Synthesis, Degradation, and Cytotoxicity of Multiblock Poly(ε-caprolactone urethane)s Containing Gemini Quaternary Ammonium Cationic Groups

Abstract

Novel cationic biodegradable multiblock poly(epsilon-caprolactone urethane)s that contain gemini quaternary ammonium side groups on the hard segments were developed. To obtain these polyurethanes, a new L-lysine-derivatized diamine containing gemini quaternary ammonium side groups (GA8) was first synthesized and characterized by Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance spectra (NMR), mass spectrometry (MS), and high-resolution mass spectra (HRMS). Then a series of gemini poly(epsilon-caprolactone urethane)s were designed and prepared using L-lysine ethyl ester diisocyanate (LDI), poly(epsilon-caprolactone) (PCL) diols, 1,4-butandiol (BDO), and GA8 and were terminated by methoxyl-poly(ethylene glycol) (m-PEG). The obtained polyurethanes were fully characterized by (1)H NMR, gel permeation chromatograph (GPC), differential scanning calorimetry (DSC), FTIR, and water contact angle (WCA) measurement. The gemini polyurethane shows a rapid rate of hydrolytic and enzymatic degradation, as demonstrated by weight loss and polarizing light microscopy (PLM) observations. In vitro cytotoxicity analysis suggests that both the polyurethanes and their degradation products do not show significant inhibition effect against fibroblasts. Our work provides a new way to synthesize nontoxic and amphiphilic multiblock polyurethanes with rapid degradation rate, and these new materials could be good candidates as biodegradable carriers for drug and gene delivery.