Insight into the self-assembly of water-soluble perylene bisimide derivatives through a combined computational and experimental approach

Emily Draper, Liam Wilbraham, Dave J. Adams, Matthew Wallace, Ralf Schweins, Martijn Zwijnenburg

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Abstract

We use a combination of computational and experimental techniques to study the self-assembly and gelation of water-soluble perylene bisimides derivatised at the imide position with an amino acid. Specifically, we study the likely structure of self-assembled aggregates of the alanine-functionalised perylene bisimide (PBI-A) and the thermodynamics of their formation using density functional theory and predict the UV-vis spectra of such aggregates using time-dependent density functional theory. We compare these predictions to experiments in which we study the evolution of the UV-Vis and NMR spectra and rheology of alkaline PBI-A solutions when gradually decreasing the pH. Based on the combined computational and experimental results, we show that PBI-A self-assembles at all pH values but that aggregates grow in size upon protonation. Hydrogel formation is driven not by aggregate growth but reduction of the aggregation surface-charge and a decrease in the colloidal stability of the aggregation with respect to agglomeration.
Original languageEnglish
Pages (from-to)15917-15928
Number of pages12
JournalNanoscale
Volume11
Issue number34
Early online date6 Aug 2019
DOIs
Publication statusPublished - 14 Sep 2019

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