Molecularly Imprinted Polymer Nanomaterials and Nanocomposites: Atom‐Transfer Radical Polymerization with Acidic Monomers

Abstract

Molecularly imprinted polymers (MIPs) are artificial receptors which can be tailored to bind target molecules specifically. A new method, using photoinitiated atom-transfer radical polymerization (ATRP) for their synthesis as monoliths, thin films and nanoparticles is described. The synthesis takes place at room temperature and is compatible with acidic monomers, two major limitations for the use of ATRP with MIPs. The method has been validated with MIPs specific for the drugs testosterone and S-propranolol. This study considerably widens the range of functional monomers and thus molecular templates which can be used when MIPs are synthesized by ATRP, as well as the range of physical forms of these antibody mimics, in particular films and lithographic patterns, and their post-functionalization from living chainends.

Photomediated controlled radical polymerization

“…Synthesis of molecularly imprinted polymer (MIP) nanoparticles was reported, which recognized testosterone and β-propanolol, based on photoATRP processes using an iridium catalyst. [154] The MIPs were crosslinked polymer matrices formed in the presence of a template molecule. The template molecules were removed after the polymerization and left a cavity that preferentially binds the template molecule.…”

Novel pitaya-inspired well-defined core–shell nanospheres with ultrathin surface imprinted nanofilm from magnetic mesoporous nanosilica for highly efficient chloramphenicol removal

“…Therefore, selective nanoadsorbents are necessary to be developed to remove CAP from water environment, especially for low concentration residue. Molecularly imprinted polymers (MIPs) have been proposed to solve the problem of the poor selectivity for conventional adsorbents [17]. Especially, surface molecularly imprinted materials had the large adsorption capacity, fast removal kinetics, easy access to binding sites, high selectivity, and complete template extraction, which established imprinted recognition sites onto the surface or approximately surface of arbitrary solid matrices [18,19].…”

Organocatalyzed Photo‐Atom Transfer Radical Polymerization of Methacrylic Acid in Continuous Flow and Surface Grafting

“…Twelve years after the effect of light on ATRP was assessed for the first time, Hawker presented a photocontrolled ATRP reaction using an iridium‐based photoredox catalyst, showing the ability to use methacrylic acid (MAA) in a statistical copolymer with benzyl methacrylate. Haupt later built on that research by surface grafting polymethacrylic acid (PMAA) in a polymer network using ethylene glycol dimethacrylate as crosslinker toward the production of surface‐grafted molecularly imprinted polymers (MIPs) . With both groups obtaining satisfying results while using an excess of nonacidic monomers, success could be achieved possibly by avoiding end cyclization to a large extent.…”

“…Haupt later built on that research by surface grafting polymethacrylic acid (PMAA) in a polymer network using ethylene glycol dimethacrylate as crosslinker toward the production of surface-grafted molecularly imprinted polymers (MIPs). [18] With both groups obtaining satisfying results while using an excess of nonacidic monomers, success could be achieved possibly by avoiding end cyclization to a large extent. Yet, in their study, crosslinking polymerization (creating a network rather than individual brushes) was employed so that livingness of polymerizations could not be assessed.…”