Yuen Alexander Y, Lopez-Martinez Elena, Gomez-Bengoa Enrique, Cortajarena Aitziber L, Aguirresarobe Robert H, Bossion Amaury, Mecerreyes David, Hedrick James L, Yang Yi Yan, Sardon Haritz
POLYMAT, University of the Basque Country UPV/EHU, Joxe Mari Korta Center, Avenida Tolosa 72, 20018 Donostia-San Sebastian, Spain.
CIC BiomaGUNE, Parque Tecnológico de San Sebastián, Paseo Miramón 182, Donostia-San Sebastián 20014, Spain.
ACS Biomater Sci Eng. 2017 Aug 14;3(8):1567-1575. doi: 10.1021/acsbiomaterials.7b00335. Epub 2017 Jul 18.
Polymers exhibiting both antimicrobial and biodegradable properties are of great interest for next generation materials in healthcare. Among those, cationic polycarbonates are one of the most promising classes of materials because of their biodegradability, low toxicity, and biocompatibility. They are typically prepared by a chemical postmodification after the polymer has been synthesized. The main problem with the latter is the challenges of ensuring and verifying complete quaternization within the polymer structure. Herein, we report the first example of synthesizing and polymerizing charged aliphatic cyclic carbonates with three different alkane pendant groups (-methyl, -butyl, and -hexyl) by ring-opening polymerization (ROP). These charged eight-membered cyclic carbonates displayed extraordinary reactivity and were even polymerizable in polar solvents (e.g., DMSO) and in catalyst free conditions that are generally unobtainable for other ring opening polymerization processes. A computational study was carried out and the findings were in agreement with the experimental data in regards to the dramatic increase in reactivity of the charged monomer over their neutral analogs. Furthermore, a series of hydrogels were prepared using the different charged eight-membered cyclic carbonates, and we found it to have a significant impact on the hydrogels' ability to swell and degrade in water. Finally, the hydrogels demonstrated antibacterial activity against (Gram-negative) and (Gram-positive). These materials could be ideal candidates for biologically relevant applications where cationic structure is required.
具有抗菌和可生物降解特性的聚合物对于医疗保健领域的下一代材料具有重大意义。其中，阳离子聚碳酸酯因其生物可降解性、低毒性和生物相容性，成为最具潜力的材料类别之一。它们通常在聚合物合成后通过化学后修饰制备。后者的主要问题在于确保并验证聚合物结构内完全季铵化所面临的挑战。在此，我们报告了首例通过开环聚合（ROP）合成并聚合带有三种不同烷烃侧基（-甲基、-丁基和-己基）的带电脂肪族环状碳酸酯的实例。这些带电的八元环状碳酸酯表现出非凡的反应活性，甚至可在极性溶剂（如二甲基亚砜）中以及无催化剂条件下聚合，而这对于其他开环聚合过程通常是无法实现的。我们进行了一项计算研究，结果表明带电单体相对于其中性类似物反应活性显著增加，这与实验数据一致。此外，我们使用不同的带电八元环状碳酸酯制备了一系列水凝胶，发现这对水凝胶在水中的溶胀和降解能力有显著影响。最后，这些水凝胶对（革兰氏阴性）和（革兰氏阳性）表现出抗菌活性。对于需要阳离子结构的生物相关应用而言，这些材料可能是理想的候选者。
