Copper Glufosinate-Based Metal–Organic Framework as a Novel Multifunctional Agrochemical

Abstract

Pesticides are agrochemical compounds used to kill pests (insects, rodents, fungi, or unwanted plants), which are key to meet the world food demand. Regrettably, some important issues associated with their widespread/extensive use (contamination, bioaccumulation, and development of pest resistances) demand a reduction in the amount of pesticide applied in crop protection. Among the novel technologies used to combat the deterioration of our environment, metal–organic frameworks (MOFs) have emerged as innovative and promising materials in agroindustry since they possess several features (high porosity, functionalizable cavities, ecofriendly composition, etc.) that make them excellent candidates for the controlled release of pesticides. Moving toward a sustainable development, in this work, we originally describe the use of pesticides as building blocks for the MOF construction, leading to a new type of agricultural applied MOFs (or AgroMOFs). Particularly, we have prepared a novel 2D-MOF (namely, GR-MOF-7) based on the herbicide glufosinate and the widely used antibacterial and fungicide Cu2+. GR-MOF-7 crystallizes attaining a monoclinic P21/c space group, and the asymmetric unit is composed of one independent Cu2+ ion and one molecule of the Glu2– ligand. Considering the significant antibacterial activity of Cu-based compounds in agriculture, the potential combined bactericidal and herbicidal effect of GR-MOF-7 was investigated. GR-MOF-7 shows an important antibacterial activity against Staphylococcus aureus and Escherichia coli (involved in agricultural animal infections), improving the results obtained with its individual or even physical mixed precursors [glufosinate and Cu­(NO3)2]. It is also an effective pesticide against germination and plant growth of the weed Raphanus sativus, an invasive species in berries and vines crops, demonstrating that the construction of MOFs based on herbicide and antibacterial/antifungal units is a promising strategy to achieve multifunctional agrochemicals. To the best of our knowledge, this first report on the synthesis of an MOF based on agrochemicals (what we have named AgroMOF) opens new ways on the safe and efficient MOF application in agriculture.

Multifunctional Metal–Organic Framework (MOF)-Based Nanoplatforms for Crop Protection and Growth Promotion

“…Interestingly, Rojas, Horcajada, and co-workers built a multifunctional herbicide-based MOF, i.e., GR-MOF-7, which featured antibacterial and herbicidal activities for the inactivation of Staphylococcus aureus and Escherichia coli and the inhibition of Raphanus sativus germination and growth (Figure 3C). 112 As a novel two-dimensional MOF, Cu 2+ as the metal nodes and herbicide glufosinate as the organic ligands were employed to synthesize GR-MOF-7 via a solvothermal reaction with an average size of ∼223 ± 43 nm. Owing to the dual ROS produced by the organic ligands and the metal ion, the asprepared GR-MOF-7 demonstrated a high antibacterial activity against S. aureus and E. coli.…”

Metal–Organic Frameworks as Potential Agents for Extraction and Delivery of Pesticides and Agrochemicals

“…In 2022, Sierra-Serrano et al integrated the herbicide glufosinate as a building block for a copper-based two-dimentional MOF, named GR-MOF-7, 89 by incorporating glufosinate as a ligand in the MOF structure, ensuring high loading capacity and providing a greener one-pot synthesis method, while using the metal cation and the linker to produce a combined synergistic effect. GR-MOF-7 proved to be water stable for up to 5 days.…”

Synthesis and Characterization of Slow-Release Chitosan Oligosaccharide Pyridine Schiff Base Copper Complexes with Antifungal Activity

“…Recently, the nascent technology of “slow-release molecule design” has attracted the attention of researchers, and this technology found applications in various fields, including medicine and agriculture. , In the pursuit of developing slow-release copper fungicides, a plethora of design strategies have surfaced, ranging from jellyfish-based hydrogel copper oxide nanoparticles to copper glufosinate-based metal–organic frameworks, providing invaluable insights into the development of novel copper fungicides. Nonetheless, due to constraints such as soil safety concerns and technological proficiency, such products have not been commercialized.…”