CRISPR/Cas12a-derived ratiometric fluorescence sensor for high-sensitive Pb2+ detection based on CDs@ZIF-8 and DNAzyme.

Benefiting from specific target recognition and trans-cleavage capabilities, the CRISPR/Cas12a system has great application prospects in the design of highly sensitive and rapid fluorescence biosensors. The CRISPR/Cas12a-based fluorophore-quencher molecular beacons exhibit single-color emission and are easily exposed to interference from environmental factors. Herein, we design a CRISPR/Cas12a-derived ratiometric fluorescence sensor for Pb2+ detection based on embedded carbon dots@zeolitic imidazolate framework-8 (CDs@ZIF-8) composites and DNAzyme. The functions of ZIF-8 about encapsulating red emissive CDs in the inner cavity and adsorbing DNA on the outer surface are integrated to establish dual fluorescence signals, thereby reducing the possibility of interference and improving sensing accuracy. The presence of Pb2+ is converted into the change of activator by the GR5 DNAzyme to activate the CRISPR/Cas12a system, which provides signal amplification through multiple turnovers of side branch cutting, achieving highly sensitive detection of Pb2+ with a low detection limit of 18 pM. This method has the advantages of simplicity, universality, and excellent quantitative ability, and has broad prospects in sensing applications.

Zeolitic Imidazolate-Framework-Engineered Heterointerface Catalysis for the Construction of Plant-Wearable Sensors.

Plant-wearable sensors provide real-time information that enables pesticide inputs to be finely tuned and play critical roles in precision agriculture. However, tracking pesticide information in living plants remains a formidable challenge owing to inadequate shape adaptabilities and low in-field sensor sensitivities. In this study, plant-wearable hydrogel discs are designed by embedding a dual-shelled upconversion-nanoparticles@zeolitic-imidazolate-framework@polydopamine (UCNPs@ZIF@PDA) composite in double-network hydrogels to deliver on-site pesticide-residue information. Benefiting from the enzyme-mimetic catalytic activity of ZIFs and enzyme triggered-responsive property of PDA shell, the hydrogel discs are endowed with high sensing sensitivity toward 2,4-dichlorophenoxyacetic acid pesticide at the nanogram per milliliter level via boosting fluorescence quenching efficiency. Notably, hydrogel discs mounted on tomato plants exhibit sufficient adaptability to profile dynamic pesticide degradation when used in conjunction with an ImageJ processing algorithm, which is practically applicable. Such hydrogel discs form a noninvasive and low-cost toolkit for the on-site acquisition of pesticide information, thereby contributing to the precise management of the health status of a plant and the judicious development of precision agriculture.

Zeolitic imidazolate framework/aptamer-based fluorescence assay for the facile and high-sensitivity detection of acetamiprid.

Accurate monitoring of trace pesticides in complex matrix remains a challenge in food safety supervision. Herein, we designed a facile zeolitic imidazolate framework (ZIF)-8/aptamer-based assay for the sensitive detection of acetamiprid. ZIF-8 efficiently adsorbs 6-carboxyfluorescein-labeled complementary DNA (cDNA-FAM) via electrostatic interaction, hydrogen bonding and Zn2+ coordination, which contributed to resistance to cDNA-FAM displacement by biological ligands. ZIF-8 serves as an "ion pump" that contains lots of Zn2+ who boosts cDNA-FAM adsorption and triggers the photoinduced electron transfer (PET) effect from FAM to ZIF-8, improving the sensing sensitivity. Acetamiprid could trigger the change in the adsorption state of cDNA-FAM, further tuning the PET effect and causing fluorescence conversion. The fluorescence assay showed a high sensitivity for monitoring acetamiprid with a detection limit of 0.05 ng mL-1 in the apple sample. This ZIF/DNA-based analytical platform provides a powerful tool for facile and low-cost screening of pesticide residues, with promising applications in food safety monitoring.

Gold nanoclusters-manganese dioxide composite-based fluorescence immunoassay for sensitive monitoring of fenitrothion degradation in Chinese cabbage.

Understanding the residues and degradation of organophosphorus pesticides (OPs) in crops has attracted increasing attention. Herein, we designed a sensitive fluorescence immunoassay (FIA) by employing nanobody-linked alkaline phosphatase (Nb-ALP) and gold nanoclusters anchored manganese dioxide (AuNCs-MnO2) composite. In immunoassay protocol, Nb-ALP is used to competitively recognize the coating antigen and pesticide. After competitive immunoreaction, alkaline phosphatase catalyzes l-ascorbic acid-2-phosphate to produce ascorbic acid that can trigger the decomposition of the AuNCs-MnO2 composite, regulating the fluorescence response. As a proof-of-concept, fenitrothion (FNT) is chosen as the target analyte. As a result, the developed FIA exhibits high detection sensitivity (IC10 = 5.78 pg/mL), which is about 56-times higher than that of the conventional enzyme-linked immunosorbent assay. The developed FIA has been successfully applied for precisely monitoring the degradation of FNT in Chinese cabbage with excellent anti-interference ability and reproducibility, paving the way for the determination of pesticide residues in real food samples.

Carbon Dot-Anchored Cobalt Oxyhydroxide Composite-Based Hydrogel Sensor for On-Site Monitoring of Organophosphorus Pesticides.

The development of a portable, quantitative, and user-friendly sensor for on-site monitoring of organophosphorus pesticides (OPs) is significantly urgent to guarantee food safety. Herein, a carbon dot/cobalt oxyhydroxide composite (CD/CoOOH)-based fluorescent hydrogel sensor is constructed for precisely quantifying OPs using a homemade portable auxiliary device. As a fluorescence signal indicator, the orange-emissive CD/CoOOH composite is encapsulated into an agarose hydrogel kit for amplifying the detection signals, shielding background interference, and enhancing stability. Acetylcholinesterase (AChE) catalyzes the hydrolysis of the substrate to produce thiocholine, which induces the decomposition of CoOOH and makes the fluorescence enhancement of the hydrogel platform possible. OPs can specifically block the AChE activity to limit thiocholine production, resulting in a decrease in platform fluorescence. The image color of the fluorescent hydrogel kit is transformed into digital information using a homemade auxiliary device, achieving on-site quantitative detection of paraoxon (model target) with a detection limit of 10 ng mL-1. Harnessing CD/CoOOH composite signatures, hydrogel encapsulation, and portable optical devices, the proposed fluorescence hydrogel platform demonstrated high sensitivity and good anti-interference performance in agricultural sample analysis, indicating considerable potential in the on-site application.

Ratiometric fluorescent hydrogel for point-of-care monitoring of organophosphorus pesticide degradation.

The residues of organophosphorus pesticides have caused the potential risk in environment and human health, arousing worldwidely great concern. Herein, we fabricated a robust gold nanoclusters/MnO2 composites-based hydrogel portable kit for accurate monitoring of paraoxon residues and degradation in Chinese cabbages. With the immobilization of gold nanoclusters/MnO2 composites into a hydrogel, a ratiometric fluorescent signal is generated by catalyzing the oxidation of o-phenylenediamine, which possesses a built-in correction with low background interference. Coupling with acetylcholinesterase catalytic reactions and pesticide inhibition effect, the portable kit can sensitively detect paraoxon residues with a detection limit of 5.0 ng mL-1. For on-site quantification, the fluorescent color variations of portable kit are converted into digital information that exhibits applicative linear range toward pesticide. Notably, the hydrogel portable kit was successfully applied for precisely monitoring the residue and degradation of paraoxon in Chinese cabbage, providing a potential pathway toward practical point-of-care testing in food safety monitoring.