Dual-source signal amplification electrochemiluminescence sensor combined with molecularly imprinted polymers for the imidacloprid detection.

A novel lanthanide metal-organic-gel (MOG)-derived material/nitrogen-doped graphdiyne (Tb-Ru-MOG/CeO2/N-GDY) composite with a dual-source signal amplification strategy was prepared and used to construct a molecularly imprinted sensor based on bifunctional monomers for the detection of imidacloprid (IMI) using electrochemiluminescence (ECL). In a green reaction environment, terbium (III) (Tb3+) can undergo multiple coordination reactions with 4'-(4-carboxyphenyl)-2,2':6',2″-terpyridine (Hcptpy) and tris(4,4'-dicarboxylicacid-2,2'-bipyridyl) ruthenium (II) dichloride (Ru(dcbpy)32+), and combine with ceria nanoparticles (CeO2 NPs) to form Tb-Ru-MOG/CeO2. Within the Tb-Ru-MOG/CeO2 framework, energy transfer from the double ligands can sensitize the central Tb3+, triggering a distinct antenna effect and energy-transfer, and its polyporous configuration offered a nanoconfined space for Ce3+/Ce4+ to effectively catalyze coreactant radicals (S2O82-), leading to in-situ endogenous activation ECL reactions. The conductive N-GDY accelerated electron movement and increased the loading on the electrode surface, enhancing the exogenous excitation of the ECL signals. Leveraging the synergistic effect of the bifunctional monomer, the synthesized molecularly imprinted polymers (MIPs) ECL sensor demonstrated a wide detection range from 10 nM to 10,000 nM for IMI, with a limit of detection (LOD) of 1.37 nM, showcasing an innovative concept for the dual-source strategy of signal amplification in integrated ECL composites to analyze food and environmental hazards.

Novel poly (N-methacryloyl-L-alanine acid) grafted chitosan microspheres based solid-phase extraction coupled with ICP-MS for simultaneous detection of trace metal elements in food.

Poly (N-methacryloyl-L-alanine acid) grafted tartaric acid-crosslinked chitosan microspheres (PNMA-TACS) were successfully synthesized and employed as a novel adsorbent for the separation and enrichment of metal ions in the food system. PNMA-TACS microspheres-based solid phase extraction (SPE) was coupled with ICP-MS for accurate quantification of trace V(V), Cr(III), As(III), Pb(II), Cd(II) and Cu(II). The obtained PNMA-TACS microspheres were characterized, and parameters influencing the method were optimized. Under optimal conditions, the calibration curves for Cu(II) and V(V) were linear within 0.01-30 µg L-1, the linear ranges of Cr(III), As(III), Pb(II) and Cd(II) were 0.01-15 µg L-1, and the detection limit of the developed approach was 1.1-3.7 ng L-1. The results were consistent with the consensus values of method validation implemented by two standards. Moreover, standard addition recovery experiments were performed in rice and milk powder, which achieved satisfactory recovery of 86.1-103.5%.

A Smartphone-Integrated Molecularly Imprinted Fluorescence Sensor for Visual Detection of Chlortetracycline Based on N,P-Codoped Carbon Dots Decorated Iron-Based Metal-Organic Frameworks.

The residue of chlortetracycline is potentially hazardous to human health; it is meaningful to exploit a portable, rapid, sensitive, and selective method for detection of chlortetracycline (CTC). In this study, a novel fluorescence bionic sensing probe (NH2-MIL-53&N,P-CDs@MIP) was successfully prepared based on the nitrogen and phosphorus codoped carbon dots decorated iron-based metal-organic frameworks combining with molecular imprinted polymer for the detection of CTC. A fluorescence intensity-responsive "on-off" detection of CTC on account of the inner-filter effect (IFE) was achieved by NH2-MIL-53&N,P-CDs@MIP. Under the optimal conditions, the fluorescence quenching degree of NH2-MIL-53&N,P-CDs@MIP presented a good linear relationship with the CTC concentration in the range 0.06-30 µg mL-1 and the limit of detection (LOD) was 0.019 µg mL-1. The fluorescent probe was applied to detect CTC in milk samples, and experimental results showed a good recovery rate (88.73%-96.28%). Additionally, a smartphone-integrated fluorescence sensing device based on NH2-MIL-53&N,P-CDs@MIP was exploited to replace the expensive and bulky fluorescence spectrophotometer for quantitative determination of CTC with the LOD of 0.033 µg mL-1. The sensing system showed high selectivity, strong stability, high specificity, and portability, which provide a great strategy for the quantitative detection of antibiotic residue.

Melamine-Ag with dual functions of electrochemiluminescence luminophore and coreactant accelerators: Construction of MIP/M-Ag@MoS2-QDs sensing platform for specific detection of thiabendazole.

A novel self-enhancement molecularly imprinted electrochemiluminescence (ECL) sensor (MIP/M-Ag@MoS2-QDs/GCE) was constructed to detect thiabendazole (TBZ) in food. Melamine was used as template to chelate Ag+ to prepare composite nanomaterials (M-Ag). M-Ag possesses both ECL properties and coreactant catalytic properties, which can realize the self-enhancement of ECL luminophore. MoS2-QDs with excellent edge activity and electrochemical reaction catalytic activity were used to accelerate the reaction rate of the microsystem and further enhance the ECL intensity. The specific detection method of TBZ was established by investigating the ECL response mechanism and specific recognition mechanism of MIP/M-Ag@MoS2-QDs/GCE. The ECL intensity was proportioned to the lg C(TBZ) in the linear range 5 × 10-8 mol L-1-5 × 10-5 mol L-1 with a limit detection of 1.42 × 10-8 mol L-1. The satisfactory recovery rate (83.57%-101.03%) was obtained in sample analysis, which was in good agreement with the analysis result of HPLC.

A Turn-Off Fluorescent Biomimetic Sensor Based on a Molecularly Imprinted Polymer-Coated Amino-Functionalized Zirconium (IV) Metal-Organic Framework for the Ultrasensitive and Selective Detection of Trace Oxytetracycline in Milk.

Developing sensitive and effective methods to monitor oxytetracycline residues in food is of great significance for maintaining public health. Herein, a fluorescent sensor (NH2-UIO-66 (Zr)@MIP) based on a molecularly imprinted polymer-coated amino-functionalized zirconium (IV) metal-organic framework was successfully constructed and first used for the ultrasensitive determination of oxytetracycline. NH2-UIO-66 (Zr), with a maximum emission wavelength of 455 nm under 350 nm excitation, was prepared using a microwave-assisted heating method. The NH2-UIO-66 (Zr)@MIP sensor with specific recognition sites for oxytetracycline was then acquired by modifying a molecularly imprinted polymer on the surface of NH2-UIO-66 (Zr). The introduction of NH2-UIO-66 (Zr) as both a signal tag and supporter can strengthen the sensitivity of the fluorescence sensor. Thanks to the combination of the unique characteristics of the molecularly imprinted polymer and NH2-UIO-66 (Zr), the prepared sensor not only exhibited a sensitive fluorescence response, specific identification capabilities and a high selectivity for oxytetracycline, but also showed good fluorescence stability, satisfactory precision and reproducibility. The fabricated sensor displayed a fluorescent linear quenching in the OTC concentration range of 0.05-40 µg mL-1, with a detection limit of 0.012 µg mL-1. More importantly, the fluorescence sensor was finally applied for the detection of oxytetracycline in milk, and the results were comparable to those obtained using the HPLC approach. Hence, the NH2-UIO-66 (Zr)@MIP sensor possesses great application potential for the accurate evaluation of trace oxytetracycline in dairy products.

"Blocking-effect" detection strategy of clenbuterol by molecularly imprinted electrochemiluminescence sensor based on multiple synergistic excitation of AgNW luminophores signal with highly active BNQDs@AuNFs nanoscale co-reaction accelerator.

A molecularly imprinted electrochemiluminescence sensor (MIECLS) is constructed to selectively detect clenbuterol (CLB) based on boron nitride quantum dots@gold nanoflowers/silver nanowires (BNQDs@AuNFs/AgNWs). The abundant amino and hydroxyl groups on the surface of the BNQDs generate an electrostatic self-assembly effect with the multi-tipped spatial structure of AuNFs, constituting a novel nanoscale co-reaction accelerator (NCRA) with high activity and large load capacity. An NCRA embedded in the network structure of the AgNW luminophores significantly promotes the reduction of peroxydisulfate (S2O82-) to sulfate anion radicals (SO4-•) through the catalysis of amino groups and boron radicals (B•) and the electron acceleration of AuNFs while also reducing the reaction distance between SO4-• and AgNWs-•, realizing the multiple synergistic amplification of the electrochemiluminescence (ECL) signal. Imprinted cavities in the molecularly imprinted polymers (MIPs) prepared by electropolymerization can generate a "blocking-effect" by recognizing CLB, realizing ECL signal quenching. Analytical results indicate that the established MIECLS detects CLB in a line concentration range of 0.5-50000 nM and detection limit of 0.00693 nM. The spiked recoveries are 85.90%-97.77%, with the relative standard deviations (RSD) under 5.1%, consistent with those of high-performance liquid chromatography (HPLC). This work demonstrates that an efficient NCRA can significantly enhance the output of the ECL signal in collaboration with the original luminophore, providing a new method to realize the ultra-detection of targeted substances by MIECLS.

A molecularly imprinted fluorescence sensor for sensitive detection of tetracycline using nitrogen-doped carbon dots-embedded zinc-based metal-organic frameworks as signal-amplifying tags.

Tetracycline (TC) residues not only endanger human health, but also are detrimental to the sustainable development of aquaculture and animal husbandry. Herein, a novel fluorescence sensor with high sensitivity and selectivity was developed based on nitrogen-doped carbon dots embedded in zinc-based metal-organic frameworks and incorporating molecularly imprinted polymer (ZIF-8&N-CDs@MIP). The physical and chemical properties of the ZIF-8&N-CDs@MIP had been characterized by SEM, TEM, FTIR, XRD, BET, TGA, etc. Under optimal conditions, the limit of detection (LOD) of the novel sensor was 0.045 µg mL-1 with the concentration of TC in the range of 0.1-4.0 µg mL-1. In addition, the prepared imprinted polymers showed superior adsorption selectivity to tetracycline compared with non-imprinted polymers, and the quenching mechanism of ZIF-8&N-CDs@MIP was demonstrated to be attributed to the inner filter effect (IFE). This work provided an effective and reliable method for the specific detection of tetracycline and was successfully applied in milk and egg samples with satisfactory recoveries (80.67-95.22%).

A smartphone-assisted optosensing platform based on chromium-based metal-organic framework signal amplification for ultrasensitive and real-time determination of oxytetracycline.

Ultrasensitive and onsite detection of oxytetracycline (OTC) is of vital significance for ensuring public health. Herein, a novel and versatile fluorescence biomimetic nanosensor, Mg,N-CDs@MIL-101@MIP, was elaborately tailored for the assay of OTC. MIL-101 with extraordinarily high surface area and porosity, as a favorable supporter, suppressed self-quenching of Mg,N-CDs and boosted mass transfer rate, realizing signal amplification. As an ultrasensitive signal transducer, high luminescent Mg,N-CDs yielded conspicuous fluorescence responses for OTC, enhancing the sensitivity of Mg,N-CDs@MIL-101@MIP. High-affinity imprinting sites further endowed Mg,N-CDs@MIL-101@MIP with superior anti-interference ability and reusability. Given prominent merits, Mg,N-CDs@MIL-101@MIP demonstrated a good linear range (0.05-40 µg mL-1) with a lower limit of detection (16.8 ng mL-1), supplying high accessibility to realize ultrasensitive and highly selective measurement of OTC in samples. Additionally, to attain precise onsite profiling of OTC, an intelligent sensing platform was developed by integrating Mg,N-CDs@MIL-101@MIP with a portable smartphone-assisted optical device. As both signal reader and analyzer, smartphone can instantly capture concentration-dependent fluorescent images and accurately digitize them, accomplishing quantitative analysis of OTC. More delightfully, the portable platform was utilized for visual determination of OTC in milk samples with satisfactory results, offering a promising tool for the high-performance onsite evaluation of food safety and environmental health.

A study on the catalytic activity of polypeptides toward the hydrolysis of glucoside compounds gastrodin, polydatin and esculin.

The self-assembly of a series of catalytically active polypeptides toward hydrolysis of glucoside compounds, namely, gastrodin, polydatin and esculin was investigated. These active peptides are composed of two functional fragments: one is the hydrophobic sequence LHLHLRL, which forms assembling segments in the presence of Zn ions (Zn2+); another functional sequence of active peptides are catalytic sites such as Glu (E), Asp (D) and His (H), where carboxylic acids (-COOH) or imidazole groups act like scissors to cleave glucoside bonds of the compounds (according to the acid-base coupling mechanism). The effects of the amino acid sequence of the peptide, Zn2+ concentration, pH and the size or steric hindrance of glucoside compounds on the hydrolytic activity were studied. It was found that the crystalline structure of assembled peptides was crucial to provide the peptide with catalytic hydrolytic activity. Noncovalent interaction index was used to analyse the noncovalent interaction of PEs with glucoside compounds, including hydrogen bonds, van der Waals, and steric effect in the complexes. The binding energy of complexes, the direction and site of nucleophilic attack during deglycosylation processes were also investigated by molecular docking and the electron density Laplace function. This revealed that the differences in the hydrolytic activity of peptides toward glucoside compounds with different sizes originated from different hydrogen bond interactions between the peptides and substrates. These active peptides may find application in the preparation of drugs by de-glycosylation of natural compounds.

Construction of a piezoelectric immunosensor for ultra-sensitive and highly selective detection of ribavirin in animal-derived foods.

In this work, a suppressive piezoelectric immunosensor based on the ultra-sensitive quartz crystal microbalance and highly specific immunosorbent assay was constructed for the detection of ribavirin for the first time. The carboxyl group was modified on the surface of the gold electrode by electropolymerization, and then the carboxyl group was combined with the amino-modified antigen, and then the corresponding antibody was able to bind to it according to the principle of immune recognition, which interlocked to cause the frequency change of the piezoelectric sensor. The preparation conditions of the sensor and the antibody concentration were optimized, and the performance of the sensor was evaluated. Under the optimal conditions, a wide linear range of 1-750 µg L-1, a low detection limit (IC15) of 2.64 µg L-1, and a good sensitivity (IC50) of 31.49 µg L-1 were obtained. The sensor was used for the detection of ribavirin in chicken and milk samples, and the recovery rate ranged from 88.01 to 94.42%, which shows satisfactory consistency with the detection results of high performance liquid chromatography. It was suggested that the proposed piezoelectric immunosensor has good sensitivity and selectivity for ribavirin, and can be applied to the detection of actual food samples.

Fluorescence sensor based on molecularly imprinted polymers and core-shell upconversion nanoparticles@metal-organic frameworks for detection of bovine serum albumin.

A novel strategy for sensing protein was proposed through combining the high selectivity of molecular imprinting technology with the excellent upconversion fluorescence of upconversion nanoparticles (UCNPs) and high specific surface area of metal-organic frameworks (MOFs). Herein, the UCNPs acted as signal reporter and MOFs were introduced to increase the rate of mass transfer. The UCNPs@MIL-100 as support material was prepared via a step-by-step method. The imprinted material-coated UCNPs@MIL-100 (UCNPs@MIL-100@MIPs) were obtained by sol-gel technique. The results showed that as the increase of the template protein concentration, the fluorescence intensity of UCNPs@MIL-100@MIPs quenched gradually, and the imprinting factor was 2.90. The linear in the range of 1.00 to 8.00 µM, and the detection limit was 0.59 µM. Therefore, the novel optosensing material is very promising for future applications.

Portable and on-site electrochemical sensor based on surface molecularly imprinted magnetic covalent organic framework for the rapid detection of tetracycline in food.

In this study, for the first time, surface molecularly imprinted magnetic covalent organic frameworks (Fe3O4@COFs@MIPs) were combined with disposable screen-printed electrode (SPE) to construct a portable and on-site electrochemical sensor for the rapid detection of tetracycline (TC). The Fe3O4@COFs@MIPs, which was prepared by layer-by-layer modification method, had good magnetism and excellent adsorption ability. With the help of disposable SPE, equipped with a magnet, the electrode modification process was simplified and the detection efficiency was improved. Under optimal conditions, the fabricated electrochemical sensor exhibited linearity ranging from 1 × 10-10 to 1 × 10-4 g mL-1. It had good selectivity, excellent reproducibility, desirable stability and remarkable applicability. The fabricated sensor was successfully applied to detect TC in real samples with satisfactory recoveries (96.15-106.20%). The detection strategy separated the recognition and adsorption process from the electrochemical detection process, providing a design idea for the application of COFs in the construction of high-efficiency molecularly imprinted electrochemical sensors.

Controllable Enhanced Ru(bpy)32+ Electrochemiluminescence Detection Systems Based on Eu@MOF253@AuNPs/GCE for the Sensitive Detection of Carbaryl in Food.

In this study, an electrochemiluminescence detection system for the sensitive detection of carbaryl was constructed based on the dual identification of Eu@MOF253, which has a recognition effect on carbaryl, and the electrochemiluminescence system of Ru(bpy)32+/S2O82-, which can react with carbaryl in a redox reaction. This method not only overcame the weakness of the electrochemiluminescence instability of the Ru(bpy)32+/S2O82- system but also changed the sensitivity of the sensing detection system to the target by adjusting the concentration of Ru(bpy)32+ and then proposed a detection strategy with a controllable detection range. After analyzing the electrochemiluminescence signal change mechanism of this system and optimizing the detection conditions, it was concluded that the strategy has good linear detection of carbaryl in the range of 1-1000 and 0.02-0.3 µg L-1, and the detection limits were 0.058 and 0.014 µg L-1. Finally, the strategy was also successfully applied to the detection of actual samples.

Detection of heterocyclic amine (PhIP) by fluorescently labelled cucurbit[7]uril.

Heterocyclic amines (HCA) are the main mutagenic factors in cooked meat products and are considered to be hazardous chemicals in the field of food safety. In this study, inspired by the "host-guest" interaction mechanism, a new technique for detecting 2-amino-1-methyl-6-phenylimidazo [4,5-b] pyridine (PhIP) was developed, taking advantage of the molecular cavities of cucurbit[7]uril (CB[7]) and the powerful guest recognition properties between CB[7] and PhIP. Based on this recognition mechanism, three steps were included in the detection procedure: firstly, regenerated cellulose (RC) membrane was oxidized by NaIO4 to generate aldehyde groups; secondly, the PhIP molecules to be detected were trapped by the aldehyde groups via amine-aldehyde conjugation chemistry; thirdly, the RC membrane with trapped PhIP was immersed into solutions of dansyl chloride-labelled CB[7] to allow the host-guest interaction to occur, so that PhIP could be quantified by fluorescence of the dansyl chloride dye. The limit of detection, linear range and recovery of this method were about 0.224 µg kg-1, 10-1000 nM and 89.0-96.4%, respectively. So far, most reported techniques for HCA detection are based on HPLC coupled with mass spectroscopy, and the method reported here might be the first quick measurement technique for HCA and may find wide application in food safety detection.

Construction of an ECL Detection Platform for Sensitive Detection of Carbaryl Based on an Eu3+-Functionalized Metal-Organic Framework Encapsulated with Nanogold.

In this work, an Eu3+-MOF-253@Au electrochemiluminescence sensor was successfully constructed for the first time by encapsulating nanogold in the metal-organic frameworks (MOFs) backbone and pore channels, and assembling Eu3+ on the MOF backbone. Firstly, the introduction of nanogold overcomes the weakness of MOFs, which was difficult to achieve, and enhances its catalytic performance, followed by the modification of Eu3+ to confer the electrochemiluminescence performance and the function of target detection on the sensor. Moreover, carbaryl was placed in an alkaline working solution to enhance the intensity of electrochemiluminescence signal, as well as to promote the hydrolysis of carbaryl into 1-naphthol, which caused the burst of Eu3+-MOF-253@Au electrochemiluminescence sensor, thereby achieving the sensitive detection of carbaryl. On this basis, the electrochemiluminescence detection conditions were optimized, the performance was analyzed, and finally it was successfully used for the detection of carbaryl with good linearity in the range of 0.2-200 µg L-1 and a low detection limit (0.14 µg L-1).

A High-Luminescence Biomimetic Nanosensor Based on N, S-GQDs-Embedded Zinc-Based Metal-Organic Framework@Molecularly Imprinted Polymer for Sensitive Detection of Octopamine in Fermented Foods.

In this study, a novel fluorescent molecularly imprinted nanosensor (N, S-GQDs@ZIF-8@MIP) based on the nitrogen and sulfur co-doped graphene quantum dots decorated zeolitic imidazolate framework-8 was constructed for the detection of octopamine (OA). Herein, ZIF-8 with a large surface area was introduced as a supporter of the sensing system, which effectively shortened the response time of the sensor. Meanwhile, high green luminescent N, S-GQDs and a maximum emission wavelength of 520 nm under 460 nm excitation and a 12.5% quantum yield were modified on the surface of ZIF-8 as a signal tag that can convert the interactions between the sensor and OA into detectable fluorescent signals. Finally, N, S-GQDs@ZIF-8@MIP was acquired through the surface molecular imprinting method. Due to the synergy of N, S-GQDs, ZIF-8, and MIP, the obtained sensor not only demonstrated higher selectivity and sensitivity than N, S-GQDs@ZIF-8@NIP, but also displayed faster fluorescence response than N, S-GQDs@MIP. Under optimal conditions, the developed sensor presented a favorable linear relationship in the range of 0.1-10 mg L-1 with a detection limit of 0.062 mg L-1. Additionally, the proposed N, S-GQDs@ZIF-8@MIP strategy was effectively applied to the detection of OA in fermented samples, and the obtained results had a satisfactory correlation with those of HPLC.

A "signal on/off" biomimetic electrochemiluminescence sensor using titanium carbide nanodots as co-reaction accelerator for ultra-sensitive detection of ciprofloxacin.

It is of great significance to explore an efficient and sensitive method for the detection of ciprofloxacin (CIP) for the protection of human health and ecological environment. In this study, a novel molecularly imprinted electrochemiluminescence sensor (MIECLS) was constructed using amino-functional titanium carbide nanodots (TNDs) as co-reactant accelerator in the cathodic electrochemiluminescence system. With K2S2O8 as co-reactant, the obvious cathode luminescence signal of carbon nitride nanosheets (CNNS) can be observed under the synergistic effect of TNDs. TNDs not only advanced the conductivity of CNNS, and the presence of amino group accelerated the reduction of the co-reactant S2O82-, which generated a rich ECL reaction intermediate SO4-• near CNNS, thus greatly enhancing the ECL signal of CNNS. In addition, the proposed MIECLS have good anti-interference, high sensitivity and selectivity by electropolymerization of o-phenylenediamine as functional monomer to form molecularly imprinted polymer (MIP) with specific recognition sites on electrode surface. The MIECLS was applied for determination of CIP, and its ECL intensity was linearly quenched with the increasing concentration of CIP from 5 × 10-9 to 5 × 10-6 mol L-1 with a detection limit of 1.20 × 10-9 mol L-1 (S/N = 3). Futhermore, in the actual sample analysis, the detection results of MIECLS showed good consistency with those of HPLC, indicating that MIECLS has a broad application prospect in the rapid and sensitive analysis of CIP in food samples.

Polythionine-mediated AgNWs-AuNPs aggregation conductive network: Fabrication of molecularly imprinted electrochemiluminescence sensors for selective capture of kanamycin.

A molecularly imprinted electrochemiluminescence (ECL) sensor was developed for the specific detection of kanamycin in food using silver nanowires-gold nanoparticles (AgNWs-AuNPs) as a luminophore. Polythionine (pThi), another key component of the luminescent layer, can be used as an accelerator of the coreactant and can promote the formation of the AgNWs-AuNPs conductive network. In addition, molecularly imprinted polymers (MIPs) were polymerized on the AgNWs-AuNPs/pThi conductive network, which laid the foundation for the specific capture of kanamycin. The preparation and testing conditions of the sensor were optimized, and the performance was characterized. Under optimal conditions, the ECL intensity of AgNWs-AuNPs/pThi/MIP/GCE showed a good linear relationship (R2 = 0.9956) with kanamycin concentration (1 × 10-10-1 × 10-6 M) and a low detection limit (3.14 × 10-11 M, S/N = 3), showing satisfactory selectivity and stability. As proof, AgNWs-AuNPs/pThi/MIP/GCE was successfully used to detect kanamycin in actual samples with satisfactory recovery (83.27-94.13%), which was in good agreement with the results of HPLC-MS/MS (82.26-95.82%). The successful preparation of AgNWs-AuNPs/pThi/MIP/GCE in this experiment provided a new pathway for designing ECL components and constructing an ultrasensitive sensing platform in the field of hazardous substance detection.

Glycosides and Their Corresponding Small Molecules Inhibit Aggregation and Alleviate Cytotoxicity of Aß40.

Polyphenols are the class of naturally synthesized compounds in the secondary metabolism of plants, which are widely distributed in fruits and vegetables. Their potential health treatment strategies have attracted wide attention in the scientific community. The abnormal aggregation of Aß to form mature fibrils is pathologically related to Alzheimer's disease (AD). Therefore, inhibiting Aß40 fibrillogenesis was considered to be the major method for the intervention and therapy of AD. Glycosides, as a cluster of natural phenolic compounds, are widely distributed in Chinese herbs, fruits, and vegetables. The inhibitory effect of glycosides (phloridzin, salidroside, polydatin, geniposide, and gastrodin) and their corresponding small molecules (phloretin, 4-hydroxyphenyl ethanol, resveratrol, genipin, and 4-hydroxybenzyl alcohol) on Aß40 aggregation and fibrils prolongation, disaggregation against mature fibrils, and the resulting cytotoxicity were studied by systematical biochemical, cell biology and molecular docking techniques, respectively. As a result, all inhibitors were observed against Aß40 aggregation and fibrils prolongation and disaggregated mature Aß40 fibrils in a dose-dependent manner. Besides, the cell validity experiments also showed that all inhibitors could effectively alleviate the cytotoxicity induced by Aß40 aggregates, and the glycoside groups played important roles in this inhibiting process. Finally, molecular docking was performed to study the interactions between these inhibitors and Aß40. Docking showed that all inhibitors were bound to the similar region of Aß40, and glycoside group formed hydrogen bonds with the pivotal residues Lys16. These results indicated that the glycoside groups could increase the inhibitory effects and reduce cytotoxicity. Glycosides have tremendous potential to be developed as an innovative type of aggregation inhibitor to control and treat neurodegenerative diseases.

Covalent molecularly imprinted electrochemical sensor modulated by borate ester bonds for hygromycin B detection based on the synergistic signal amplification of Cu-MOF and MXene.

A molecularly imprinted electrochemical sensor (MIES) modified with Cu-MOF and Ti3C2Tx was successfully prepared for the detection of hygromycin B in food. According to the pH sensitive property of reversible borate ester bonds, a molecularly imprinted polymers (MIP) were constructed on the modified gold electrode (GE) surface by electropolymerization to realize the controllable elution and adsorption of template molecules. Cu-MOF with large specific surface area and Ti3C2Tx with excellent electrical conductivity cooperate to improve the overall analytical performance of MIES. The morphology and electrochemical performance of the sensor were evaluated. Under the optimal experimental conditions, the method showed superior selectivity to hygromycin B with a linear range of 5 × 10-9-5 × 10-6 M and a detection limit of 1.92 × 10-9 M (S/N = 3). The detection results of this method are in good agreement with HPLC-MS/MS, which proves that the method has reliable practicability and accuracy.