Cobaltocenium-Containing Methacrylate Homopolymers, Block Copolymers, and Heterobimetallic Polymers via RAFT Polymerization

Abstract

Cobaltocenium-containing methacrylate homopolymer, poly(2-(methacrylolyoxy)ethyl cobaltoceniumcarboxylate hexafluorophosphate) (PMAECoPF 6 ), was prepared by reversible addition−fragmentation chain transfer polymerization (RAFT). Using the homopolymer as a macroinitiator, three different diblock copolymers, including a novel heterobimetallic diblock copolymer with ferrocene units as the second block, were synthesized via chain extension. Kinetic studies showed that all chain extension followed a controlled/ living process under relatively lower conversion. The heterobimetallic diblock copolymer self-assembled into spherical micelles in selective solvents. The formation of aggregates depended on the location of the ferrocene block in the micelles. While the ferrocene units were susceptible to oxidation toward decomposition, the cobaltocenium moiety exhibited extraordinary stability to maintain its structure integrity.

Synthesis of amphiphilic block copolymers containing ferrocene–boronic acid and their micellization, redox-responsive properties and glucose sensing

“…The product was precipitated in cold water and then washed thrice with distilled water to obtained pure brownish solid. 1 …”

“…Poly-2-(methacrylolyoxy)ethyl ferrocenecarboxylate) (PMAEFc) was synthesized according to previously reported procedure [1]. MAEFc (2.00 g, 5.84 mmol), AIBN (0.47 mg, 0.0058 mmol) and DDMAT (10 mg, 0.0292 mmol) were dissolved in DMF (1.2 mL).…”

“…Kinetic study was performed by following the reported procedure [1]. For example, HEMA (800 mg, 2.34 mmol), AIBN (1.76 mg, 0.009 mmol) and DDMAT (8.36 mg, 0.035 mmol) were dissolved in DMF (1.2 mL).…”

“…The introduction of different functional groups into the polymer greatly enhances its practical applications in biodiagnosis, separation media and therapeutics [1][2][3]. The selection of monomers depends on their intended applications.…”

“…Among CRP techniques, reversible addition-fragmentation chain transfer (RAFT) polymerization is the most versatile technique and used for the synthesis of well-defined functional polymers with controlled molecular weight distributions and narrow PDI. Typically, RAFT offers the advantages of conventional free radical polymerization and requires milder reaction conditions than ionic polymerization [1,[14][15][16][17]. Polymers with boronic acid (BA) groups are versatile, especially for saccharide sensing applications.…”