The delicate balance between gelation and crystallisation: structural and computational investigations
- 1 January 2010
- journal article
- Published by Royal Society of Chemistry (RSC) in Soft Matter
- Vol. 6 (17), 4144-4156
- https://doi.org/10.1039/c0sm00409j
Abstract
Predicting the ability of low molecular weight molecules to form hydrogels is difficult. Here, we have examined the self-assembly behavior of two chemically and structurally similar functionalized dipeptides, one of which is found to form a meta-stable hydrogel (1) and the other forming a crystalline solid (2). To investigate the reasons for these differences, we have employed computational methods to explore the crystal energy landscapes of the two molecules and examined differences in their preferred packing arrangements. We show that this method accurately predicts the packing for the crystalline solid, 2. Furthermore, the predictions for the gel-former 1 suggest that one-dimensional hydrogen-bonding arranged into tightly coiled molecular columns is a preferred mode of packing for this system, but is unfavorable for 2. The different tendencies of forming these columns could provide an explanation for the different behavior of the two molecules and demonstrate that this approach could be useful for the future predictable design of low molecular weight gelators.Keywords
This publication has 50 references indexed in Scilit:
- Self-Assembly and Hydrogelation of an Amyloid Peptide FragmentBiochemistry, 2008
- De Novo Design of Strand-Swapped β-Hairpin HydrogelsJournal of the American Chemical Society, 2008
- Composites of N,N′-bis-(pyridyl) urea-dicarboxylic acid as new hydrogelators—a crystal engineering approachTetrahedron, 2007
- Gelation Kinetics of β-Hairpin Peptide Hydrogel NetworksMacromolecules, 2006
- Self-assembling β-Sheet Tape Forming PeptidesSupramolecular Chemistry, 2006
- Design and Application of Self‐Assembled Low Molecular Weight HydrogelsEuropean Journal of Organic Chemistry, 2005
- Retrieval of Crystallographically-Derived Molecular Geometry InformationJournal of Chemical Information and Computer Sciences, 2004
- Water Gelation by Small Organic MoleculesChemical Reviews, 2004
- Self‐Assembling Peptide Polyelectrolyte β‐Sheet Complexes Form Nematic HydrogelsAngewandte Chemie-International Edition, 2003
- pH as a Trigger of Peptide β-Sheet Self-Assembly and Reversible Switching between Nematic and Isotropic PhasesJournal of the American Chemical Society, 2003