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



Draper, Emily R, Wilbraham, Liam, Adams, Dave J, Wallace, Matthew, Schweins, Ralf and Zwijnenburg, Martijn A
(2019) Insight into the self-assembly of water-soluble perylene bisimide derivatives through a combined computational and experimental approach. NANOSCALE, 11 (34). pp. 15917-15928.

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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 the rheology and neutron scattering 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.

Item Type: Article
Depositing User: Symplectic Admin
Date Deposited: 09 Dec 2019 15:29
Last Modified: 19 Jan 2023 00:13
DOI: 10.1039/c9nr03898a
Open Access URL: https://doi.org/10.1039/C9NR03898A
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URI: https://livrepository.liverpool.ac.uk/id/eprint/3065610