In Situ Eco Encapsulation of Bioactive Agrochemicals within Fully Organic Nanotubes

Abstract

Agrochemical encapsulation agents used up to now are commonly based on polymeric compounds or metal particles, but the employment of other natural products such as host structures has not been tackled in detail. In the work reported here, fully organic nanotubes composed of human bile acid (lithocholic acid) have been synthesized. These nanotubes were employed to encapsulate potential disulfide herbicide mimics that have previously shown relevant inhibitory activity against weeds. The three-dimensional chemical information from scanning transmission electron microscope analytical tomography with subnanometer scale resolution convincingly demonstrates for the first time the occurrence of efficient encapsulation within a fully organic nanotube of different organic molecules with activity as herbicides. The encapsulation was achieved in a one-pot synthesis, in an aqueous environment and under in situ conditions without using any marker or coating with contrast materials, which renders the process greener than those routinely used. The nanotubes allow complete water solubilization, with an encapsulation percentage of up to 78% in all of the herbicide compounds. Furthermore, nanotubes showed a flattened arrangement due to the host-guest interaction. The synthetic approach represents a step forward in solving the key problem of the quite limited solubility of natural agrochemicals in aqueous environments. In addition, the process presents a breakthrough in the use of natural products produced by the human body as encapsulating agents, which expands possible future applications. The preliminary docking approach clarifies that the 2o01 transmembrane transport protein seems to be the prior channel of the organic nanotube in the delivery process to vegetable cells. The etiolated wheat coleoptile bioassay demonstrated that the encapsulated herbicides have improved the bioactivity of free compounds, keeping 60% of inhibition of the weed at least for every disulfide, a requisite for their fruitful application as agrochemicals.

Keywords: TEM tomography; drug encapsulation; organic nanotube; phytotoxicity; weed control.