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

Abstract

Novel cationic biodegradable multiblock poly(ε-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(ε-caprolactone urethane)s were designed and prepared using L-lysine ethyl ester diisocyanate (LDI), poly(ε-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.

Synthesis and antibacterial characterization of waterborne polyurethanes with gemini quaternary ammonium salt

“…And it is well known that primary amine group has much higher reactivity than hydroxyl group with the isocyanate group under mild conditions [26]. Hence, to obtain new waterborne polyurethane materials with good antibacterial properties, the lysine derivative of GQAS with two primary amine groups EG12 as chain extender was first designed (Scheme 1).…”

“…The strong bands at 1,105 cm -1 are overlapped by the C-O-C stretching vibration adsorption of ether groups in PTMG and PEG [30]. Characteristic peaks around 1,440 cm -1 of C-H deformation vibration in the methyl and methylene groups linked with N positive ions are also observed [26,31], which increase with the increase in GQAS contents. Again, these results demonstrate that these waterborne antibacterial polyurethanes have been successfully synthesized.…”

“…Nevertheless, T g, soft of these GWPU samples are much lower compared with those of normal PTMG-based polyurethanes (around -45°C) [32], and these T g, soft have only tiny changes that increase firstly and then reduce with the increase in GQAS contents in GWPU (Table 1). This is due to a strong polarity difference between soft segment and hard segment containing polar lysine and GQAS moieties, leading to high degree of microphase separation in these GWPU matrixes [26,35]. As a result, the amount of EG12 and lysine introduced in hard segments has no significant effect on aggregation state of hard and soft segments in GWPU samples.…”

Synthesis of PEG-PCL-based polyurethane nanoparticles by miniemulsion polymerization

“…24 hours was chosen based on previous literature, which has shown that the PU products of degradations are not cytotoxic at least up to 24 h [41] and [42]. From the results (Fig.…”

“…In this work, cell viability decrease when SDS and Tween 80 was used as surfactant for the experiments carried out at 5 mg/ml of PEG400-PU-PCL530 are in agreement with those reported by Mendes et al [27], who evaluated cell viability for 24 and 48 h, by MTT and neutral red assays (NR) in the presence of nanoparticles with diameters between 130 and 200 nm, and zeta potential between -6.8 and -19.5 mV, for these conditions, increasing nanoparticles concentration induced cell death for both cell types, suggesting that, a negatively influence on cell viability depend of the nanoparticle type and nanoparticles concentration in the dispersion. Ding et al (2009) [42], evaluated the cytotoxicity of multiblock poly(ε-caprolactone urethane) discs synthesized using Gemini Quaternary Ammonium as cationic surfactant by 3T3 cells. The polymers did not show significant cytotoxicity against fibroblasts.…”