Sulfoxide-Containing Polyacrylamides Prepared by PICAR ATRP for Biohybrid Materials

Abstract

Water-soluble and biocompatible polymers are of interest in biomedicine as the search for alternatives to PEG-based materials becomes more important. In this work, the synthesis of a new sulfoxide-containing monomer, 2-(methylsulfinyl)ethyl acrylamide (MSEAM), is reported. Well-defined polymers were prepared by photoinduced initiators for continuous activator regeneration atom transfer radical polymerization (PICAR ATRP). The polymerizations were performed in water under biologically relevant conditions in a small volume without degassing the reaction mixture. DNA-PMSEAM and protein-PMSEAM hybrids were also synthesized. The lower critical solution temperature (LCST) of PMSEAM was estimated to be approximately 170 °C by extrapolating the LCST for a series of copolymers with variable content of N-isopropylacrylamide. The cytotoxicity studies showed excellent biocompatibility of PMSEAM, even at concentrations up to 2.5 mg/mL. Furthermore, the MSEAM monomer exhibited relatively lower toxicity than similar (meth)acrylate-based monomers at comparable concentrations.

Open-air green-light-driven ATRP enabled by dual photoredox/copper catalysis

“…Anchoring polymers to proteins protects protein-polymer hybrids from denaturation, delays their clearance from the body, and reduces the immunological response toward them. 98 ATRP is very useful for the preparation of polymer-protein conjugates, 45,[99][100][101][102][103][104][105][106] but degassing prior to polymerization can trigger aggregation. 107 The dual EY/Cu system was applied in protein modications.…”

Fully Oxygen-Tolerant Visible-Light-Induced ATRP of Acrylates in Water: Toward Synthesis of Protein-Polymer Hybrids

“…ATRP at μL-scale is an attractive method for grafting from expensive initiators such as therapeutic proteins and DNA. − However, conventional ATRP at small volumes is challenging because rigorous deoxygenation can lead to solvent loss, affecting polymerization kinetics. In addition, inert gas sparging or freeze–pump–thaw degassing can cause a loss of enzymatic activity of protein-polymer hybrids …”

Antifouling polymers for nanomedicine and surfaces: recent advances

“…126 This could potentially pave the way for the use of sulfoxide-containing polymers in biohybrid materials. 127 3.3 PEG, poly(glycerol)s, and poly( propylene glycol) for surface coatings Just as PEG and its derivatives serve an important role as antifouling platforms in nanomedicine, these polymers have also been featured in antifouling coating technologies on surfaces, interfaces, and various nanomaterials in recent years. Although some recent studies reporting nonspecific interactions of PEGs with proteins in vivo as well as undesirable sequestration by the immune system, PEG's antifouling ability is still hailed as the gold standard in the pharmaceutical and biomedical industries.…”