Document VersionPublisher's PDF, also known as Version of Record (includes final page, issue and volume numbers)Please check the document version of this publication:• A submitted manuscript is the author's version of the article upon submission and before peer-review. There can be important differences between the submitted version and the official published version of record. People interested in the research are advised to contact the author for the final version of the publication, or visit the DOI to the publisher's website.• The final author version and the galley proof are versions of the publication after peer review.• The final published version features the final layout of the paper including the volume, issue and page numbers. Link to publication Citation for published version (APA):Appel, R., Fuchs, J., Tyrrell, S. M., Korevaar, P. A., Stuart, M. C. A., Voets, I. K., ... Besenius, P. (2015). Steric constraints induced frustrated growth of supramolecular nanorods in water. Chemistry -A European Journal, 21(52), 19257-19264. DOI: 10.1002/chem.201503616 General rights Copyright and moral rights for the publications made accessible in the public portal are retained by the authors and/or other copyright owners and it is a condition of accessing publications that users recognise and abide by the legal requirements associated with these rights.• Users may download and print one copy of any publication from the public portal for the purpose of private study or research.• You may not further distribute the material or use it for any profit-making activity or commercial gain • You may freely distribute the URL identifying the publication in the public portal ? Take down policyIf you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediately and investigate your claim. Ilja K. Voets, [d, f] Monika Schçnhoff, [c] and Pol Besenius* [a, b] Abstract: Au nique example of supramolecular polymerisation in waterb ased on monomers with nanomolara ffinities, which yield rod-like materials with extraordinarily high thermodynamic stability, yet of finite length, is reported. A small libraryo fc harge-neutral dendritic peptide amphiphiles was prepared,w ith ab ranched nonaphenylalanine-based core that was conjugated to hydrophilic dendrons of variable steric demand. Below ac ritical size of the dendron,the monomers assemble into nanorod-like polymers,w hereas for larger dendritic side chainsf rustratedg rowth into near isotropic particles is observed.T he supramolecular morphologies observed by electron microscopy,X -ray scattering and diffusion NMR spectroscopy studies are in agreement with the mechanistic insights obtained from fitting polymerisationp rofiles:n on-cooperative isodesmic growth leads to degrees of polymerisation that matcht he experimentally determined nanorod contour lengths of close to 70 nm. The reportedd esignsf or aqueous self-assembly into well-defined anisotropic particles has promising potentialf or biomedical applicat...

We report the synthesis of a series of anionic dendritic peptide amphiphiles of increasing hydrophobic character. By establishing state diagrams we describe their pH and ionic strength triggered self-assembly into supramolecular nanorods in water and highlight the impact of hydrophobic shielding in the supramolecular polymerisation process. Via the incorporation of fluorinated peptide side chains the pH-triggered monomer to polymer transition at physiological ionic strength is shifted from pH 5.0 to pH 7.4. We thereby show that compensating attractive non-covalent interactions and hydrophobic effects with repulsive electrostatic forces, a concept we refer to as frustrated growth, is a sensitive tool in order to manipulate one-dimensional supramolecular polymerisation processes in water.

The permeability of the polymer walls of polyalkylcyanoacrylate nanocapsules varies by different degrees of chemical cross-linking. For this reason, different amounts of bivalent alkylcyanoacrylates are added to the monovalent alkylcyanoacrylate prior to an interfacial polymerization step in order to generate capsules with various cross-linking densities. The obtained nanocapsules are characterized by observing the water molecules via pulsed field-gradient nuclear magnetic resonance using a stimulated echo sequence. The resulting echo decay plots reveal the exchange rate of the water molecules between the free and encapsulated states. The observed dwell times of water molecules in the encapsulated state are characteristic parameters for the permeability of the given capsule membranes. They show a clear dependence on the degree of cross-linking, proving the potential of this approach for a controlled variation of the capsule permeability. Also, the cross-linked nanocapsules exhibit a significantly decreased solubility in tetrahydrofuran which may lead to new applications for polyalkylcyanoacrylate nanocapsules in organic solvents.