The glucose‐responsive behavior of a block copolymer featuring boronic acid and glycine

Abstract

This manuscript is dedicated to Professor Mitsuo Sawamoto's outstanding achievements in polymer chemistry and recognizes his recent retirement from 40 years of exceptional service to Kyoto University.ABSTRACT: Glucose responsive block copolymer featuring boronic acid as a glucose responsive moiety and glycine are reported. The first block is polymerized through reversible additionfragmentation chain transfer (RAFT) polymerization and the resulting poly(N-acryloylmorpholine) 113 (PAcM) is employed as a macro-chain transfer agent for chain extension with pentafluorophenyl acrylate (PFPA) yielding a well-defined PAcM 113 -block-poly (pentafluorophenyl acrylate) 84 (PPFPA). The PPFPA block is then reacted with functional (3-aminomethyl) phenyl boronic acid and glycine via post-polymerization modification and the structure of the block copolymer is confirmed by proton nuclear magnetic resonance (NMR), 19 F NMR, Fourier transform infrared, and gel permeation chromatography. By copolymerizing glycine into the polymer backbone, the relative pK a of the block copolymer is significantly lowered. The block copolymer can self-assemble into core-shell micelles in aqueous solution and disassemble in response to glucose at the physiological pH. Furthermore, the encapsulation and release of Nile red (NR) as a hydrophobic model drug is studied under the physiological pH. The influence of the glucose concentration on the NR release from the polymeric micelles is demonstrated. These results suggested that the glucose-responsive poly[(AcM) 113 -b-(3-(aminomethyl)phenylboronic acid hydrochloride(-co-Gly) 84 ] block copolymer has potential applications as a glucose-responsive polymer for insulin delivery.Additional supporting information may be found in the online version of this article.

Glucose and pH Dual‐Responsive Nanogels for Efficient Protein Delivery

“…For protein drug carriers, nanostructures formed by spontaneously self‐assembly in aqueous solution is preferred. Among them, boronate is a kind of chemical bond which can spontaneously form in aqueous solution by phenyl boronic acid and cis‐diol . In addition, the boronate is pH and glucose dual‐responsive.…”

Harnessing Endogenous Stimuli for Responsive Materials in Theranostics

“…The versatility of the PBA group means it can be easily incorporated into a variety of polymeric materials, including nanogels, polymer micelles, − vesicles, , and polymer ionic complexes . The PBA moiety has been used in materials for diverse applications, from glucose sensing and insulin delivery to cancer therapies, shape memory materials, and artificial muscles.…”

Pentafluorophenyl Groups as Remote Substituents in Ni(II) Polymerization Catalysis

“…The importance of perfluoraromatic molecules has grown over the decades and become subject of considerable interest in different chemical fields. − As a prominent representative, the pentafluorophenyl group is well known for its highly electron-withdrawing character due to the inductive effects of the fluorine atoms. , In contrast with saturated electron-withdrawing groups, the aromatic character enables a broad variety of tunable π interactions that differ from nonfluorine counterparts. − These unique properties allow for various applications as a crucial substituent, for example, in active esters for the synthesis of functional macromolecules. − The discovery of tris­(pentafluoro­phenyl)­borane − as a milestone of boron chemistry unlocked a broad variety of bond activation reactions , and was key in the development of the “frustrated Lewis pair” chemistry − or of weakly coordinating anions in catalysis. − …”