Sequence/structure relationships in aromatic dipeptide hydrogels formed under thermodynamic control by enzyme-assisted self-assembly

Meghan Hughes, Pim W. J. M. Frederix, Jaclyn Raeburn, Louise S. Birchall, Jan Sadownik, Fiona C. Coomer, I-Hsin Lin, Edmund J. Cussen, Neil T. Hunt, Tell Tuttle, Simon J. Webb, Dave J. Adams, Rein V. Ulijn

Research output: Contribution to journalArticle

58 Citations (Scopus)

Abstract

Self-assembled supramolecular structures of peptide derivatives often reflect a kinetically trapped state rather than the thermodynamically most favoured structure, which presents a challenge when trying to elucidate the molecular design rules for these systems. In this article we use thermodynamically controlled self-assembly, driven by enzymatic condensation of amino acid derivatives, to elucidate chemical composition/nanostructure relationships for four closely related Fmoc-dipeptide-methyl esters which form hydrogels; SF, SL, TF and TL. We demonstrate that each of the four systems self-assemble to form extended arrays of beta-sheets which interlock via pi-stacking of Fmoc-moieties, yet with subtle differences in molecular organisation as supported by rheology, fluorescence emission spectroscopy, infrared spectroscopy, X-ray diffraction analysis and molecular mechanics minimisation.

LanguageEnglish
Pages5595-5602
Number of pages8
JournalSoft Matter
Volume8
Issue number20
DOIs
Publication statusPublished - 2012

Fingerprint

Hydrogels
Dipeptides
rheology
Self assembly
peptides
amino acids
self assembly
enzymes
esters
chemical composition
condensation
infrared spectroscopy
Thermodynamics
Derivatives
fluorescence
thermodynamics
Molecular mechanics
optimization
Fluorescence spectroscopy
Emission spectroscopy

Keywords

  • peptide derivatives
  • supramolecular structures
  • spectroscopy
  • infrared spectroscopy
  • X-ray diffraction analysis

Cite this

Hughes, Meghan ; Frederix, Pim W. J. M. ; Raeburn, Jaclyn ; Birchall, Louise S. ; Sadownik, Jan ; Coomer, Fiona C. ; Lin, I-Hsin ; Cussen, Edmund J. ; Hunt, Neil T. ; Tuttle, Tell ; Webb, Simon J. ; Adams, Dave J. ; Ulijn, Rein V. / Sequence/structure relationships in aromatic dipeptide hydrogels formed under thermodynamic control by enzyme-assisted self-assembly. In: Soft Matter. 2012 ; Vol. 8, No. 20. pp. 5595-5602.
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abstract = "Self-assembled supramolecular structures of peptide derivatives often reflect a kinetically trapped state rather than the thermodynamically most favoured structure, which presents a challenge when trying to elucidate the molecular design rules for these systems. In this article we use thermodynamically controlled self-assembly, driven by enzymatic condensation of amino acid derivatives, to elucidate chemical composition/nanostructure relationships for four closely related Fmoc-dipeptide-methyl esters which form hydrogels; SF, SL, TF and TL. We demonstrate that each of the four systems self-assemble to form extended arrays of beta-sheets which interlock via pi-stacking of Fmoc-moieties, yet with subtle differences in molecular organisation as supported by rheology, fluorescence emission spectroscopy, infrared spectroscopy, X-ray diffraction analysis and molecular mechanics minimisation.",
keywords = "peptide derivatives, supramolecular structures , spectroscopy, infrared spectroscopy, X-ray diffraction analysis",
author = "Meghan Hughes and Frederix, {Pim W. J. M.} and Jaclyn Raeburn and Birchall, {Louise S.} and Jan Sadownik and Coomer, {Fiona C.} and I-Hsin Lin and Cussen, {Edmund J.} and Hunt, {Neil T.} and Tell Tuttle and Webb, {Simon J.} and Adams, {Dave J.} and Ulijn, {Rein V.}",
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doi = "10.1039/c2sm25224d",
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Hughes, M, Frederix, PWJM, Raeburn, J, Birchall, LS, Sadownik, J, Coomer, FC, Lin, I-H, Cussen, EJ, Hunt, NT, Tuttle, T, Webb, SJ, Adams, DJ & Ulijn, RV 2012, 'Sequence/structure relationships in aromatic dipeptide hydrogels formed under thermodynamic control by enzyme-assisted self-assembly' Soft Matter, vol. 8, no. 20, pp. 5595-5602. https://doi.org/10.1039/c2sm25224d

Sequence/structure relationships in aromatic dipeptide hydrogels formed under thermodynamic control by enzyme-assisted self-assembly. / Hughes, Meghan; Frederix, Pim W. J. M.; Raeburn, Jaclyn; Birchall, Louise S.; Sadownik, Jan; Coomer, Fiona C.; Lin, I-Hsin; Cussen, Edmund J.; Hunt, Neil T.; Tuttle, Tell; Webb, Simon J.; Adams, Dave J.; Ulijn, Rein V.

In: Soft Matter, Vol. 8, No. 20, 2012, p. 5595-5602.

Research output: Contribution to journalArticle

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T1 - Sequence/structure relationships in aromatic dipeptide hydrogels formed under thermodynamic control by enzyme-assisted self-assembly

AU - Hughes, Meghan

AU - Frederix, Pim W. J. M.

AU - Raeburn, Jaclyn

AU - Birchall, Louise S.

AU - Sadownik, Jan

AU - Coomer, Fiona C.

AU - Lin, I-Hsin

AU - Cussen, Edmund J.

AU - Hunt, Neil T.

AU - Tuttle, Tell

AU - Webb, Simon J.

AU - Adams, Dave J.

AU - Ulijn, Rein V.

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AB - Self-assembled supramolecular structures of peptide derivatives often reflect a kinetically trapped state rather than the thermodynamically most favoured structure, which presents a challenge when trying to elucidate the molecular design rules for these systems. In this article we use thermodynamically controlled self-assembly, driven by enzymatic condensation of amino acid derivatives, to elucidate chemical composition/nanostructure relationships for four closely related Fmoc-dipeptide-methyl esters which form hydrogels; SF, SL, TF and TL. We demonstrate that each of the four systems self-assemble to form extended arrays of beta-sheets which interlock via pi-stacking of Fmoc-moieties, yet with subtle differences in molecular organisation as supported by rheology, fluorescence emission spectroscopy, infrared spectroscopy, X-ray diffraction analysis and molecular mechanics minimisation.

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KW - supramolecular structures

KW - spectroscopy

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