Biocompatible Polymeric Analogues of DMSO Prepared by Atom Transfer Radical Polymerization

Abstract

The synthesis of a sulfoxide-based water-soluble polymer, poly(2-(methylsulfinyl)ethyl acrylate) (polyMSEA), a polymeric analogue of DMSO, by atom transfer radical polymerization (ATRP) is reported. Well-defined linear polymers were synthesized using relatively low amounts of copper catalyst (1000 or 100 ppm). Two types of star polymers were synthesized by either an “arm-first” approach or a “core-first” approach using a biodegradable β-cyclodextrin core. The glass transition temperatures of both the linear polymer (16 °C) and star polymer (32 °C) were determined by differential scanning calorimetry (DSC). The lower critical solution temperature (LCST) of poly(MSEA) was estimated to be ca. 140 °C by extrapolating the LCST of a series of copolymers with NIPAM. Cytotoxicity tests revealed that both the linear and star polymers have low toxicity, even at concentrations up to 3 mg/mL.

Oxidation‐Responsive Materials: Biological Rationale, State of the Art, Multiple Responsiveness, and Open Issues

“…Finally, it is worth mentioning that MetO materials are generally considered as non‐fouling, as Deming has demonstrated using copolypeptides with Met blocks in the stemness of neural progenitor cells, which fits with the exceptionally low toxicity of side chain sulfoxides obtained by Matyjaszewski and co‐workers …”

Nano‐Star‐Shaped Polymers for Drug Delivery Applications

“…ATRP may be used for both “arm‐first” and “core‐first” methods, depending on the choice of functional initiators, monomers, and most critically, the timing and sequence of addition of the comonomers . A caveat is that addition of the cross‐linker should only happen strictly before or after polymerization, otherwise, the reaction might result in random branching of polymers or random cross‐linking of gel networks .…”

Degradable cellulose‐based polymer brushes with controlled grafting densities

“…Subsequently, the generated ATRP initiation sites were used to graft methyl methacrylate and styrene. The bottlebrush copolymers were also prepared with variable grafting densities of poly( n ‐butyl acrylate) (PBA) as well as poly(2‐(methylsulfinyl)ethyl acrylate) side chains, using the LiCl/DMAc solvent system. Fractional precipitation of the prepared cellulose macroinitiators resulted in backbones of well‐defined lengths.…”