Effects of acid dissociation and ionic solutions on the Aggregation of 2-pyrone-4,6-dicarboxylic acid

11 June 2024, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


The conversion of lignin can produce biomass-derived aromatic compounds such as 2-pyrone-4,6-dicarboxylic acid (PDC), which is a potential sustainable precursor of bioplastics. PDC is a pseudoaromatic dicarboxylic acid that can aggregate in aqueous solution. Aggregation depends upon PDC-PDC, PDC-water, and PDC-ion interactions that are representative of interactions in similar charged, aromatic compounds. These interactions both dictate PDC aggregation and the likelihood that PDC aggregates exhibit parallel stacking configurations that may promote PDC crystallization, which can be leveraged to separate PDC from solution. However, the interplay of interactions that drive aggregation and structure formation, and how these depend upon the charge of PDC and ionic species present in solution, remains unclear. In this work, we investigate PDC aggregation in diverse ionic solutions using all-atom molecular dynamics simulations and molecular clustering analysis. We consider ion-induced dipole interactions by using a modified Lennard-Jones non-bonded model for divalent ions in solutions. From molecular clustering analysis, we derive characteristic parameters to quantify aggregate sizes and parallel stacking configurations. We show that acid dissociation facilitates PDC aggregation in ionic solutions via ion-mediated interactions, and different ionic solutions influence both the likelihood of aggregation and the formation of parallel aggregates. In particular, we find that parallel stacking is primarily found in solutions with monovalent ions, whereas divalent ions promote larger, but less structured, aggregates. These results provide molecular-scale insight into the effects of specific ions on the aggregation of like-charged PDC molecules to inform understanding of related separation processes.


Molecular dynamics
Metal ions
Biomass valorization
Ion-mediated interactions

Supplementary materials

Supporting Information
Additional methods, results, and simulation details.


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