Convergent Approach to Boronic Acid Functionalized Polycarbonates: Accessing New Dynamic Material Platforms

Abstract

Polycarbonates are routinely utilized for diverse medicinal applications and are highly efficacious scaffolds for drug delivery and antimicrobial treatments. In order to provide for robust, dynamic platforms for biomedical applications, we have developed new routes for the incorporation of boronic acids into the polycarbonate backbone. These routes take advantage of straightforward postsynthesis modification of established polycarbonate backbones, enabling the preparation of a diverse array of boronic acid functionalized polycarbonates from readily accessible polycarbonates. In particular, this approach circumvents the need for de novo monomer synthesis, functional group incompatibilities, and deprotection steps that often limit other methods. This strategy has been demonstrated using a broad array of unprotected boronic acids to produce both neutral and cationic boronic acid functionalized polycarbonates.

Functional biodegradable polymers via ring-opening polymerization of monomers without protective groups

“…Polymers were additionally functionalized by quaternization with phosphines, the chloride in polymers from C32 was substituted with NaN 3 and subsequently clicked to various alkynes, 276 or functionalized with boronic acid derivatives. 277 Besides the use of a pentafluorophenyl ester MTC (C33) as a precursor for preparation of functionalized monomers (Scheme 22, route III), 234 C33 itself was polymerized to highly reactive PCs. Hedrick and coworkers proved post-modification with different amines 278,279 to use them e.g.…”

“…as stealth materials, 280 with persistent radicals, or with boronic acid derivatives. 277 They selfassembled them to nanoparticles or used them as MRI agents. 281 Liu and coworkers 282 reported a further active ester MTC monomer, functionalized with a NHS ester (5-methyl-5 0 -(succinimide-Noxycarbonyl)-1,3-dioxan-2-one, C34), which was copolymerized with caprolactone and the copolymers modified by aminolysis with ethylene diamine to yield hydrophilic amido-amine pendant chains.…”

Monoether-Tagged Biodegradable Polycarbonate Preventing Platelet Adhesion and Demonstrating Vascular Cell Adhesion: A Promising Material for Resorbable Vascular Grafts and Stents

“…Many PTMC-based biomaterials have recently been investigated for applications in a broad range of implantable and/or resorbable devices. Chemically functionalized PTMC analogues with different pendant groups are derived from their corresponding cyclic monomers, demonstrating a diverse alteration of physicochemical properties. − However, most of these analogues have been designed to be used as solutions, such as in drug/gene delivery, hydrogels, and antimicrobials. − In contrast, composites of PTMC and copolymers, including trimethylene carbonate (TMC), have been studied for bulk applications such as scaffolds for bone, cartilage, and nerve regeneration. − In addition, applications in blood vessels and as vascular stents are a targeted area of PTMC-based materials because the inherent flexible property of PTMC is well-suited for the required task. − However, as with other hydrophobic biodegradable polymers that require concomitant administration of anticoagulants and antiplatelets for applications in blood-contacting devices, blood compatibility, and in particular the ability to suppress platelet adhesion, is indispensable for the PTMC-based materials. We have previously reported that no synthetic biodegradable polymers possessing high antithrombotic properties have been developed …”

Post-polymerization functionalization of aliphatic polycarbonates using click chemistry

“…83 Due to the unique properties of boronic acid polymers, access to facile and well-defined boronic acid functional polycarbonates has been presented by utilizing 6-membered cyclic carbonate monomers and by taking advantage of post-polymerization modification. 84 Furthermore, a distinctive approach for post-polymerization via transesterification between pentafluorophenyl ester functional polycarbonates and different alcohols has been achieved under milder conditions to afford functional polycarbonates. 85 In a recent and topical publication, an amphiphilic sulfonated polycarbonate was synthesized which rapidly inactivates SARS-CoV-2.…”