Probing the surface chemistry of self-assembled peptide hydrogels using solution-state NMR spectroscopy

Wallace, M., Iggo, J. A. and Adams, D. J. (2017) Probing the surface chemistry of self-assembled peptide hydrogels using solution-state NMR spectroscopy. Soft Matter, 13(8), pp. 1716-1727. (doi: 10.1039/C6SM02404A) (PMID:28165092)

Abstract

The surface chemistry of self-assembled hydrogel fibres – their charge, hydrophobicity and ion-binding dynamics – is recognised to play an important role in determining how the gels develop as well as their suitability for different applications. However, to date there are no established methodologies for the study of this surface chemistry. Here, we demonstrate how solution-state NMR spectroscopy can be employed to measure the surface chemical properties of the fibres in a range of hydrogels formed from N-functionalised dipeptides, an effective and versatile class of gelator that has attracted much attention. By studying the interactions with the gel fibres of a diverse range of probe molecules and ions, we can simultaneously study a number of surface chemical properties of the NMR invisible fibres in an essentially non-invasive manner. Our results yield fresh insights into the materials. Most notably, gel fibres assembled using different tiggering methods bear differing amounts of negative charge as a result of a partial deprotonation of the carboxylic acid groups of the gelators. We also demonstrate how chemical shift imaging (CSI) techniques can be applied to follow the formation of hydrogels along chemical gradients. We apply CSI to study the binding of Ca2+ and subsequent gelation of peptide assemblies at alkaline pH. Using metal ion-binding molecules as probes, we are able to detect the presence of bound Ca2+ ions on the surface of the gel fibres. We briefly explore how knowledge of the surface chemical properties of hydrogels could be used to inform their practical application in fields such as drug delivery and environmental remediation.

• Item Type: Articles
• Additional Information: The authors thank the EPSRC for funding (EP/C005643/1 and EP/K039687/1). DA thanks the EPSRC for a Fellowship (EP/L021978/1).
• Status: Published
• Refereed: Yes
• Glasgow Author(s) Enlighten ID: Adams, Dave
• Authors: Wallace, M., Iggo, J. A., and Adams, D. J.
• College/School: College of Science and Engineering > School of Chemistry
• Journal Name: Soft Matter
• Publisher: Royal Society of Chemistry
• ISSN: 1744-683X
• ISSN (Online): 1744-6848
• Published Online: 31 January 2017
• Copyright Holders: Copyright © 2017 The Authors
• First Published: First published in Soft Matter 13(8):1716-1727
• Publisher Policy: Reproduced under a Creative Commons License