pH-Controlled Chiral Packing and Self-Assembly of a Coumarin Tetrapeptide

A coumarin-tetrapeptide conjugate, EFEK(DAC)-NH2 (1), is reported to undergo a pH-dependent interconversion between nanotubes and nanoribbons. An examination of zeta potential measurements, circular dichroism (CD) spectra, and microscopy imaging (transmission electron microscopy and atomic force mic...

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Veröffentlicht in:Langmuir : the ACS journal of surfaces and colloids. - 1992. - 35(2019), 38 vom: 24. Sept., Seite 12460-12468
1. Verfasser: Mason, McKensie L (VerfasserIn)
Weitere Verfasser: Lalisse, Remy F, Finnegan, Tyler J, Hadad, Christopher M, Modarelli, David A, Parquette, Jon R
Format: Online-Aufsatz
Sprache:English
Veröffentlicht: 2019
Zugriff auf das übergeordnete Werk:Langmuir : the ACS journal of surfaces and colloids
Schlagworte:Journal Article Research Support, N.I.H., Extramural Research Support, Non-U.S. Gov't Coumarins Nanotubes, Carbon Oligopeptides
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520 |a A coumarin-tetrapeptide conjugate, EFEK(DAC)-NH2 (1), is reported to undergo a pH-dependent interconversion between nanotubes and nanoribbons. An examination of zeta potential measurements, circular dichroism (CD) spectra, and microscopy imaging (transmission electron microscopy and atomic force microscopy) identified three different self-assembly regimes based on pH: (1) pH 2-5, positively charged, left-handed helical nanotubes; (2) pH 6-8, negatively charged, right-handed helical nanoribbons; and (3) pH ≥ 9.0, a monomeric/disassembled peptide. The nanotubes exhibited uniform diameters of 41 ± 5 nm and wall thicknesses of 4.8 ± 0.8 nm, whereas the nanoribbons existed as either flat or twisted sheets ranging in width from 11 to 60 nm with heights of 8 ± 1 nm. The UV-vis and CD spectra of the most common antiparallel, β-sheet conformation of 1-dimer were simulated at the B3LYP/def2svpd level of theory in implicit water. These studies indicated that the transition from nanotubes to nanoribbons was coupled to an M → P helical inversion of the coumarin packing orientation, respectively, within the nanostructures. The assembly process was driven by β-sheet aggregation and π-π interactions, leading to the formation of nanoribbons, which progressively wound into helical ribbons and laterally grew into smooth nanotubes as the pH decreased 
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650 7 |a Nanotubes, Carbon  |2 NLM 
650 7 |a Oligopeptides  |2 NLM 
700 1 |a Lalisse, Remy F  |e verfasserin  |4 aut 
700 1 |a Finnegan, Tyler J  |e verfasserin  |4 aut 
700 1 |a Hadad, Christopher M  |e verfasserin  |4 aut 
700 1 |a Modarelli, David A  |e verfasserin  |4 aut 
700 1 |a Parquette, Jon R  |e verfasserin  |4 aut 
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