Micelle Forming Linear-Dendritic Block Copolymers: A Theoretical Comparison between Random Hyperbranched and Precise Dendrimer Polymer Architectures

TL;DR

This study compares micelle structures formed by hyperbranched and dendritic block copolymers, demonstrating that hyperbranched copolymers produce more stable, functionalizable, and drug-encapsulating micelles, with advantages increasing with polydispersity.

Contribution

It provides a theoretical comparison showing hyperbranched copolymers outperform dendritic ones in stability, drug loading, and functionalization potential.

Findings

LHBC micelles are more stable than LDBC micelles.

LHBC micelles have a lower critical micelle concentration.

LHBC micelles accommodate larger drug payloads.

Abstract

Hyperbranched block copolymers offer a simpler and more efficient synthesis route compared to more traditional dendritic systems, while still providing exceptional control over surface functionality and self-assembly. This makes them ideal candidates for engineering nanoparticles with tailored properties for applications such as drug delivery and sensing. Here we use self-consistent field calculations to compare the micelle structures formed by copolymers with a polydisperse hyperbranched (LHBC), monodisperse dendritic (LDBC), and linear solvophilic blocks. Representative LHBC structures were generated by molecular dynamics simulations mimicking the slow-monomer addition protocol. We find that LHBC micelles are more stable, have a lower critical micelle concentration, and are better at accommodating larger drug payloads than LDBC micelles, and these properties further improve with increasing polydispersity. LHBC micelles also offer more terminal ends for functionalization than LDBC micelles for LDBCs with up to four branching generations, with the number of terminal ends being surprisingly independent of the LHBC polydispersity. Our findings highlight the superiority of LHBC micelles in flexibility and performance over LDBC micelles.