Impact of Copolymer Architecture on Demicellization and Cargo Release via Head-to-Tail Depolymerization of Hydrophobic Blocks or Branches

Author:

Gioldasis Christos1,Gkamas Apostolos1ORCID,Vlahos Costas1ORCID

Affiliation:

1. Chemistry Department, University of Ioannina, 45110 Ioannina, Greece

Abstract

Utilizing molecular dynamics simulations, we explored the demicellization and cargo release dynamics of linear and miktoarm copolymers, featuring one, two, and three hydrophobic blocks or branches, each capable of head-to-tail depolymerization. Our findings revealed that, under stoichiometric trigger molecule concentrations, miktoarms with three branches exhibited consistently faster depolymerization rates than those with two branches and linear copolymers. Conversely, at constant trigger molecule concentrations, the depolymerization rates of copolymers exhibited more complex behaviors influenced by two opposing factors: the excess of trigger molecules, which increased with a decrease in the number of hydrophobic branches or blocks, and simultaneous head-to-tail depolymerization, which intensified with an increasing number of branches. Our study elucidates the intricate interplay between copolymer architecture, trigger molecule concentrations, and depolymerization dynamics, providing valuable insights for the rational design of amphiphilic copolymers with tunable demicellization and cargo release properties.

Publisher

MDPI AG

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