Issue 1, 2020

Intramolecular micellization and nanopatterning in pH- and thermo-responsive molecular brushes

Abstract

Conformational transitions and nanoscale self-organization triggered in double pH- and thermo-responsive molecular brushes by varying environmental conditions are studied by means of analytical mean-field theory and numerical Scheutjens–Fleer self-consistent field modelling. Such molecular brushes are composed of multiple thermo-responsive side chains end-grafted onto the main chain (backbone) and are capable of acquiring ionic charges via reversible (de)protonation of the monomer units. Competition of long-range Coulomb repulsion with short-range solvophobic interactions leads to complex patterns in the intramolecular self-organization of molecular brushes. In particular, we observed formation of pearl necklace-like structures with multiple dense nanodomains formed by weakly ionized collapsed side chains and stabilized by a fraction protruding into the solution and strongly ionized ones. Such structures are thermodynamically stable in a certain parameter range and can be termed as intramolecular micelles. The stimuli-induced intramolecular nanopatterning occurs via a sequence of quasi-first order phase transitions corresponding to splitting/fusion of collapsed domains accompanied by jumps in the average degree of ionization and macromolecular dimensions. A re-entrant sequence of transitions is observed when the salt concentration is used as a control parameter. These theoretical predictions provide guidelines for design of smart unimolecular devices, for example multicompartment nanocarriers of active substances or nanosensors.

Graphical abstract: Intramolecular micellization and nanopatterning in pH- and thermo-responsive molecular brushes

Supplementary files

Article information

Article type
Paper
Submitted
30 Sep 2019
Accepted
15 Nov 2019
First published
18 Nov 2019

Soft Matter, 2020,16, 208-218

Intramolecular micellization and nanopatterning in pH- and thermo-responsive molecular brushes

V. M. Prokacheva, O. V. Rud, F. Uhlík and O. V. Borisov, Soft Matter, 2020, 16, 208 DOI: 10.1039/C9SM01961H

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