Selenol-Based Nucleophilic Reaction for the Preparation of Reactive Oxygen Species-Responsive Amphiphilic Diblock Copolymers

Abstract

Selenide-containing amphiphilic copolymers have shown significant potential for application in drug release systems. Herein, we present a methodology for the design of a reactive oxygen species-responsive amphiphilic diblock selenide-labeled copolymer. This copolymer with controlled molecular weight and narrow molecular weight distribution was prepared by sequential organoselenium-mediated reversible addition fragmentation chain transfer (Se-RAFT) polymerization and selenol-based nucleophilic reaction. Nuclear magnetic resonance (NMR) and matrix-assisted laser desorption/ionization time-to-flight (MALDI-TOF) techniques were used to characterize its structure. Its corresponding nanomicelles successfully formed through self-assembly from the copolymer itself. Such nanomicelles could rapidly disassemble under oxidative conditions due to the fragmentation of the Se–C bond. Therefore, this type of nanomicelle based on selenide-labeled amphiphilic copolymers potentially provides a new platform for drug delivery.

Synthesis and Applications of Organic Selenols

“…Aminolysis and Se-Michael addition reaction of selenol intermediates with poly(ethylene glycol) methyl ether methacrylate (PEGMA) enabled to accomplish suitable polymer chain end modifications for the development of new potential platform for drug delivery. [95] Notably, a variety of macromonomers could be synthesised through this approach, relying on the generation of selenol-ended polymers via Se-RAFT polymerisation-aminolysis sequence and further nucleophilic functionalisation. [96] Benzeneselenol, butaneselenol and diselenol 3 a (vide supra) were employed for the preparation of new linear and macrocyclic (diphosphine)Ni-bridged butterfly Fe/Se cluster complexes.…”

“…Sequential organoselenium‐mediated reversible addition fragmentation chain transfer polymerization (Se‐RAFT) was used to access diselenocarbonate polymer precursors. Aminolysis and Se‐Michael addition reaction of selenol intermediates with poly(ethylene glycol) methyl ether methacrylate (PEGMA) enabled to accomplish suitable polymer chain end modifications for the development of new potential platform for drug delivery [95] . Notably, a variety of macromonomers could be synthesised through this approach, relying on the generation of selenol‐ended polymers via Se‐RAFT polymerisation‐aminolysis sequence and further nucleophilic functionalisation [96]…”