Citation: Kang-mi Shen, Yue-jun Yao, Hong-hao Zheng, Chang-you Gao. Synthesis and Properties of Biodegradable Unsaturated Polyurethanes with Reductive Responsiveness[J]. Acta Polymerica Sinica, ;2019, 50(6): 623-632. doi: 10.11777/j.issn1000-3304.2019.18275 shu

Synthesis and Properties of Biodegradable Unsaturated Polyurethanes with Reductive Responsiveness

MOE Key Laboratory of Macromolecular Synthesis and Functionalization, Department of Polymer Science and Engineering, Zhejiang University, Hangzhou 310027

Corresponding author: Chang-you Gao, cygao@zju.edu.cn
Received Date: 25 December 2018
Revised Date: 19 January 2019
Available Online: 28 March 2019

A novel type of unsaturated polyurethanes (PPFU-SS) containing disulfide bonds was synthesized by using poly(propylene fumarate) as the soft segment and dimethyl L-cystinate dihydrochloride as the chain extender. In order to improve the mechanical properties, polycaprolactone diol (PCL) was copolymerized as the soft segment as well to obtain the novel unsaturated copolymerized polyurethanes (PPFU-CO-SS). Moreover, unsaturated polyurethane (PPFU-Lys) without disulfide bonds was synthesized and used as the control group. The chemical structures of PPFU-SS, PPFU-Lys, and PPFU-CO-SS were characterized by ¹H-NMR, IR, and Raman spectroscopy, revealing that there were many carbon-carbon double bonds and disulfide bonds in PPFU-SS and PPFU-CO-SS. The thermal properties of these three types of PPFU materials were characterized by DSC and TGA, which demonstrated their good thermal stability below 150 °C. The mechanical properties of these PPFUs were analyzed by universal mechanical testing, showing that the tensile strength of PPFU-CO-SS polymer was the highest with a value of 0.8 MPa. Therefore, the copolymerization with PCL has successfully improved the mechanical property of the novel unsaturated polyurethanes. The degradation of reduction-responsive PPFU-SS and PPFU-CO-SS was significantly accelerated in glutathione solution compared with that in phosphate buffered saline, whereas the degradation of PPFU-Lys had no obvious difference in these two types of solutions. Comparatively, PPFU-CO-SS showed a stronger hydrophobicity, water contact angle (93.5°) significantly larger than those of PPFU-SS (73.9°) and PPFU-Lys (74.4°). Culture of smooth muscle cells in vitro demonstrated that none of PPFU-SS, PPFU-Lys, and PPFU-CO-SS had obvious cytotoxicity. The cells cultured on the PPFU-SS and PPFU-Lys surfaces showed faster proliferation rates than those cultured on TCPS, whereas the cell proliferation rate on PPFU-CO-SS was comparable to that on TCPS. In conclusion, these results demonstrated that the reduction-responsive polyurethanes possess good mechanical strength, thermal stability, degradability in response to reductants, low cytotoxicity, and cell coMPatibility, and thus hold great potential in fields of drug delivery, tissue engineering, regenerative medicine, and therapy of diseases. Furthermore, the unsaturated and high active carbon-carbon double bonds can be used to graft desired molecules, enabling the diverse functionalization and thereby applications.
- Reduction-sensitive,
- Poly(propylene fumarate),
- Polyurethane,
- Biodegradable,
- Cell compatibility
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