % in the milk samples with relative standard deviation less than 4.8 %, which revealing that the 2D PC biosensor has the excellent performance on the KANA detection in complex conditions.

An aptamer-functionalized photonic crystal sensor for ultrasensitive and label-free detection of aflatoxin B1.

As a novel optical responsive material, photonic crystal is a promising sensing material in the recognition and detection of small molecules. Herein, a label-free composite sensor for aflatoxin B1 (AFB1) based on aptamer-functionalized photonic crystal arrays was successfully developed. Three-dimensional photonic crystals (3D PhCs) with a controllable number of layers were produced by a layer-by-layer (LBL) approach, and the introduction of gold nanoparticles (AuNPs) facilitated the immobilization procedure of recognition element aptamers, thus creating the AFB1 sensing detection system (AFB1-Apt 3D PhCs). The sensing system AFB1-Apt 3D PhCs exhibited a good linearity in the wide range of 1 pg mL-1-100 ng mL-1 AFB1 with a limit of detection (LOD) of 0.28 pg mL-1. Furthermore AFB1-Apt 3D PhC was successfully applied in the determination of AFB1 in the millet and beer samples with good recovery. The sensing system performed ultrasensitive and label-free detection to the target, which could be further applied in the fields of food safety, clinical diagnosis or environmental monitoring, establishing an efficient and rapid universal detection platform.

Highly Efficient Solar-Driven Dry Reforming of Methane on a Rh/LaNiO3 Catalyst through a Light-induced Metal-To-Metal Charge Transfer Process.

As an energy-saving and green method, solar-driven dry reforming of methane (DRM) is expected to introduce new activation processes and prevent sintering and coking of the catalysts. However, it still lacks an efficient way to coordinate the regulation of activation of reactants and lattice oxygen migration. In this study, Rh/LaNiO3 is designed as a highly efficient photothermal catalyst for solar-driven DRM, which performs production rates of 452.3 mmol h-1  gRh -1 for H2 and 527.6 mmol h-1  gRh -1 for CO2 under a light intensity of 1.5 W cm-2 , with an excellent stability. Moreover, a remarkable light-to-chemical energy efficiency (LTCEE) of 10.72% is achieved under a light intensity of 3.5 W cm-2 . The characterizations of surface electronic and chemical properties and theoretical analysis demonstrate that strong adsorption for CH4 and CO2 , light-induced metal-to-metal charge transfer (MMCT) process and high oxygen mobility together bring Rh/LaNiO3 excellent performance for solar-driven DRM.

Multi-stimuli responsive molecularly imprinted nanoparticles with tailorable affinity for modulated specific recognition of human serum albumin.

A kind of novel multi-stimuli responsive molecularly imprinted polymers with bovine serum albumin (BSA) as a dummy template (MSR-BSA-MIPs) was fabricated for specific recognition of human serum albumin (HSA) with modulated affinity. The MSR-BSA-MIPs were prepared through free radical polymerization using vinyl modified magnetic nanoparticles as substrates, bovine serum albumin (BSA), with high amino acid sequence similarity but low price compared to HSA, as the dummy template, N-(3-(dimethylamino)-propyl)-methacrylamide (DMAPMA) and N-isopropylacrylamide (NIPAm) as functional monomers with ionic strength and temperature response. The conditions of polymerization, adsorption and elution were systematically investigated. As expected, the obtained MSR-BSA-MIPs exhibited rapid dispersion or separation states under magnetic control, flexible conversion of adsorption and desorption for the target protein under temperature or ionic strength adjustment. Ten adsorption-desorption cycles were carried out with a little decrease in adsorption capacity under two different elution methods, which also inspired us to combine two elution methods while considering both the stability and adsorption capacity of MSR-BSA-MIPs. The adsorption capacity (Q) and imprinting factor (IF) of MSR-BSA-MIPs for HSA are 43.01 mg g-1 and 4.26, respectively. Furthermore, the blood was opted as a realistic specimen for evaluating the adsorption capability of the proposed adsorbent, emphasizing its good practicality for target protein recognition and enrichment.

The electrospun polyacrylonitrile/covalent organic framework nanofibers for efficient enrichment of trace sulfonamides residues in food samples.

In this work, the electrospun polyacrylonitrile/covalent organic frameworks Tp-BD nanofibers (PAN/Tp-BD) were synthesized and applied as an adsorbent for thin film microextraction (TFME) of seven sulfonamides in animal derived food samples. The morphology, structure, porosity, and stability of the prepared nanofibers were investigated. The PAN/Tp-BD nanofibers exhibited good chemical stability, high flexibility, porous fibrous structure, and excellent extraction efficiency. Based on the PAN/Tp-BD nanofibers as the adsorbent, a thin film microextraction-high performance liquid chromatography (TFME-HPLC) method for the determination of seven sulfonamides (SAs) in food samples was developed. Under the optimal conditions, the TFME-HPLC exhibited the low limit of detection (0.10-0.18 ng·mL-1), the low limit of quantitation (0.33-0.60 ng·mL-1), the wide linear range (0.5-50 ng·mL-1) with correlation coefficients between 0.994 and 0.998, and good enrichment factors between 39.7 to 170.1 towards 20 ng/mL SAs solution. The relative standard deviation (RSD) was lower than 11% in the interday and intraday analysis. Furthermore, the applicability of PAN/Tp-BD nanofibers was demonstrated for measuring trace SAs residues in the spiked food samples with recoveries ranging from 85.3% to 115.2%. The results demonstrated that the PAN/Tp-BD nanofibers have great potential for the efficient extraction of sulfonamides from complex food samples.

Covalent Organic Framework/Polyacrylonitrile Electrospun Nanofiber for Dispersive Solid-Phase Extraction of Trace Quinolones in Food Samples.

The extraction of quinolone antibiotics (QAs) is crucial for the environment and human health. In this work, polyacrylonitrile (PAN)/covalent organic framework TpPa-1 nanofiber was prepared by an electrospinning technique and used as an adsorbent for dispersive solid-phase extraction (dSPE) of five QAs in the honey and pork. The morphology and structure of the adsorbent were characterized, and the extraction and desorption conditions for the targeted analytes were optimized. Under the optimal conditions, a sensitive method was developed by using PAN/TpPa-1 nanofiber as an adsorbent coupled with high-performance liquid chromatography (HPLC) for five QAs detection. It offered good linearity in the ranges of 0.5-200 ng·mL-1 for pefloxacin, enrofloxacin, and orbifloxacin, and of 1-200 ng·mL-1 for norfloxacin and sarafloxacin with correlation coefficients above 0.9946. The limits of detection (S/N = 3) of five QAs ranged from 0.03 to 0.133 ng·mL-1. The intra-day and inter-day relative standard deviations of the five QAs with the spiked concentration of 50 ng·mL-1 were 2.8-4.0 and 3.0-8.8, respectively. The recoveries of five QAs in the honey and pork samples were 81.6-119.7%, which proved that the proposed method has great potential for the efficient extraction and determination of QAs in complex samples.

Highly fluorinated magnetic covalent organic framework for efficient adsorption and sensitive detection of microcystin toxin in aqueous samples.

The effective adsorption and sensitive determination of microcystin-LR (MC-LR) are crucial for the environment and human health. In this work, a highly fluorinated magnetic covalent organic framework (denoted as Fe3O4@TabTfa-F4) was synthesized through a simple strategy. The morphology and structure of the as-prepared Fe3O4@TabTfa-F4 were investigated and Fe3O4@TabTfa-F4 showed that it had a high specific surface area (442.3 m² g-1), high fluorine content (6.0%), large pore volume (0.255 cm³ g-1), and strong magnetic responses (31.0 emu g-1). The new sorbent Fe3O4@TabTfa-F4 was applied for MC-LR adsorption. The adsorption behavior was investigated, and the results followed pseudo-second-order kinetics and the Langmuir adsorption model. The excellent adsorption capacities for MC-LR (Qmax = 495.1 mg g-1) may be due to the formation of numerous hydrogen bonds, hydrophobic interaction, and π-π stacking interaction between MC-LR and Fe3O4@TabTfa-F4. Afterward, Fe3O4@TabTfa-F4 was used to extract MC-LR from aqueous samples, followed by high-performance liquid chromatography incorporated with UV spectroscopy. The major parameters that influenced the extraction performance were investigated. The developed method exhibited good linearity in the range of 0.25-20 ng L-1. Under the optimum conditions, limits of detection (S/N=3), limits of quantitation (S/N=10), enrichment factor and relative standard deviation were calculated to be 0.041 ng mL-1, 0.13 ng mL-1, 425, and 9.6%, respectively. The spiked recoveries ranged within 75.3%-108.6%. These findings indicate that Fe3O4@TabTfa-F4 has potential application to the adsorption and sensitive detection of MC-LR from aqueous samples.