Study of (Cyclic Peptide)–Polymer Conjugate Assemblies by Small‐Angle Neutron Scattering

Abstract

Copyright and reuse:The Warwick Research Archive Portal (WRAP) makes this work by researchers of the University of Warwick available open access under the following conditions. Copyright © and all moral rights to the version of the paper presented here belong to the individual author(s) and/or other copyright owners. To the extent reasonable and practicable the material made available in WRAP has been checked for eligibility before being made available.Copies of full items can be used for personal research or study, educational, or not-for profit purposes without prior permission or charge. Provided that the authors, title and full bibliographic details are credited, a hyperlink and/or URL is given for the original metadata page and the content is not changed in any way. A note on versions:The version presented here may differ from the published version or, version of record, if you wish to cite this item you are advised to consult the publisher's version. Please see the 'permanent WRAP url' above for details on accessing the published version and note that access may require a subscription. AbstractWe present a fundamental study into the self-assembly of (cyclic peptide)-polymer conjugates as a versatile supramolecular motif to engineer nanotubes with defined structure and dimensions, as characterised in solution using small angle neutron scattering (SANS).This work demonstrates the ability of the grafted polymer to stabilise and/or promote the formation of unaggregated nanotubes by the direct comparison to the unconjugated cyclic peptide precursor. This ideal case permitted a further study into the growth mechanism of self-assembling cyclic peptides, allowing an estimation of the cooperativity. Furthermore we show the dependency of the nanostructure on the polymer and peptide chemical functionality in solvent mixtures that vary in the ability to compete with the intermolecular associations between cyclic peptides and ability to solvate the polymer shell.

Probing the Dynamic Nature of Self‐Assembling Cyclic Peptide–Polymer Nanotubes in Solution and in Mammalian Cells

“…SANS is a powerful technique to characterize complex systems in order to understand any structural parameters, interactions, and changes due to environmental stimuli occurring in solution . Previously, our group has used SANS to analyze a wide‐range of CPNTs in different solvents, polymer conjugations, and in response to different stimuli (pH and temperature) . Here, SANS was used to confirm the formation of nanotubes for a mixture of conjugates 10 and 12 , and to analyze how the presence of a fluorophore affected their stacking potential compared to the nondye‐conjugated control (PEG–CP–alkyl, 11 ).…”

“…The core radius has been shown to be 0.34 nm in previous studies and was used as a fixed parameter in the fitting process. [25a] From the values obtained, the number of aggregation ( N agg ) can be determined by dividing the length of the tube by the distance between two single cyclic peptide unimers (0.47 nm), shown in Table 1 . [25a,26] Visually analyzing the scattering profiles reveals a major difference in the Guinier region ( q = 0.00416–0.01).…”

“…[25a] From the values obtained, the number of aggregation ( N agg ) can be determined by dividing the length of the tube by the distance between two single cyclic peptide unimers (0.47 nm), shown in Table 1 . [25a,26] Visually analyzing the scattering profiles reveals a major difference in the Guinier region ( q = 0.00416–0.01). Given that the Guinier region provides information on larger structures within the system, deviations here indicate nanotubes of different lengths.…”

Tubular supramolecular alternating copolymers fabricated by cyclic peptide–polymer conjugates

“…Using SASt soware, the data could be tted using a cylindrical micelle model (Table S1 †), suggesting it forming tubular supramolecular polymers in water. 59 The formed supramolecular polymers were visualized by TEM and AFM. As presented in Fig.…”

Royal Australian Chemical Institute Awards

“…Jolliffe's research interests are focused on the development of new methods for the synthesis of cyclic peptides and the use of peptides and peptidomimetics as scaffolds in supramolecular chemistry. She has reported in Chemistry—A European Journal on the self‐assembly of (cyclic peptide)–polymer conjugates …”