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

Author(s)
Ivany Romero-Sanchez, Ilian Pihlajamaa, Natasa Adžić, Laura E. Castellano, Emmanuel Stiakakis, Christos N. Likos, Marco Laurati
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.

Organisation(s)
Computational and Soft Matter Physics
External organisation(s)
University of Florence, Universidad de Guanajuato, Eindhoven University of Technology, Forschungszentrum Jülich
Journal
ACS Nano
Volume
16
Pages
2133–2146
No. of pages
14
ISSN
1936-0851
DOI
https://doi.org/10.1021/acsnano.1c07799
Publication date
2021
Peer reviewed
Yes
Austrian Fields of Science 2012
103015 Condensed matter
Keywords
ASJC Scopus subject areas
General Materials Science, General Engineering, General Physics and Astronomy
Portal url
https://ucrisportal.univie.ac.at/en/publications/eed47932-a5c0-4b76-956a-d8a12fd08c2e