Cyclodextrin polymer-valved MoS2-embedded mesoporous silica nanopesticides toward hierarchical targets via multidimensional stimuli of biological and natural environments.

Targeted delivery of pesticides towards pests and pathogens can significantly improve the bioavailability and efficacy of pesticides and minimize the impact on the environment. Cyclodextrin polymer (CDP)-valved, benzimidazole functionalized, MoS2-embedded mesoporous silica (MoS2@MSN@CDP) nanopesticides were constructed toward hierarchical biological targets of pests, pathogens, and foliage. The splash and bounce of the aqueous droplets containing MoS2@MSN@CDP nanoparticles in the presence of Aersosol OT on superhydrophobic surfaces were well inhibited available for excellent wetting to prevent pesticides from losing to the environment. The multivalent supramolecular nanovalves between CDP and the functionalized benzimidazole moieties could be activated for the controlled release of pesticides in the cases of low pH and α-amylase. It is the first time to report the foliage-triggered controlled release of pesticides, owing to the competitive binding of epicuticular wax components to CDP. Furthermore, thermogenic MoS2 cores triggered the controlled release of pesticides under irradiation of near infrared light. The fungicidal efficacies of the stimuli-responsive nanopesticides against pathogenic fungi Rhizoctonia solani and Fusarium graminearum were demonstrated. It is clear that the smart nanopesticides could realize the controlled release of pesticides toward hierarchical biological targets for enhanced pesticide bioavailability and efficacy via the multidimensional stimuli of pH, α-amylase, epicuticular waxes, and sunlight.

An Intelligent AIEgen with Nonmonotonic Multiresponses to Multistimuli.

Intelligent stimulus-response (S/R) systems are the basis of natural process and machine control, which are intensively explored in biomimetic design and analytical/biological applications. However, nonmonotonic multi-S/R systems are still rarely studied so far. In this work, a rational design strategy is proposed to achieve such a unique S/R system by integrating opposite luminescence behaviors in one molecule. When solvent polarity increases, many heterocyclic or carbonyl-containing compounds often become more emissive due to the suppression of the proximity effect, whereas molecules with donor-acceptor (D-A) structures tend to be less emissive because of the twisted intramolecular charge transfer. Meanwhile, protonation on D/A moieties will weaken/strengthen the D-A interaction to result in blue/redshifted emissions. By combining a protonatable heterocyclic acceptor and a protonatable donor together in one molecule, nonmonotonic brightness responses to polarity stimuli and nonmonotonic color responses to pH stimuli can be achieved. The design strategy is successfully verified by a simple molecule named 4-(dimethylamino)styryl)quinoxalin-2(1H)-one (ASQ). ASQ exhibits nonmonotonic responses to polarity and pH stimuli, and aggregation-induced emission (AIE) with a nonmonotonic AIE curve. Meanwhile, ASQ can be adjusted to emit white light in an acidic environment, and it shows multivalent functionalities including albumin protein sensing, ratiometric pH sensing, and amine gas sensing.

Erratum: An Intelligent AIEgen with Nonmonotonic Multiresponses to Multistimuli.

[This corrects the article DOI: 10.1002/advs.202001845.].

Specific and Quantitative Detection of Albumin in Biological Fluids by Tetrazolate-Functionalized Water-Soluble AIEgens.

The analysis of albumin has clinical significance in diagnostic tests and obvious value to research studies on the albumin-mediated drug delivery and therapeutics. The present immunoassay, instrumental techniques, and colorimetric methods for albumin detection are either expensive, troublesome, or insensitive. Herein, a class of water-soluble tetrazolate-functionalized derivatives with aggregation-induced emission (AIE) characteristics is introduced as novel fluorescent probes for albumin detection. They can be selectively lighted up by site-specific binding with albumin. The resulting albumin fluorescent assay exhibits a low detection limit (0.21 nM), high robustness in aqueous buffer (pH = 6-9), and a broad tunable linear dynamic range (0.02-3000 mg/L) for quantification. The tetrazolate functionality endows the probes with a superior water solubility (>0.01 M) and a high binding affinity to albumin (KD = 0.25 µM). To explore the detection mechanism, three unique polar binding sites on albumin are computationally identified, where the multivalent tetrazolate-lysine interactions contribute to the tight binding and restriction of the molecular motion of the AIE probes. The key role of lysine residues is verified by the detection of poly-l-lysine. Moreover, we applied the fluorogenic method to quantify urinary albumin in clinical samples and found it a feasible and practical strategy for albumin analysis in complex biological fluids.