Smart, degradable, and eco-friendly carboxymethyl cellulose-CaII hydrogel-like networks gated MIL-101(FeIII) nanoherbicides for paraquat delivery

Abstract

Nanopesticides have been selected as one of the top 10 chemical innovations for enhancing the efficacy and safety of agrochemicals. Herein, smart, degradable, and eco-friendly metal−organic framework MIL-101(FeIII) nanoherbicides coated with carboxymethyl cellulose-CaII (CMC-CaII) cross-linking hydrogel-like networks are synthesized via a simple strategy. The coating of the CMC-CaII hydrogel-like gatekeepers is oriented by the coordination unsaturated FeIII clusters on the surfaces of the MIL-101(FeIII) nanocarriers to form a dense film network to prevent paraquat (PQ) leakage. Based on the stimuli factors (acid/basic pH, GSH, phosphates, and EDTA) of physiological and natural environments of target plants, the nanoherbicides are combined with five stimuli-responsive properties to attain the various controlled release of packaged PQ by the disassembly of the gatekeepers and/or the degradation of the MOF skeleton structure. More importantly, based on the stimuli-responsive controlled release mechanisms, the eco-friendly nanocarriers are ultimately degraded against bioaccumulation in plants or soil. The coating of natural CMC could promote the spreading of PQ owing to improvement of wettability for aqueous droplets of nanoherbicides on hydrophobic foliage. The PQ trapped in nanocarriers can effectively prevent PQ degradation, which showed that cumulative degradation rate is ca. 2.6 times lower than that of technical PQ under UV irradiation. The prepared nanoherbicides loaded with PQ show good control efficacy against weeds by controlling the release of PQ; good safety on seed germination (germination rate 97.32–99.67 %), seedling emergence (emergence rate 95.53–99.67 %), and are beneficial for the growth of wheat seedling (increase rate of plant height 1.89–6.97 % and 0.54–5.67 % after 7 and 15 days of seedling emergence, respectively) in the greenhouse; good biosafety for honeybees (Apis mellifera L.), which shows that lethal rates were 2.04 and 2.55 times lower than technical PQ for incubation 24 and 48 h, respectively. The nanoherbicides have potential applications in the field for PQ green agriculture.