Nanopesticides were selected as one of the top 10 emerging technologies in chemistry that will change our world in 2019. Facile, smart, and degradable metal−organic framework MIL-101(Fe III ) nanopesticides gated with Fe III -tannic acid (TA) networks are created using a universal strategy. The capping of the Fe III -TA network gatekeepers is instinctively oriented by the coordinatively unsaturated Fe III sites on the surfaces of the MIL-101(Fe III ) nanocarriers; thus, their combination is perfectly matched. This is the first example that one smart gated nanoparticle is integrated with seven stimuli-responsive performances to meet the diverse controlled release of encapsulated cargos by the disassembly of the gatekeepers and/or the degradation of the nanocarriers. More importantly, each of the seven stimuli (acidic/alkaline pH, H 2 O 2 , glutathione, phosphates, ethylenediaminetetraacetate, and near-infrared light of sunlight) is closely related to the biological and natural environments of crops, and the biocompatible nanocarriers are eventually degraded against bioaccumulation even if the nanopesticides enter crops. These mechanisms of the stimuli-responsive controlled release are identified and clearly elaborated. It is found that the natural polyphenol can improve the wettability of aqueous droplets of nanopesticides on model hydrophobic foliage for pesticide adhesion and retention. The nanopesticides encapsulated with the fungicide tebuconazole show high fungicidal activities against pathogenic fungi Rhizoctonia solani (rice sheath blight) and Fusarium graminearum (wheat head blight); good safety on seed germination, seedling emergence, and plant height of wheat by seed dressing; and satisfactory control efficacy in wheat powdery mildew caused by Blumeria graminis in the greenhouse. The nanopesticides have potential applications in the field for high quality and yield of agricultural production.

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This paper reports dual enhanced electrochemiluminescence (ECL) of CdS quantum dot (QD)-decorated aminated Au@SiO 2 core/shell (Au@SiO 2 -NH 2 /CdS) superstructures. A maximum ECL emission of the Au@SiO 2 -NH 2 /CdS superstructures (Au core, ca. 55 nm) with a silica shell of 38 nm was 35-fold stronger than that of the counterparts (containing neither Au cores nor amino groups) with H 2 O 2 as a coreactant. The fold of ECL enhancement is the largest, and the optical path of maximum ECL enhancement is the longest reported so far. The larger the Au cores in the superstructures, the stronger the ECL emission of CdS QDs was. Two types of ECL enhancement mechanisms were clearly proposed for the dual enhanced ECL of the Au@SiO 2 -NH 2 /CdS superstructures. One was the electromagnetic field enhancement induced by localized surface plasmon resonance of Au cores, and the other was the chemical enhancement from amino groups modified on the silica surface involved in the ECL process in the assistance of H 2 O 2 . It is the first time to put forward the new concept of chemical enhanced ECL that was directly related to the participation of other chemicals, which caused a decrease in the difference in the redox potential between emitters and coreactants for the increase of their redox currents. The constructed ECL platform was demonstrated to have promising applications in highly sensitive detection of glutathione (GSH), and the response mechanism of GSH was also explored.

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Two novel stimuli-responsive drug delivery systems (DDSs) were successfully created from bovine serum albumin- or myoglobin-gated upconversion nanoparticle-embedded mesoporous silica nanovehicles (UCNP@mSiO2) via diselenide (Se–Se)-containing linkages. More importantly, multiple roles of each scaffold of the nanovehicles were achieved. The controlled release of the encapsulated drug doxorubicin (DOX) within the mesopores was activated by triple stimuli (acidic pH, glutathione, or H2O2) of tumor microenvironments, owing to the conformation/surface charge changes in proteins or the reductive/oxidative cleavages of the Se–Se bonds. Upon release of DOX, the Förster resonance energy transfer between the UCNP cores and encapsulated DOX was eliminated, resulting in an increase in ratiometric upconversion luminescence for DOX release tracking in real time. The two protein-gated DDSs showed some differences in the drug release performances, relevant to structures and properties of the protein nanogates. The introduction of the Se–Se linkages not only increased the versatility of reductive/oxidative cleavages but also showed less cytotoxicity to all cell lines. The DOX-loaded protein-gated nanovehicles showed the inhibitory effect on tumor growth in tumor-bearing mice and negligible damage/toxicity to the normal tissues. The constructed nanovehicles in a spatiotemporally controlled manner have fascinating prospects in targeted drug delivery for cancer chemotherapy.

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The construction of nanoplatforms for the multimodal cancer therapy still remains an enormous challenge. Ultrathin porous nitrogen-doped carbon coated stoichiometric copper selenide heterostructures (CuSe/NC) are prepared using a facile and green one-pot hydrothermal method. Interestingly, CuSe/NC itself can achieve both photothermal therapy (PTT) and photocatalytic therapy (PCT) under irradiation of a single near-infrared (NIR) light (808 nm), which is convenient and safe for clinical applications. Importantly, the triple-enhanced NIR light-activated PCT, including O2-independent free radicals, Fenton-like reaction, and glutathione (GSH) depletion, breaks through the limitations of hypoxia and overexpressed GSH in cancer cells. Furthermore, CuSe/NC is loaded with doxorubicin (DOX) via metal coordination and then decorates with DNA to construct the CuSe/NC-DOX-DNA nanoplatform. Surprisingly, the facile nanoplatform has an advanced biocomputing capability of an “AND” Boolean logic gate with the smart “AND” logic controlled release of DOX upon combined stimuli of pH and GSH for precise cancer chemotherapy. The synergistic mechanism of proton-mediated ligand exchange between DOX and GSH is proposed for the “AND” logic controlled drug release from CuSe/NC-DOX-DNA. In vitro and in vivo studies demonstrate that CuSe/NC-DOX-DNA has excellent anticancer efficacy and negligible toxicity. This innovative nanoplatform with multienhanced anticancer efficacy provides a paradigm for combination cancer therapy of PTT, PCT, and chemotherapy.