Rationalising Supramolecular Hydrogelation of Bis‐Urea‐Based Gelators through a Multiscale Approach

Ruben Van Lommel, Laurens A. J. Rutgeerts, Wim M. De Borggraeve, Frank De Proft, Mercedes Alonso

Research output: Contribution to journalArticlepeer-review

7 Citations (Scopus)
51 Downloads (Pure)

Abstract

The current approach to designing low‐molecular‐weight gelators relies on a laborious trial‐and‐error process, mainly because of the lack of an accurate description of the noncovalent interactions crucial for supramolecular gelation. In this work, we report a multiscale bottom‐up approach composed of several computational techniques to unravel the key interactions in a library of synthesized bis‐urea‐based gelators and rationalize their experimentally observed hydrogelation performance. In addition to density functional theory calculations and molecular dynamics, the noncovalent interaction index is applied as a tool to visualise and identify the different types of noncovalent interactions. Interestingly, as well as hydrogen bonds between urea moieties, hydrogen bonds between a urea moiety and a pyridine ring were shown to play a detrimental role in the early aggregation phase. These findings enabled us to explain the hydrogelation performance observed in a library of twelve bis‐urea derivatives, which were synthesized with 58–95 % yields. From this library, three compounds were discovered to effectively gel water, with the most efficient hydrogelator only requiring a concentration of 0.2 w/v%.
Original languageEnglish
Pages (from-to)267-276
Number of pages10
JournalChemPlusChem
Volume85
Issue number2
Early online date19 Oct 2019
DOIs
Publication statusPublished - Feb 2020

Bibliographical note

Funding Information:
The authors are grateful to Karel Duerinckx (KU Leuven) for the assistance with NMR measurements. Tier2 computational resources and services were provided by the Shared ICT Services Centre Funded by the Vrije Universiteit Brussel, the Flemish Supercomputer Center (VSC) and FWO. The authors thank Prof. Paula Moldenaers for the use of rheometers. The Strategic Research Program funding of the VUB is thanked for financial support. F. D. P. also acknowledges the Francqui foundation for a position as “Francqui research professor”. R. V. L. thanks FWO for the PhD fellowship received (1185219 N). M. A. thanks the FWO for a postdoctoral fellowship (12F4416 N) and the VUB for financial support.

Publisher Copyright:
© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

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