Side-chain-controlled self-assembly of polystyrene-polypeptide miktoarm star copolymers

Handle URI:
http://hdl.handle.net/10754/562136
Title:
Side-chain-controlled self-assembly of polystyrene-polypeptide miktoarm star copolymers
Authors:
Junnila, Susanna; Houbenov, Nikolay; Karatzas, A.; Hadjichristidis, Nikolaos ( 0000-0003-1442-1714 ) ; Hirao, Akira; Iatrou, Hermis; Ikkala, Olli T.
Abstract:
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.
KAUST Department:
Physical Sciences and Engineering (PSE) Division; Chemical Science Program; KAUST Catalysis Center (KCC); Polymer Synthesis Laboratory
Publisher:
American Chemical Society (ACS)
Journal:
Macromolecules
Issue Date:
27-Mar-2012
DOI:
10.1021/ma202747h
Type:
Article
ISSN:
00249297
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; Chemical Science Program; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorJunnila, Susannaen
dc.contributor.authorHoubenov, Nikolayen
dc.contributor.authorKaratzas, A.en
dc.contributor.authorHadjichristidis, Nikolaosen
dc.contributor.authorHirao, Akiraen
dc.contributor.authorIatrou, Hermisen
dc.contributor.authorIkkala, Olli T.en
dc.date.accessioned2015-08-03T09:45:38Zen
dc.date.available2015-08-03T09:45:38Zen
dc.date.issued2012-03-27en
dc.identifier.issn00249297en
dc.identifier.doi10.1021/ma202747hen
dc.identifier.urihttp://hdl.handle.net/10754/562136en
dc.description.abstractWe 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.en
dc.publisherAmerican Chemical Society (ACS)en
dc.titleSide-chain-controlled self-assembly of polystyrene-polypeptide miktoarm star copolymersen
dc.typeArticleen
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.contributor.departmentChemical Science Programen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.contributor.departmentPolymer Synthesis Laboratoryen
dc.identifier.journalMacromoleculesen
dc.contributor.institutionMolecular Materials, Department of Applied Physics, Aalto University, Previously Helsinki University of Technology, P.O. Box 15100, 00076 Aalto, Finlanden
dc.contributor.institutionDepartment of Chemistry, University of Athens, Panepistimiopolis, Zografou, 15771 Athens, Greeceen
dc.contributor.institutionPolymeric and Organic Materials Department, Graduate School of Science and Engineering, Tokyo Institute of Technology, Tokyo 152-8552, Japanen
kaust.authorHadjichristidis, Nikolaosen
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