Carboxymethyl Cellulose Surface Modification Alleviates the Toxicity of Fe-MOFs to Rice and Improves Iron Absorption.

Abstract

Iron-based metal-organic frameworks (Fe-MOFs) are widely used for agricultural chemical delivery due to their high loading capacity, and they also have the potential to provide essential iron for plant growth. Therefore, they hold significant promise for agricultural applications. Evaluating the plant biotoxicity of Fe-MOFs is crucial for optimizing their use in agriculture. In this study, we used the natural biomacromolecule carboxymethyl cellulose (CMC) to encapsulate the Fe-MOF NH₂-MIL-101 (Fe) (MIL). Through hydroponic experiments, we investigated the biotoxic effects of Fe-MOFs on rice before and after CMC modification. The results show that the accumulation of iron in rice is dependent on the dose and the exposure concentration of Fe-MOFs. CMC modification (MIL@CMC) can reduce the release rate of Fe ions from Fe-MOFs in aqueous solutions with different pH values (5 and 7). Furthermore, MIL@CMC treatment significantly increases the absorption of iron by both the aboveground and root parts of rice. MIL@CMC significantly alleviated the growth inhibition of rice seedlings and increased the aboveground biomass of rice under medium- to high-exposure conditions. Specifically, in rice roots, MIL induced a more intense oxidative stress response, with significant increases in the activities of related antioxidant enzymes (CAT, POD, and SOD) and MDA content. Our results demonstrated that the encapsulation of NH₂-MIL-101(Fe) using CMC effectively alleviated oxidative damage and promoted the uptake and growth of iron in rice. These findings suggest that rational modification can have a positive effect on reducing the potential phytotoxicity of MOFs and improving their biosafety in agricultural applications.