Precise control over supramolecular nanostructures via manipulation of H-bonding in π-amphiphiles

Abstract

Self-assembled supramolecular architectures are ubiquitous in nature. A synchronized combination of dynamic noncovalent interactions is the major driving force in forming unique structures with high-precision control over the self-assembly of supramolecular materials. Herein, we have achieved programmable nanostructures by introducing single/multiple H-bonding units in a supramolecular building block. A diverse range of nanostructures can be generated in aqueous medium by subtly tuning the structure of π-amphiphiles. 1D-cylindrical micelles, 2D-nanoribbons and hollow nanotubes are produced by systematically varying the number of H-bonding units (0–2) in structurally near identical π-amphiphiles. Spectroscopic measurements revealed the decisive role of H-bonding units for different modes of molecular packing. We have demonstrated that a competitive self-assembled state (a kinetically controlled aggregation state and a thermodynamically controlled aggregation state) can be generated by fine tuning the number of noncovalent forces present in the supramolecular building blocks. The luminescence properties of conjugated dithiomaleimide (DTM) provided insight into the relative hydrophobicity of the core in these nanostructures. In addition, fluorescence turn-off in the presence of thiophenol enabled us to probe the accessibility of the hydrophobic core in these assembled systems toward guest molecules. Therefore the DTM group provides an efficient tool to determine the relative hydrophobicity and accessibility of the core of various nanostructures which is very rarely studied in supramolecular assemblies.

Publication DOI: https://doi.org/10.1039/D1NR04882A
Divisions: College of Engineering & Physical Sciences
College of Engineering & Physical Sciences > School of Infrastructure and Sustainable Engineering > Chemical Engineering & Applied Chemistry
College of Engineering & Physical Sciences > Aston Institute of Materials Research (AIMR)
College of Engineering & Physical Sciences > Aston Polymer Research Group
Additional Information: This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence
Uncontrolled Keywords: Materials Science(all)
Publication ISSN: 2040-3372
Last Modified: 20 Feb 2024 08:20
Date Deposited: 07 Dec 2021 15:44
Full Text Link:
Related URLs: https://pubs.rs ... 1/NR/D1NR04882A (Publisher URL)
http://www.scop ... tnerID=8YFLogxK (Scopus URL)
PURE Output Type: Article
Published Date: 2021-12-21
Published Online Date: 2021-11-30
Accepted Date: 2021-10-18
Authors: Aikder, Amrita
Xie, Yujie
Thomas, Marjolaine
Derry, Matthew (ORCID Profile 0000-0001-5010-6725)
O'Reilly, Rachel K.

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