title: Steric Constraints Induced Frustrated Growth of Supramolecular Nanorods in Water.
abstract: A unique example of supramolecular polymerisation in water based on monomers with nanomolar affinities, which yield rod-like materials with extraordinarily high thermodynamic stability, yet of finite length, is reported. A small library of charge-neutral dendritic peptide amphiphiles was prepared, with a branched nonaphenylalanine-based core that was conjugated to hydrophilic dendrons of variable steric demand. Below a critical size of the dendron, the monomers assemble into nanorod-like polymers, whereas for larger dendritic side chains frustrated growth into near isotropic particles is observed. The supramolecular morphologies observed by electron microscopy, X-ray scattering and diffusion NMR spectroscopy studies are in agreement with the mechanistic insights obtained from fitting polymerisation profiles: non-cooperative isodesmic growth leads to degrees of polymerisation that match the experimentally determined nanorod contour lengths of close to 70 nm. The reported designs for aqueous self-assembly into well-defined anisotropic particles has promising potential for biomedical applications and the development of functional supramolecular biomaterials, with emerging evidence that anisotropic shapes in carrier design outperform conventional isotropic materials for targeted imaging and therapy.
authors.affiliation: Institute of Organic Chemistry and CeNTech, University of Muenster, Corrensstrasse 40, 48149 Münster (Germany).|Institute of Organic Chemistry, University of Mainz, Duesbergweg 10-14, 55128 Mainz (Germany).
authors.forename: Ralph
authors.initials: R
authors.lastname: Appel
authors.affiliation: Institute of Physical Chemistry, University of Muenster, Corrensstrasse 28/30, 48149 Münster (Germany).
authors.forename: Jonas
authors.initials: J
authors.lastname: Fuchs
authors.affiliation: Institute of Physical Chemistry, University of Muenster, Corrensstrasse 28/30, 48149 Münster (Germany).
authors.forename: Sara M
authors.initials: SM
authors.lastname: Tyrrell
authors.affiliation: Institute for Complex Molecular Systems and, Laboratory for Macromolecular and Organic Chemistry, Eindhoven University of Technology (The Netherlands).
authors.forename: Peter A
authors.initials: PA
authors.lastname: Korevaar
authors.affiliation: Department of Biophysical Chemistry, Groningen Biomolecular Sciences and Biotechnology Institute, University of Groningen, Nijenborgh 7, 9747 AG Groningen (The Netherlands).
authors.forename: Marc C A
authors.initials: MC
authors.lastname: Stuart
authors.affiliation: Institute for Complex Molecular Systems and, Laboratory for Macromolecular and Organic Chemistry, Eindhoven University of Technology (The Netherlands).|Laboratory for Physical Chemistry, Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven (The Netherlands).
authors.forename: Ilja K
authors.initials: IK
authors.lastname: Voets
authors.affiliation: Institute of Physical Chemistry, University of Muenster, Corrensstrasse 28/30, 48149 Münster (Germany).
authors.forename: Monika
authors.initials: M
authors.lastname: Schönhoff
authors.affiliation: Institute of Organic Chemistry and CeNTech, University of Muenster, Corrensstrasse 40, 48149 Münster (Germany). besenius@uni-mainz.de.|Institute of Organic Chemistry, University of Mainz, Duesbergweg 10-14, 55128 Mainz (Germany). besenius@uni-mainz.de.
authors.forename: Pol
authors.initials: P
authors.lastname: Besenius
keywords: amphiphiles; nanomaterials; polymers; self-assembly; supramolecular chemistry