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Issue 3, 2018
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Self-assembly pathways and polymorphism in peptide-based nanostructures

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Dipeptide derivative molecules can self-assemble into space-filling nanofiber networks at low volume fractions (<1%), allowing the formation of molecular gels with tunable mechanical properties. The self-assembly of dipeptide-based molecules is reminiscent of pathological amyloid fibril formation by naturally occurring polypeptides. Fluorenylmethoxycarbonyl-diphenylalanine (Fmoc-FF) is the most widely studied such molecule, but the thermodynamic and kinetic phenomena giving rise to Fmoc-FF gel formation remain poorly understood. We have previously presented evidence that the gelation process is a first order phase transition characterized by low energy barriers to nucleation, short induction times, and rapid quasi-one-dimensional crystal growth, stemming from solvent–solute interactions and highly specific molecular packing. Here, we discuss the phase behavior of Fmoc-FF in different solvents. We find that Fmoc-FF gel formation can be induced in apolar solvents, in addition to previously established pathways in aqueous systems. We further show that in certain solvent systems anisotropic crystals (nanofibers) are an initial metastable state, after which macroscopic crystal aggregates with no preferred axis of growth are formed. The molecular conformation is sensitive to solvent composition during assembly, indicating that Fmoc-FF may be a simple model system to study complex thermodynamic and kinetic phenomena involved in peptide self-assembly.

Graphical abstract: Self-assembly pathways and polymorphism in peptide-based nanostructures

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Publication details

The article was received on 09 Sep 2017, accepted on 21 Dec 2017 and first published on 22 Dec 2017

Article type: Paper
DOI: 10.1039/C7NR06724K
Citation: Nanoscale, 2018,10, 1508-1516
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    Self-assembly pathways and polymorphism in peptide-based nanostructures

    N. A. Dudukovic, B. C. Hudson, A. K. Paravastu and C. F. Zukoski, Nanoscale, 2018, 10, 1508
    DOI: 10.1039/C7NR06724K

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