Amphiphilic/fluorous random copolymers as a new class of non-cytotoxic polymeric materials for protein conjugation

Abstract

Herein, amphiphilic/fluorous random copolymers bearing poly(ethylene glycol) (PEG) chains and perfluorinated alkane pendants were developed as novel non-cytotoxic polymers for protein conjugation. Three kinds of random copolymers with different initiating terminals (carboxylic acid, pyridyl disulfide, N-hydroxysuccinimide ester) were prepared by reversible addition-fragmentation chain transfer (RAFT) copolymerization of a PEG methyl ether methacrylate and a perfluorinated alkane methacrylate with corresponding functional chain transfer agents. All of the polymers were soluble in water to form nanostructures with perfluorinated compartments via fluorous interaction: large aggregates from the intermolecular multi-chain association and compact unimer micelles from the intramolecular single-chain folding. Such a PEGylated and perfluorinated random copolymer was non-cytotoxic to NIH 3T3 mouse embryonic fibroblast cells and human umbilical vein endothelial cells (HUVECs). Additionally, a random copolymer with a pyridyl disulfide terminal was also successfully conjugated with a thiolated lysozyme.

Molecular Dynamics of Amphiphilic Random Copolymers in the Bulk: A 1H and 19F NMR Relaxometry Study

“…Nuclear magnetic resonance (NMR) spectroscopy and NMR relaxometry are extremely powerful in assessing the phase and dynamic properties of polymeric systems . Recently, 1 H and 19 F NMR experiments were used to obtain information on the state of hydrophilic and hydrophobic side chains of amphiphilic poly(methacrylate) copolymers forming self‐folded structures and larger multichain micelles in water solution . In this work, we exploited the measurement and analysis of 1 H and 19 F spin–spin (T 2 ) and spin–lattice (T 1 ) nuclear relaxation times at variable copolymer composition and temperature for obtaining detailed information on the motions of the polymer backbone and the chemically different PEGMA and FA side chains over a wide frequency window, from tens of kilohertz to hundreds of megahertz .…”

Prolate and Temperature‐Responsive Self‐Assemblies of Amphiphilic Random Copolymers with Perfluoroalkyl and Polyoxyethylene Side Chains in Solution

“…Typical precursors of the hydrophilic component of single‐chain nanoassemblies have been reported to be either ionic monomers, such as 2‐acrylamido‐2‐methylpropanesulfonate, or non‐ionic monomers, such as poly(ethylene glycol) methyl ether methacrylate (PEGMA) or acrylamide (PEGAAm) . Random copolymers based on the latter type of monomers have the advantage to be soluble in both water and organic solvents and to be thermally responsive in water solution, due to the occurrence of a lower critical solution temperature‐type (LCST) transition .…”

Hyperbranched polytriazine grafted reduced graphene oxide and its application

“…All solution concentrations are 3 mg/L. The results showed that HBP‐RGO formed a stable colloidal dispersion in these solvents, and no precipitation was observed even after 15 days, which implied that the HBP‐RGO is amphipathic …”