Poly(d-glucose carbonate) Block Copolymers: A Platform for Natural Product-Based Nanomaterials with Solvothermatic Characteristics

Abstract

A natural product-based polymer platform, having the characteristics of being derived from renewable materials and capable of breaking down, ultimately, into natural byproducts, has been prepared through the ring-opening polymerization (ROP) of a glucose-based bicyclic carbonate monomer. ROP was carried out via chain extension of a polyphosphoester (PPE) macroinitiator in the presence of 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) organocatalyst to afford the PPE-b-poly(D-glucose carbonate) (PDGC) block copolymer. This new copolymer represents a functional architecture that can be rapidly transformed through thiol-yne reactions along the PPE segment into a diverse variety of amphiphilic polymers, which interestingly display stimuli-sensitive phase behavior in the form of a lower critical solution temperature (LCST). Below the LCST, they undergo self-assembly to form spherical core-shell nanostructures that display a poorly defined core-shell morphology. It is expected that hydrophobic patches are exposed within the micellar corona, reminiscent of the surface complexity of proteins, making these materials of interest for triggered and reversible assembly disassembly processes.

A Synthetic Bioinspired Carbohydrate Polymer with Mucoadhesive Properties

“…Alternatively, purely synthetic routes to such polymers are equally challenging as many of the desirable chemical characteristics of polysaccharides for biological applications (pyranose backbone, numerous hydroxyl functionalities, defined stereochemistry) necessitate rigorous and lengthy synthesis to prepare even oligosaccharides (<10 repeating units) . Consequently, efforts are ongoing to develop carbohydrate‐inspired polymers with non O ‐glycosidic linkages such as amide, carbonate, and phosphodiester linkages. These novel materials, however, fail to recapitulate all of the key physicochemical and biointerfacial properties of polysaccharides.…”

“…These novel materials, however, fail to recapitulate all of the key physicochemical and biointerfacial properties of polysaccharides. Indeed, previously reported carbohydrate‐inspired polymers largely suffer from poor aqueous solubility to complete insolubility, a lack of deprotected functional groups important for biological interaction (e.g., hydroxyls, amines, phosphates, carboxylates), and/or rapid degradation in acidic or basic pH . Moreover, the rigid pyranose ring backbone absent in some carbohydrate‐mimic and glyco‐polymers plays an essential role in polymer structure and resulting macroscale properties .…”

Stimuli‐Responsive Phosphorus‐Based Polymers

“…An alternative, facile post‐polymerization method for polyphosphoesters was presented by Wooley and co‐workers[14a] who presented an alkyne functionalized polyphosphoester facilitating functionalization via classical click chemistry methods such as azide–alkyne Huisgen cycloaddition and thiol‐yne addition. The latter has also been used to prepare thermoresponsive polymers, for example poly(d‐glucose carbonate) block copolymers with polyphosphoesters which undergo self‐assembly to form spherical core–shell nanostructures in an LCST driven response (Figureà).…”

Holistic Assessment of Covalently Labeled Core–Shell Polymeric Nanoparticles with Fluorescent Contrast Agents for Theranostic Applications

“…1–3 Recent development of such platforms has shifted from the use of non-degradable polymeric materials towards biodegradable polymer components, 2, 4–6 including poly(glucose carbonates), 7–10 polyphosphoesters 11–13 and poly(lactic acid). 14–16 However, with this shift comes an intrinsic complexity to the preparation, characterization and utilization of degradable materials that must be considered with rigorous experimental investigation.…”