Open AccessThermoreversible and Injectable ABC Polypeptoid Hydrogels: Controlling the Hydrogel Properties through Molecular Design
Author(s) -
Sunting Xuan,
Chang Uk Lee,
Cong Chen,
Andrew B. Doyle,
Yueheng Zhang,
Li Guo,
Vijay T. John,
Daniel J. Hayes,
Donghui Zhang
Publication year - 2016
Publication title -
chemistry of materials
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 3.741
H-Index - 375
eISSN - 1520-5002
pISSN - 0897-4756
DOI - 10.1021/acs.chemmater.5b03528
Subject(s) - self healing hydrogels , polymer , monomer , materials science , polymer chemistry , polymerization , chemical engineering , dynamic mechanical analysis , modulus , copolymer , chemistry , composite material , engineering
A series of ABC triblock copolypeptoids [i.e., poly( N -allyl glycine)- b -poly( N -methyl glycine)- b -poly( N -decyl glycine) (AMD)] with well-defined structure and varying composition have been synthesized by sequential primary amine-initiated ring-opening polymerization of the corresponding N-substituted N -carboxyanhydride monomers (Al-NCA, Me-NCA, and De-NCA). The ABC block copolypeptoids undergo sol-to-gel transitions with increasing temperature in water and biological media at low concentrations (2.5-10 wt %). The sol-gel transition is rapid and fully reversible with a narrow transition window, evidenced by the rheological measurements. The gelation temperature ( T gel ) and mechanical stiffness of the hydrogels are highly tunable: T gel in the 26.2-60.0 °C range, the storage modulus ( G ') and Young's modulus ( E ) in the 0.2-780 Pa and 0.5-2346 Pa range, respectively, at the physiological temperature (37 °C) can be readily accessed by controlling the block copolypeptoid composition and the polymer solution concentration. The hydrogel is injectable through a 24 gauge syringe needle and maintains their shape upon in contact with surfaces or water baths that are kept above the sol-gel transition temperature. The hydrogels exhibit minimal cytotoxicity toward human adipose derived stem cells (hASCs), evidenced from both alamarBlue and PicoGreen assays. Furthermore, quantitative PCR analysis revealed significant up-regulation of the Col2a1 gene and down-regulation of ANGPT1 gene, suggesting that the hydrogel exhibit biological activity in inducing chondrogenesis of hASCs. It was also demonstrated that the hydrogel can be used to quantitatively encapsulate water-soluble enzymes (e.g., horseradish peroxidase) by manipulating the sol-gel transition. The enzymatic activity of HRP remain unperturbed after encapsulation at 37 °C for up to 7 d, suggesting that the hydrogel does not adversely affect the enzyme structure and thereby the enzymatic activity. These results suggest that the polypeptoid hydrogel a promising synthetic platform for tissue engineering or protein storage applications.