Citation: Ting Yang, Fu-sheng Du, Zi-chen Li. Glucose-responsive Dynamic Covalent Hydrogels Based on PVA-b-PEO-b-PVA and Phenylboronic Acid Substituted PEO Crosslinker[J]. Acta Polymerica Sinica, ;2019, 50(5): 516-526. doi: 10.11777/j.issn1000-3304.2019.19017 shu

Glucose-responsive Dynamic Covalent Hydrogels Based on PVA-b-PEO-b-PVA and Phenylboronic Acid Substituted PEO Crosslinker

Beijing National Laboratory for Molecular Sciences, Key Laboratory of Polymer Chemistry and Physics of Ministry of Education, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871

Corresponding author: Zi-chen Li, zcli@pku.edu.cn
Received Date: 25 January 2019
Revised Date: 14 March 2019
Available Online: 11 April 2019

Boronic acid can form dynamic covalent boronic ester bonds with 1,2-diol or 1,3-diol moieties. This property has been used to prepare malleable and self-healing covalent polymer networks as well as glucose-responsive hydrogels. It remains a challenge to fabricate strong hydrogels with fast glucose-responsivity. Glucose-responsive dynamic covalent hydrogels were prepared by crosslinking poly(vinyl alcohol) (PVA) containing triblock copolymer and poly(ethylene oxide) (PEO) containing phenylboric acid. Specifically, we synthesized a new type of α,ω-phenylboronic acid substituted PEO crosslinker. The feature of the crosslinker is that amino-groups are introduced to the neighboring position of boronic acid, which will accelerate the boronic ester exchange. The gelation of this crosslinker with three PVA-b-PEO-b-PVA triblock copolymers at physiological pH was examined. Time-dependent dynamic storage and loss modulus of the hydrogels were monitored by rheological measurements. Formation of hydrogels turned out be very fast after mixing the crosslinker and triblock copolymer solutions. Stable dynamic covalent hydrogels were obtained after incubating the hydrogels for 12 h. The copolymer composition, PVA chain length, and content of crosslinker were found to greatly affect the hydrogel properties. Higher polymer concentration, longer PVA chains, and more PEO crosslinker endowed hydrogels with higher modulus. Gels with high yield stress were obtained by utilizing block copolymer with longer PVA segments or adding more crosslinker. Both pH and temperature affected the hydrogel properties. The formed hydrogels displayed higher modulus at pH = 7.4 than those at pH = 6.0, and the stability of the hydrogel could still be maintained at 37 °C. In addition, the hydrogels exhibited good structural recovery ability due to the covalent dynamic crosslinking. Finally, the hydrogels could load FITC-BSA, and the release profile of FITC-BSA was accelerated in the presence of glucose.
- Phenylboronic acid,
- Poly(ethylene oxide),
- Poly(vinyl alcohol),
- Hydrogel,
- Glucose-responsive
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