@article{2959186, title = "Self-Assembly of Telechelic Tyrosine End-Capped PEO Star Polymers in Aqueous Solution", author = "Charlotte J. C. Edwards-Gayle and Francesca Greco and Ian W. Hamley and Robert P. Rambo and Mehedi Reza and Janne Ruokolainen and Dimitrios Skoulas and Hermis Iatrou", journal = "Biomacromolecules", year = "2017", volume = "19", number = "1", pages = "167--177", publisher = "American Chemical Society (ACS)", issn = "1525-7797, 1526-4602", doi = "10.1021/acs.biomac.7b01420", keywords = "Amino acids; Circular dichroism spectroscopy; Dichroism; Ethylene; High resolution transmission electron microscopy; Peptides; Polyethylene oxides; Ring opening polymerization; Solutions; Transmission electron microscopy; X ray scattering, Critical aggregation concentration; Cryogenic transmission electron microscopy; Fluorescence probes; Low concentrations; N-Carboxyanhydride; Peptide conformation; pH responsive biomaterials; Poly (ethylene oxide) (PEO), Self assembly, macrogol; polymer; tyrosine; tyrosine derivative; macrogol; peptide; tyrosine; water, aqueous solution; Article; beta sheet; chemical structure; circular dichroism; conjugate; density; fibril; micelle; pH; polymerization; priority journal; transmission electron microscopy; X ray crystallography; cell line; chemistry; human; hydrogel; infrared spectroscopy; nuclear magnetic resonance spectroscopy; size exclusion chromatography; small angle scattering; solution and solubility; X ray diffraction, Cell Line; Chromatography, Gel; Circular Dichroism; Humans; Hydrogels; Magnetic Resonance Spectroscopy; Microscopy, Electron, Transmission; Peptides; Polyethylene Glycols; Polymerization; Scattering, Small Angle; Solutions; Spectroscopy, Fourier Transform Infrared; Tyrosine; Water; X-Ray Diffraction", abstract = "We investigate the self-assembly of two telechelic star polymer-peptide conjugates based on poly(ethylene oxide) (PEO) four-arm star polymers capped with oligotyrosine. The conjugates were prepared via N-carboxy anhydride-mediated ring-opening polymerization from PEO star polymer macroinitiators. Self-assembly occurs above a critical aggregation concentration determined via fluorescence probe assays. Peptide conformation was examined using circular dichroism spectroscopy. The structure of self-assembled aggregates was probed using small-angle X-ray scattering and cryogenic transmission electron microscopy. In contrast to previous studies on linear telechelic PEO-oligotyrosine conjugates that show self-assembly into β-sheet fibrils, the star architecture suppresses fibril formation and micelles are generally observed instead, a small population of fibrils only being observed upon pH adjustment. Hydrogelation is also suppressed by the polymer star architecture. These peptide-functionalized star polymer solutions are cytocompatible at sufficiently low concentration. These systems present tyrosine at high density and may be useful in the development of future enzyme or pH-responsive biomaterials. © 2017 American Chemical Society." }