Tuning Local Order in Starch Nanoparticles Exploiting Nonsolvency with "Green" Solvents

Starch is a renewable biopolymer that can be sourced from agricultural waste and used to produce nanoparticles (SNPs). In particular, amorphous SNPs have potential application in numerous fields, including the consolidation of weakened paintings in the cultural heritage preservation. Starch dissolution followed by nanoprecipitation in nonsolvents is an advantageous synthetic route, but new methodologies are needed to feasibly control the physicochemical properties of the SNPs. Here, we explored nanoprecipitation by nonsolvency using a set of "green" solvents to obtain amorphous SNPs, rather than starch nanocrystals already reported in the literature. The effect of the nonsolvent on the ordering of polymer chains in the obtained SNPs was studied. The recovery of local order (e.g., isolated V-type helices) after dissolution was shown to depend on the type of solvents used in the dissolution and precipitation steps, while long-range order (extended arrays of helices) is lost. Aqueous dispersions of the SNPs provided effective consolidation of powdery painted layers, showing that the selection of particle synthetic routes can be dictated by sustainability and scalability criteria. These "green" formulations are candidates as new consolidants in art preservation, and the possibility of tuning local order in amorphous starch assemblies might also impact fields like food chemistry, pharmaceutics, and nanocomposites, where SNPs with tunable amorphousness are more advantageous than nanocrystals.