ZIF-8@Hydroxyapatite Composite as a High Potential Material for Prolonged Delivery of Agrochemicals

Abstract

Although agrochemical practices can enhance agricultural productivity, their intensive application has resulted in the deterioration of ecosystems. Therefore, it is necessary to develop more efficient and less toxic methods against pests and infections while improving crop productivity. Moving toward sustainable development, in this work, we originally described the preparation of a composite (ZIF-8@HA) consisting of the coating of zeolitic-like metal−organic framework (MOF) ZIF-8 (based on Zn, an essential micronutrient in plants with antibacterial, antifungal, and antifouling properties) with hydroxyapatite (HA) nanoparticles (i.e., nanofertilizer). The interaction between the HA and ZIF-8 has been characterized through a combination of techniques, such as microscopic techniques, where the presence of a HA coating is demonstrated; or by analysis of the surface charge with a dramatic change in the Z-potential (from +18.7 ± 0.8 to −27.6 ± 0.7 mV for ZIF-8 and ZIF-8@HA, respectively). Interestingly, the interaction of HA with ZIF-8 delays the MOF degradation (from 4 h for pristine ZIF-8 to 168 h for HA-coated material), providing a slower and gradual release of zinc. After a comprehensive characterization, the potential combined fertilizer and bactericidal effect of ZIF-8@HA was investigated in wheat (Triticum aestivum) seeds and Pseudomonas syringae (Ps). ZIF-8@HA (7.3 ppm) demonstrated a great fertilizer effect, increasing shoot (9.4 %) and root length (27.1 %) of wheat seeds after 11 days at 25 °C under dark conditions, improving the results obtained with HA, ZIF-8, or ZnSO4 or even physically mixed constituents (HA + ZIF-8). It was also effective in the growth inhibition (>80 % of growth inhibition) of Ps, a vegetal pathogen causing considerable crop decline. Therefore, this work demonstrates the potential of MOF@HA composites and paves the way as a promising agrochemical with improved fertilizer and antibacterial properties.