Supramolecular Additive-Initiated Controlled Atom Transfer Radical Polymerization of Zwitterionic Polymers on Ureido-pyrimidinone-Based Biomaterial Surfaces

Abstract

Surface-initiated controlled radical polymerization is a popular technique for the modification of biomaterials with, for example, antifouling polymers. Here, we report on the functionalization of a supramolecular biomaterial with zwitterionic poly(sulfobetaine methacrylate) via atom transfer radical polymerization from a macroinitiator additive, which is embedded in the hard phase of the ureido-pyrimidinone-based material. Poly(sulfobetaine methacrylate) was successfully polymerized from these surfaces, and the polymerized sulfobetaine content, with corresponding antifouling properties, depended on both the macroinitiator additive concentration and polymerization time. Furthermore, the polymerization from the macroinitiator additive was successfully translated to functional electrospun scaffolds, showing the potential for this functionalization strategy in supramolecular material systems.

Precise Control of Li+ Directed Transport via Electronegative Polymer Brushes on Polyolefin Separators for Dendrite‐Free Lithium Deposition

“…Afterward, the terminal Br atom on Celgard acted as the initial grafting point to induce SI‐ATRP reaction and achieve high‐density PPFPA polymer brushes. [ 39 ] The scan electron microscope (SEM) image of PPFPA‐g‐Celgard with uniform elemental distributions ( Figure a) shows almost no morphological change compared with those of Celgard and PDA‐Br@Celgard separators (Figure S6, Supporting Information). It was also reflected by the 3D surface topography in atomic force microscope (AFM) images (Figure 2b), with a slighter change in surface roughness in comparison with the Celgard separator (Figure S7, Supporting Information).…”

Supramolecular Polymer Brushes

“…Different ratios of both components allowed control over the initiator density and the morphology of the resulting polymeric material. 84 Supramolecular polymer brushes have also been used as biosensors. A recent example uses SI-ATRP from supramolecular host−guest based initiators for the electrochemical detection of cocaine.…”

“…These polymer brushes were grafted from substrates that were obtained by mixing a UPy-functionalized isobutyryl bromide derivative with a polycaprolactone polymer that was modified with one UPy unit at each chain end. Different ratios of both components allowed control over the initiator density and the morphology of the resulting polymeric material . Supramolecular polymer brushes have also been used as biosensors.…”

Biomedical Uses of Sulfobetaine-Based Zwitterionic Materials

“…79 SB coatings have been created on supramolecular materials prepared from ureido-pyrimidinone motifs through inclusion of a similar alkyl halide ATRP initiator. 80 In earlier work on graftfrom SB coatings, ATRP was instead initiated from peroxide surface groups obtained through ozonation, 81 which showed promising results in reducing adsorption of platelet-rich plasma. 82 When a hydroxyl group is present on the substrate, a ceric ion (in the form of Ce(NO 3 ) 4 ) can also be used as an initiator to achieve graft-from ATRP polymerization.…”