期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 21, 期 52, 页码 19257-19264出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201503616
关键词
amphiphiles; nanomaterials; polymers; self-assembly; supramolecular chemistry
资金
- Fonds der Chemischen Industrie (FCI)
- Marie-Curie Actions FP7 (Career Integration Grant, SupraBioMat) [PCIG10-GA-2011-303872]
- Nordrhein-Westfalische Akademie der Wissenschaften und der Kunste for a Fellowship via the Junges Kolleg
- COST Action [CM1005]
- Netherlands Organization for Scientific Research (NWO ECHO-STIP) [717.013.005]
- Dutch Ministry of Education, Culture and Science (Gravity program) [024.001.035]
- European Research Council (FP7)
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.
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