Synthesis of Nonequilibrium Supramolecular Peptide Polymers on a Microfluidic Platform

Thomas O. Mason, Thomas C.T. Michaels, Aviad Levin, Ehud Gazit, Christopher M. Dobson, Alexander K. Buell*, Tuomas P.J. Knowles

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review


The self-assembly of peptides and peptide mimetics into supramolecular polymers has been established in recent years as a route to biocompatible nanomaterials with novel mechanical, optical, and electronic properties. The morphologies of the resulting polymers are usually dictated by the strengths as well as lifetimes of the noncovalent bonds that lead to the formation of the structures. Together with an often incomplete understanding of the assembly mechanisms, these factors limit the control over the formation of polymers with tailored structures. Here, we have developed a microfluidic flow reactor to measure growth rates directly and accurately on the axial and radial faces of crystalline peptide supramolecular polymers. We show that the structures grow through two-dimensional nucleation mechanisms, with rates that depend exponentially on the concentration of soluble peptide. Using these mechanistic insights into the growth behavior of the axial and radial faces, we have been able to tune the aspect ratio of populations of dipeptide assemblies. These results demonstrate a general strategy to control kinetically self-assembly beyond thermodynamic products governed by the intrinsic properties of the building blocks in order to attain the required morphology and function.

Original languageEnglish
Pages (from-to)9589-9596
Number of pages8
JournalJournal of the American Chemical Society
Issue number30
StatePublished - 3 Aug 2016


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