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Title: Supramolecular structures of self-assembled oligomers under confinement
Authors: Paturej, Jarosław
Koperwas, Kajetan
Tarnacka, Magdalena
Jurkiewicz, Karolina
Grelska, Joanna
Paluch, Marian
Kamiński, Kamil
Maksym, Paulina
Keywords: molecular origin of a prepeak; self-assembled oligomers; PMMS; poly(methylmercaptopropyl)- grafted-hexylmethacrylate; PMMS-g-HMA; poly(methylphenyl)siloxane; PMPS
Issue Date: 2022
Citation: "Soft Matter" (2022), art. no. 00343k
Abstract: We study the molecular origin of a prepeak (PP) observed at low q values in the structure factors of three oligomers in a bulk (poly(mercaptopropyl)methylsiloxane, PMMS, poly(methylmercaptopropyl)- grafted-hexylmethacrylate, PMMS-g-HMA, and poly(methylphenyl)siloxane, PMPS) in order to understand the lowering of the PP intensity detected for oligomers confined in cylindrical pores with low diameter. For this purpose, we use a combination of X-ray diffraction measurements and coarsegrained bead-spring molecular dynamics simulations. Our molecular modelling demonstrated that the planarity of the pendant groups triggers the self-association of oligomers into nanoaggregates. However, the formation of oligomeric nanodomains is not sufficient for building-up the PP. The latter requires spatial disturbance in the arrangement of the side groups of oligomers within clusters. Importantly, our numerical analysis revealed that the increasing degree of the confinement of oligomers limits their aggregation and consequently lowers the amplitude of the PP observed in the experimental data.
DOI: 10.1039/D2SM00343K
ISSN: 1744-6848
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