Blunt-End Driven Re-entrant Ordering in Quasi Two-Dimensional Dispersions of Spherical DNA Brushes

Ivany Romero-Sanchez, Ilian Pihlajamaa, Natasa Adžić, Laura E. Castellano, Emmanuel Stiakakis, Christos N. Likos (Korresp. Autor*in), Marco Laurati (Korresp. Autor*in)

Veröffentlichungen: Beitrag in FachzeitschriftArtikelPeer Reviewed

Abstract

We investigate the effects of crowding on the conformations and assembly of confined, highly charged, and thick polyelectrolyte brushes in the osmotic regime. Particle tracking experiments on increasingly dense suspensions of colloids coated with ultralong double-stranded DNA (dsDNA) fragments reveal nonmonotonic particle shrinking, aggregation, and re-entrant ordering. Theory and simulations show that aggregation and re-entrant ordering arise from the combined effect of shrinking, which is induced by the osmotic pressure exerted by the counterions absorbed in neighbor brushes and of a short-range attractive interaction competing with electrostatic repulsion. An unconventional mechanism gives origin to the short-range attraction: blunt-end interactions between stretched dsDNA fragments of neighboring brushes, which become sufficiently intense for dense and packed brushes. The attraction can be tuned by inducing free-end backfolding through the addition of monovalent salt. Our results show that base stacking is a mode parallel to hybridization to steer colloidal assembly in which attractions can be fine-tuned through salinity and, potentially, grafting density and temperature.
OriginalspracheEnglisch
Seiten (von - bis)2133–2146
Seitenumfang14
FachzeitschriftACS Nano
Jahrgang16
Ausgabenummer2
Frühes Online-Datum7 Feb. 2022
DOIs
PublikationsstatusVeröffentlicht - 22 Feb. 2022

ÖFOS 2012

  • 103015 Kondensierte Materie

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