Chinese Journal of Applied Chemistry ›› 2019, Vol. 36 ›› Issue (2): 146-154.DOI: 10.11944/j.issn.1000-0518.2019.02.180106

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Preparation and Properties of Dual Responsive Self-healing Bio-based Hydrogels

HUANG He,LI Yayu,GUO Ziyan,SHI Dongjian(),ZHANG Hongji,CHEN Mingqing   

  1. The Key Laboratory of Synthetic and Biological Colloids,Ministry of Education,School of Chemical and Material Engineering,Jiangnan University,Wuxi,Jiangsu 214122,China
  • Received:2018-04-10 Published:2019-02-01 Online:2019-01-31
  • Contact: SHI Dongjian
  • Supported by:
    Supported by the Postgraduate Research & Practice Innovation Program of Jiangsu Province(No.KYCX_1470)

Abstract:

Phenylboronic acid and derivatives that conjugate with diol units to form a reversible ester bond can be used to prepare self-healing and stimuli-responsive materials. Stimuli-responsive hydrogels based on phenylboronic acid have been reported to have excellent self-healing properties. However, in these examples, employed polymers are not fully degradable nor have low biocompatibility. Therefore, this study aims to prepare a bio-based hydrogel for potential biomedical applications. Poly(γ-glutamic acid-g-3-aminophenylboronic acid)(γ-PGA-g-APBA) was synthesized by grafting 3-aminophenylboronic acid(APBA) in the presence of 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide(EDC) and N-hydroxysuccinimide(NHS) as catalysts, and guar gum was modified by cationic etherification agent, 2,3-epoxypropyltrimethylammonium chloride(CHGTA). These two modified bio-polymers were characterized by Fourier transform infrared(FT-IR) spectroscopy, nuclear magnetic resonance(1H NMR), and ultraviolet-visible(UV-Vis) spectrophotometer, and were mixed to form hydrogels. Mechanical properties of the prepared hydrogels were characterized by the rheometer. The results show that(γ-PGA-g-APBA/CGG) hydrogels have self-healing and pH-responsive properties. The structure of the gels is damaged with large strain and reconstructed completely with small strain, indicating that the hydrogel have the self-healing property and the repeatability. With the increase of pH value from 7 to 9, the hydrogels are formed and their strengths increase with pH, due to the conversion of the trigonal boronic-ester bond to tetrahedral boronic-ester bond. In the presence of 4 g/L glucose, the formed gel dissociates and changes to sol, because of the competing reaction between glucose and guar gum with PBA group. Moreover, rheology test indicates the shear-thinning and injectable properties of the hydrogels. Thus, the bio-based(γ-PGA-g-APBA/CGG) hydrogels have the potential applications in sensors, medicine and tissue engineering.

Key words: self-healing, stimuli-responsive gel, polyglutamic acid, guar gum