Side-chain-controlled self-assembly of polystyrene-polypeptide miktoarm star copolymers
Type
ArticleAuthors
Junnila, SusannaHoubenov, Nikolay
Karatzas, A.
Hadjichristidis, Nikos

Hirao, Akira
Iatrou, Hermis
Ikkala, Olli T.
KAUST Department
Biological and Environmental Sciences and Engineering (BESE) DivisionChemical Science Program
KAUST Catalysis Center (KCC)
Physical Science and Engineering (PSE) Division
Polymer Synthesis Laboratory
Date
2012-03-07Online Publication Date
2012-03-07Print Publication Date
2012-03-27Permanent link to this record
http://hdl.handle.net/10754/562136
Metadata
Show full item recordAbstract
We show how the self-assembly of miktoarm star copolymers can be controlled by modifying the side chains of their polypeptide arms, using A 2B and A 2B 2 type polymer/polypeptide hybrids (macromolecular chimeras). Initially synthesized PS 2PBLL and PS 2PBLL 2 (PS, polystyrene; PBLL, poly(ε-tert-butyloxycarbonyl-l-lysine) ) miktoarms were first deprotected to PS 2PLLHCl and PS 2PLLHCl 2 miktoarms (PLLHCl, poly(l-lysine hydrochloride)) and then complexed ionically with sodium dodecyl sulfonate (DS) to give the supramolecular complexes PS 2PLL(DS) and PS 2(PLL(DS)) 2. The solid-state self-assemblies of these six miktoarm systems were studied by transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), and small- and wide-angle X-ray scattering (SAXS, WAXS). The side chains of the polypeptide arms were observed to have a large effect on the solubility, polypeptide conformation, and self-assembly of the miktoarms. Three main categories were observed: (i) lamellar self-assemblies at the block copolymer length scale with packed layers of α-helices in PS 2PBLL and PS 2PBLL 2; (ii) charge-clustered polypeptide micelles with less-defined conformations in a nonordered lattice within a PS matrix in PS 2PLLHCl and PS 2PLLHCl 2; (iii) lamellar polypeptide-surfactant self-assemblies with β-sheet conformation in PS 2PLL(DS) and PS 2(PLL(DS)) 2 which dominate over the formation of block copolymer scale structures. Differences between the 3- and 4-arm systems illustrate how packing frustration between the coil-like PS arms and rigid polypeptide conformations can be relieved by the right number of arms, leading to differences in the extent of order. © 2012 American Chemical Society.Citation
Junnila, S., Houbenov, N., Karatzas, A., Hadjichristidis, N., Hirao, A., Iatrou, H., & Ikkala, O. (2012). Side-Chain-Controlled Self-Assembly of Polystyrene–Polypeptide Miktoarm Star Copolymers. Macromolecules, 45(6), 2850–2856. doi:10.1021/ma202747hPublisher
American Chemical Society (ACS)Journal
Macromoleculesae974a485f413a2113503eed53cd6c53
10.1021/ma202747h