Synthesis of 3-carene-derived nanocellulose/1,3,4-thiadiazole-amide complexes with antifungal activity for plant protection.

Background: Nanopesticides have been proved to be a powerful and promising tool to solve the issues in agriculture. The purpose of the present study was to develop ecofriendly nanopesticide systems by the strategy of comprehensive utilization of two natural biomass resources (bagasse and turpentine oil) because of their incomparable advantages.

Results: In this research, a series of nanocellulose carriers ETOCN-1-ETOCN-4 (ETOCN, esterified TEMPO-oxidized cellulose nanofibers) with different degrees of substitution were prepared and characterized by Fourier-transform infrared (FTIR), X-ray diffraction (XRD) and transmission electron microscopy (TEM). Then, 21 1,3,4-thiadiazole-amide compounds 8a-8u containing gem-dimethylcyclopropane ring were designed, synthesized and characterized. A preliminary bioassay indicated that compound 8i (R = p-Br Ph) exhibited broad-spectrum antifungal activity against the tested fungi. Furthermore, drug-loading complexes 8i/ETOCN-1-8i/ETOCN-4 were fabricated by integration of nanocellulose-based carriers ETOCN-1-ETOCN-4 with bioactive compound 8i, and the drug-loading capacities, microstructures and sustained-releasing performance of these complexes were also investigated. According to the observation of scanning electron microscopy (SEM) images of complex 8i/ETOCN-2, the small-molecule drug and the carrier formed a well-distributed and compact complex, which led to the excellent drug-loading capacity and sustained-releasing performance in the ethanol/water (1:1, v/v) system.

Conclusions: Complexes 8i/ETOCN-1-8i/ETOCN-4 deserved further study as the promising candidates for the development of nanopesticides. © 2022 Society of Chemical Industry.