title: Synthesis of Nonequilibrium Supramolecular Peptide Polymers on a Microfluidic Platform.
abstract: 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.
authors.affiliation: Department of Chemistry, University of Cambridge , Cambridge CB2 1EW, United Kingdom.
authors.forename: Thomas O
authors.initials: TO
authors.lastname: Mason
authors.affiliation: Department of Chemistry, University of Cambridge , Cambridge CB2 1EW, United Kingdom.
authors.forename: Thomas C T
authors.initials: TC
authors.lastname: Michaels
authors.affiliation: Department for Molecular Microbiology and Biotechnology, University of Tel Aviv , Tel Aviv 6997801, Israel.
authors.forename: Aviad
authors.initials: A
authors.lastname: Levin
authors.affiliation: Department for Molecular Microbiology and Biotechnology, University of Tel Aviv , Tel Aviv 6997801, Israel.|Department of Materials Science and Engineering, Tel Aviv University , Tel Aviv 6997801, Israel.
authors.forename: Ehud
authors.initials: E
authors.lastname: Gazit
authors.affiliation: Department of Chemistry, University of Cambridge , Cambridge CB2 1EW, United Kingdom.
authors.forename: Christopher M
authors.initials: CM
authors.lastname: Dobson
authors.affiliation: Department of Chemistry, University of Cambridge , Cambridge CB2 1EW, United Kingdom.|Institute of Physical Biology, Heinrich-Heine-University Düsseldorf , Düsseldorf 40225, Germany.
authors.forename: Alexander K
authors.initials: AK
authors.lastname: Buell
authors.affiliation: Department of Chemistry, University of Cambridge , Cambridge CB2 1EW, United Kingdom.
authors.forename: Tuomas P J
authors.initials: TP
authors.lastname: Knowles
mesh_terms: D060326:Chemistry Techniques, Synthetic / Q000295:instrumentation*; D056656:Lab-On-A-Chip Devices; D057786:Peptidomimetics / Q000138:chemical synthesis* / Q000737:chemistry; D011108:Polymers / Q000737:chemistry*
chemical_list: D057786:Peptidomimetics; D011108:Polymers