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

Draper, E. R. , Wilbraham, L. , Adams, D. J. , Wallace, M., Schweins, R. and Zwijnenburg, M. 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. (doi: 10.1039/C9NR03898A) (PMID:31414112)

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: Articles
• Status: Published
• Refereed: Yes
• Glasgow Author(s) Enlighten ID: Draper, Emily and Adams, Dave and Wilbraham, Mr Liam
• Authors: Draper, E. R., Wilbraham, L., Adams, D. J., Wallace, M., Schweins, R., and Zwijnenburg, M. A.
• College/School: College of Science and Engineering > School of Chemistry
• Journal Name: Nanoscale
• Publisher: Royal Society of Chemistry
• ISSN: 2040-3364
• ISSN (Online): 2040-3372
• Published Online: 06 August 2019
• Copyright Holders: Copyright © 2019 The Royal Society of Chemistry
• First Published: First published in Nanoscale 11(34): 15917-15928
• Publisher Policy: Reproduced under a Creative Commons License

Project Code	Award No	Project Name	Principal Investigator	Funder's Name	Funder Ref	Lead Dept
174028		Integration of Computation and Experiment for Accelerated Materials Discovery	Dave Adams	Engineering and Physical Sciences Research Council (EPSRC)	CCR10895 (EP/N004884/1)	Chemistry