Self-assembled polymer nanostructures controlled by molecular architecture and polypeptide conformation

Susanna Junnila

Self-assembled polymer nanostructures controlled by molecular architecture and polypeptide conformation

Julkaisun otsikon käännös: Polymeerien nanorakenteiden itsejärjestymisen ohjaaminen molekyyliarkkitehtuurilla ja polypeptidien konformaatioilla

Susanna Junnila

Teknillisen fysiikan laitos

Tutkimustuotos: Doctoral Thesis › Collection of Articles

Abstrakti

Supramolekyylikemia, lohkopolymeerien itsejärjestyminen ja biopolymeerien konformaatiot ovat tärkeitä työkaluja nanomittakaavan rakenteiden luomisessa. Tässä työssä tutkimme, kuinka polypeptidipohjaisten materiaalien itsejärjestymistä voidaan ohjata surfaktanttien, lipidien ja lohkopolymeerien molekyyliarkkitehtuureilla ja polypeptidien konformaatioilla kiinteässä olomuodossa. Surfaktanttiarkkitehtuurin vaikutusta homopolypeptidi-surfaktantti-kompleksien itsejärjestymiseen on tutkittu julkaisuissa I ja II. Surfaktantin haaroittuminen vaikuttaa polypeptidin konformaatioon, kampamaisten supramolekyylikompleksien itsejärjestymiseen, alkyylihäntien kiteytymiseen ja nanorakenteen periodisuuteen. Näiden rakenteiden ulkoisesti ohjatut muutokset ovat mahdollisia kiinteässä olomuodossa. Lisäksi hauraat stoikiometriset kompleksit voidaan plastisoida lisäämällä ylimäärä surfaktantteja orgaanisessa liuottimessa. Lipidiarkkitehtuurin vaikutusta homopolypeptidi-lipidi-kompleksien itsejärjestymiseen on tutkittu julkaisussa III. Kolmihäntäiset lipidit koostuvat kahdesta alkyylihännästä ja yhdestä polyetyleeniglykolihännästä. Tyydyttyneet alkyyliketjut pystyvät kiteytymään huoneenlämpötilassa, jolloin alpha-kierteiset polypeptidiketjut ovat järjestyneet vinokulmaiseen hilaan, kun taas tyydyttymättömät alkyyliketjut pysyvät amorfisina ja kompleksit ovat järjestyneet heksagonaaliseen hilaan. Jälkimmäinen rakenne saavutetaan myös sulattamalla kiteiset alkyyliketjut, mikä todistaa, että alkyyliketjujen kiteisyys määrittää alpha-kierteisten kompleksien pakkautumissymmetrian. Lämpötilalla aikaansaatu faasitransitio on täydellinen ja palautuva. Julkaisuissa IV ja V on tutkittu epäsymmetristen tähtilohkopolymeerien ABC-, A2B- ja A2B2-arkkitehtuureita. Polypeptidiketjujen sauvamainen alpha-kierteinen konformaatio johtaa kaikissa arkkitehtuureissa lohkopolymeeritason lamellirakenteeseen sekä lisäksi ABC-arkkitehtuurissa hierarkiseen smektiseen rakenteeseen. Polymeerimolekyylin keskipisteestä haarautuvien lohkojen lukumäärä vaikuttaa nanorakenteen järjestyneisyyteen ja alpha-kierteiden pakkautumiseen. Polypeptidien sivuketjuja modifioimalla voidaan puolestaan vaikuttaa polypeptidilohkon konformaatioon, joka vaikuttaa oleellisesti molekyylien pakkautumiseen.

Julkaisun otsikon käännös	Polymeerien nanorakenteiden itsejärjestymisen ohjaaminen molekyyliarkkitehtuurilla ja polypeptidien konformaatioilla
Alkuperäiskieli	Englanti
Pätevyys	Tohtorintutkinto
Myöntävä instituutio	Aalto-yliopisto
Valvoja/neuvonantaja	Ikkala, Olli, Vastuuprofessori Ikkala, Olli, Ohjaaja
Kustantaja	Aalto University
Painoksen ISBN	978-952-60-4763-8
Sähköinen ISBN	978-952-60-4764-5
Tila	Julkaistu - 2012
OKM-julkaisutyyppi	G5 Artikkeliväitöskirja

Tutkimusalat

itsejärjestyminen
polypeptidi
lohkopolymeeri
surfaktantti
lipidi
konformaatio
supramolekyyli

Pääsy asiakirjaan

http://urn.fi/URN:ISBN:978-952-60-4764-5

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@phdthesis{5dded3614c6148b0af6c8bdcc68e8dd8,

title = "Self-assembled polymer nanostructures controlled by molecular architecture and polypeptide conformation",

abstract = "Supramolecular chemistry, block copolymer self-assembly and biopolymer conformations are powerful tools for controlling structure formation in the nanoscale. In this thesis, we have studied how self-assembly of polypeptide-based materials can be controlled in the bulk solid state by molecular architecture of surfactants, lipids and block copolymers and by polypeptide conformation. The effect of surfactant architecture on the conformation and self-assembly of homopolypeptide-surfactant complexes has been studied in Publications I and II. The branching of the surfactant influences the polypeptide conformation, self-assembly of the supramolecular comb-shaped complexes, crystallization of the alkyl tails and periodicity of organization in the material after precipitation from aqueous solution. Externally triggered conformational and structural transformations are accessible in the solid state. In addition, the brittle complexes can be plasticized by adding excess surfactants in organic solvent. The effect of lipid architecture on the self-assembly of homopolypeptide-lipid complexes has been studied in Publication III. The PEGylated triple-tail lipids include two alkyl tails and one polyethylene glycol tail. Saturated lipid alkyl tails are able to crystallize at room temperature, and polypeptide alpha-helices are arranged in an oblique lattice. Unsaturated tails remain amorphous, and a hexagonal cylindrical morphology is observed. This morphology is also achieved by melting of the crystalline alkyl tails, proving that crystallization of the alkyl side chains plays a significant role in determining the packing symmetry of alpha-helical complexes. The temperature-controlled order-order transition is full and reversible. In Publications IV and V, miktoarm star copolymers with ABC, A2B and A2B2 architectures have been studied. The rod-like packing of alpha-helical polypeptide arms leads to lamellar block copolymer morphologies in all of the architectures and, in addition, to a hierarchical smectic packing in the ABC miktoarm architecture. The number of arms influences the degree of organization and packing of the rigid alpha-helices. Polypeptide side chain modification, on the other hand, influences the polypeptide conformation which has a major effect on the packing of the molecules.",

keywords = "self-assembly, polypeptide, block copolymer, surfactant, lipid, conformation, supramolecule, itsej{\"a}rjestyminen, polypeptidi, lohkopolymeeri, surfaktantti, lipidi, konformaatio, supramolekyyli, self-assembly, polypeptide, block copolymer, surfactant, lipid, conformation, supramolecule",

author = "Susanna Junnila",

year = "2012",

language = "English",

isbn = "978-952-60-4763-8",

series = "Aalto University publication series DOCTORAL DISSERTATIONS",

publisher = "Aalto University",

number = "112",

address = "Finland",

school = "Aalto University",

}

TY - BOOK

T1 - Self-assembled polymer nanostructures controlled by molecular architecture and polypeptide conformation

AU - Junnila, Susanna

PY - 2012

Y1 - 2012

N2 - Supramolecular chemistry, block copolymer self-assembly and biopolymer conformations are powerful tools for controlling structure formation in the nanoscale. In this thesis, we have studied how self-assembly of polypeptide-based materials can be controlled in the bulk solid state by molecular architecture of surfactants, lipids and block copolymers and by polypeptide conformation. The effect of surfactant architecture on the conformation and self-assembly of homopolypeptide-surfactant complexes has been studied in Publications I and II. The branching of the surfactant influences the polypeptide conformation, self-assembly of the supramolecular comb-shaped complexes, crystallization of the alkyl tails and periodicity of organization in the material after precipitation from aqueous solution. Externally triggered conformational and structural transformations are accessible in the solid state. In addition, the brittle complexes can be plasticized by adding excess surfactants in organic solvent. The effect of lipid architecture on the self-assembly of homopolypeptide-lipid complexes has been studied in Publication III. The PEGylated triple-tail lipids include two alkyl tails and one polyethylene glycol tail. Saturated lipid alkyl tails are able to crystallize at room temperature, and polypeptide alpha-helices are arranged in an oblique lattice. Unsaturated tails remain amorphous, and a hexagonal cylindrical morphology is observed. This morphology is also achieved by melting of the crystalline alkyl tails, proving that crystallization of the alkyl side chains plays a significant role in determining the packing symmetry of alpha-helical complexes. The temperature-controlled order-order transition is full and reversible. In Publications IV and V, miktoarm star copolymers with ABC, A2B and A2B2 architectures have been studied. The rod-like packing of alpha-helical polypeptide arms leads to lamellar block copolymer morphologies in all of the architectures and, in addition, to a hierarchical smectic packing in the ABC miktoarm architecture. The number of arms influences the degree of organization and packing of the rigid alpha-helices. Polypeptide side chain modification, on the other hand, influences the polypeptide conformation which has a major effect on the packing of the molecules.

AB - Supramolecular chemistry, block copolymer self-assembly and biopolymer conformations are powerful tools for controlling structure formation in the nanoscale. In this thesis, we have studied how self-assembly of polypeptide-based materials can be controlled in the bulk solid state by molecular architecture of surfactants, lipids and block copolymers and by polypeptide conformation. The effect of surfactant architecture on the conformation and self-assembly of homopolypeptide-surfactant complexes has been studied in Publications I and II. The branching of the surfactant influences the polypeptide conformation, self-assembly of the supramolecular comb-shaped complexes, crystallization of the alkyl tails and periodicity of organization in the material after precipitation from aqueous solution. Externally triggered conformational and structural transformations are accessible in the solid state. In addition, the brittle complexes can be plasticized by adding excess surfactants in organic solvent. The effect of lipid architecture on the self-assembly of homopolypeptide-lipid complexes has been studied in Publication III. The PEGylated triple-tail lipids include two alkyl tails and one polyethylene glycol tail. Saturated lipid alkyl tails are able to crystallize at room temperature, and polypeptide alpha-helices are arranged in an oblique lattice. Unsaturated tails remain amorphous, and a hexagonal cylindrical morphology is observed. This morphology is also achieved by melting of the crystalline alkyl tails, proving that crystallization of the alkyl side chains plays a significant role in determining the packing symmetry of alpha-helical complexes. The temperature-controlled order-order transition is full and reversible. In Publications IV and V, miktoarm star copolymers with ABC, A2B and A2B2 architectures have been studied. The rod-like packing of alpha-helical polypeptide arms leads to lamellar block copolymer morphologies in all of the architectures and, in addition, to a hierarchical smectic packing in the ABC miktoarm architecture. The number of arms influences the degree of organization and packing of the rigid alpha-helices. Polypeptide side chain modification, on the other hand, influences the polypeptide conformation which has a major effect on the packing of the molecules.

KW - self-assembly

KW - polypeptide

KW - block copolymer

KW - surfactant

KW - lipid

KW - conformation

KW - supramolecule

KW - itsejärjestyminen

KW - polypeptidi

KW - lohkopolymeeri

KW - surfaktantti

KW - lipidi

KW - konformaatio

KW - supramolekyyli

KW - self-assembly

KW - polypeptide

KW - block copolymer

KW - surfactant

KW - lipid

KW - conformation

KW - supramolecule

M3 - Doctoral Thesis

SN - 978-952-60-4763-8

T3 - Aalto University publication series DOCTORAL DISSERTATIONS

PB - Aalto University

ER -

Self-assembled polymer nanostructures controlled by molecular architecture and polypeptide conformation

Abstrakti

Tutkimusalat

Pääsy asiakirjaan

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