Double smectic self-assembly in block copolypeptide complexes

Handle URI:
http://hdl.handle.net/10754/562409
Title:
Double smectic self-assembly in block copolypeptide complexes
Authors:
Haataja, Johannes S.; Houbenov, Nikolay; Iatrou, Hermis; Hadjichristidis, Nikolaos ( 0000-0003-1442-1714 ) ; Karatzas, A.; Faul, Charl F. J.; Rannou, Patrice; Ikkala, Olli T.
Abstract:
We show double smectic-like self-assemblies in the solid state involving alternating layers of different polypeptide α-helices. We employed rod-coil poly(γ-benzyl l-glutamate)-block-poly(l-lysine) (PBLG-b-PLL) as the polymeric scaffold, where the PLL amino residues were ionically complexed to di-n-butyl phosphate (diC4P), di(2-ethylhexyl) phosphate (diC2/6P), di(2-octyldodecyl) phosphate (diC8/12P), or di-n-dodecyl phosphate (diC12P), forming PBLG-b-PLL(diC4P), PBLG-b-PLL(diC2/6P), PBLG-b-PLL(diC8/12P), and PBLG-b-PLL(diC12P) complexes, respectively. The complexes contain PBLG α-helices of fixed diameter and PLL-surfactant complexes adopting either α-helices of tunable diameters or β-sheets. For PBLG-b-PLL(diC4P), that is, using a surfactant with short n-butyl tails, both blocks were α-helical, of roughly equal diameter and thus with minor packing frustrations, leading to alternating PBLG and PLL(diC4P) smectic layers of approximately perpendicular alignment of both types of α-helices. Surfactants with longer and branched alkyl tails lead to an increased diameter of the PLL-surfactant α-helices. Smectic alternating PBLG and PLL(diC2/6P) layers involve larger packing frustration, which leads to poor overall order and suggests an arrangement of tilted PBLG α-helices. In PBLG-b-PLL(diC8/12P), the PLL(diC8/12P) α-helices are even larger and the overall structure is poor. Using a surfactant with two linear n-dodecyl tails leads to well-ordered β-sheet domains of PLL(diC12P), consisting of alternating PLL and alkyl chain layers. This dominates the whole assembly, and at the block copolypeptide length scale, the PBLG α-helices do not show internal order and have poor organization. Packing frustration becomes an important aspect to design block copolypeptide assemblies, even if frustration could be relieved by conformational imperfections. The results suggest pathways to control hierarchical liquid-crystalline assemblies by competing interactions and by controlling molecular packing frustrations. © 2012 American Chemical Society.
KAUST Department:
Biological and Environmental Sciences and Engineering (BESE) Division; Physical Sciences and Engineering (PSE) Division; Chemical Science Program; KAUST Catalysis Center (KCC); Polymer Synthesis Laboratory
Publisher:
American Chemical Society (ACS)
Journal:
Biomacromolecules
Issue Date:
12-Nov-2012
DOI:
10.1021/bm3010275
PubMed ID:
22970916
Type:
Article
ISSN:
15257797
Sponsors:
We acknowledge financial support from Academy of Finland and European Research Council. C.F.J.F. thanks the University of Bristol for support and Aalto for a visiting professorship. Access to and use of the microscopy facilities of the Aalto Nanomicroscopy Center is gratefully acknowledged.
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; Chemical Science Program; KAUST Catalysis Center (KCC); Biological and Environmental Sciences and Engineering (BESE) Division

Full metadata record

DC FieldValue Language
dc.contributor.authorHaataja, Johannes S.en
dc.contributor.authorHoubenov, Nikolayen
dc.contributor.authorIatrou, Hermisen
dc.contributor.authorHadjichristidis, Nikolaosen
dc.contributor.authorKaratzas, A.en
dc.contributor.authorFaul, Charl F. J.en
dc.contributor.authorRannou, Patriceen
dc.contributor.authorIkkala, Olli T.en
dc.date.accessioned2015-08-03T10:37:10Zen
dc.date.available2015-08-03T10:37:10Zen
dc.date.issued2012-11-12en
dc.identifier.issn15257797en
dc.identifier.pmid22970916en
dc.identifier.doi10.1021/bm3010275en
dc.identifier.urihttp://hdl.handle.net/10754/562409en
dc.description.abstractWe show double smectic-like self-assemblies in the solid state involving alternating layers of different polypeptide α-helices. We employed rod-coil poly(γ-benzyl l-glutamate)-block-poly(l-lysine) (PBLG-b-PLL) as the polymeric scaffold, where the PLL amino residues were ionically complexed to di-n-butyl phosphate (diC4P), di(2-ethylhexyl) phosphate (diC2/6P), di(2-octyldodecyl) phosphate (diC8/12P), or di-n-dodecyl phosphate (diC12P), forming PBLG-b-PLL(diC4P), PBLG-b-PLL(diC2/6P), PBLG-b-PLL(diC8/12P), and PBLG-b-PLL(diC12P) complexes, respectively. The complexes contain PBLG α-helices of fixed diameter and PLL-surfactant complexes adopting either α-helices of tunable diameters or β-sheets. For PBLG-b-PLL(diC4P), that is, using a surfactant with short n-butyl tails, both blocks were α-helical, of roughly equal diameter and thus with minor packing frustrations, leading to alternating PBLG and PLL(diC4P) smectic layers of approximately perpendicular alignment of both types of α-helices. Surfactants with longer and branched alkyl tails lead to an increased diameter of the PLL-surfactant α-helices. Smectic alternating PBLG and PLL(diC2/6P) layers involve larger packing frustration, which leads to poor overall order and suggests an arrangement of tilted PBLG α-helices. In PBLG-b-PLL(diC8/12P), the PLL(diC8/12P) α-helices are even larger and the overall structure is poor. Using a surfactant with two linear n-dodecyl tails leads to well-ordered β-sheet domains of PLL(diC12P), consisting of alternating PLL and alkyl chain layers. This dominates the whole assembly, and at the block copolypeptide length scale, the PBLG α-helices do not show internal order and have poor organization. Packing frustration becomes an important aspect to design block copolypeptide assemblies, even if frustration could be relieved by conformational imperfections. The results suggest pathways to control hierarchical liquid-crystalline assemblies by competing interactions and by controlling molecular packing frustrations. © 2012 American Chemical Society.en
dc.description.sponsorshipWe acknowledge financial support from Academy of Finland and European Research Council. C.F.J.F. thanks the University of Bristol for support and Aalto for a visiting professorship. Access to and use of the microscopy facilities of the Aalto Nanomicroscopy Center is gratefully acknowledged.en
dc.publisherAmerican Chemical Society (ACS)en
dc.titleDouble smectic self-assembly in block copolypeptide complexesen
dc.typeArticleen
dc.contributor.departmentBiological and Environmental Sciences and Engineering (BESE) Divisionen
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.journalBiomacromoleculesen
dc.contributor.institutionAalto Univ Sch Sci, Dept Appl Phys, FI-02015 Espoo, Finlanden
dc.contributor.institutionUniv Athens, Dept Chem, Athens 15771, Greeceen
dc.contributor.institutionUniv Bristol, Sch Chem, Bristol BS8 1TS, Avon, Englanden
dc.contributor.institutionUniv Grenoble 1, Lab Elect Mol Organ & Hybride, CNRS, CEA,SPrAM,UMR5819,INAC,CEA Grenoble, F-38054 Grenoble 9, Franceen
kaust.authorHadjichristidis, Nikolaosen

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