The National Creative Research Initiative Center for Intelligent Hybrids, Department of Chemical and Biological Engineering, Seoul National University, Seoul, 08826, Republic of Korea.
Department of Chemical Engineering, Hongik University, Seoul, 04066, Republic of Korea.
Macromol Rapid Commun. 2022 Jun;43(12):e2100618. doi: 10.1002/marc.202100618. Epub 2021 Nov 16.
ABC triblock copolymers composed of hydrophobic poly(ε-caprolactone) (PCL), zwitterionic poly(carboxybetaine methacrylate) midblock, and P(PEGMA-UPy ) containing supramolecular ureidopyrimidinone moieties, poly(ε-caprolactone-block-carboxybetaine methacrylate-block-[poly(ethylene glycol) methyl ether methacrylate-co-(α-methacryloyl-ω-(6-(3-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)ureido)hexylcarbamoyloxy)poly(ethylene glycol))]), are investigated to achieve multifunctional antifreeze hydrogels. The PCL and P(PEGMA-UPy ) blocks induce the formation of physical network with a hierarchical nanostructure comprising hydrophobic PCL cores and supramolecular junctions, respectively. The super-hydrophilic nature of polyzwitterion midblocks and the confinement effect of the supramolecular junctions enhance the antifreeze performance, where the majority of water molecules remains supercooled below sub-zero temperature. The hydrogel relaxation characterized over a wide range of timescale reveals that the facile dynamics of the supramolecular junctions lead to the self-healing and injectability of the hydrogels. In conjunction with the biodegradable PCL cores, the antifreeze and rheological characteristics of the triblock copolymer hydrogels provide significant potential to use for cryo-preservable and bio-injectable drug storage and delivery.
由疏水性聚（ε-己内酯）（PCL）、两性离子聚（羧酸甜菜碱甲基丙烯酸酯）中嵌段和含有超分子尿嘧啶二酮部分的 P（PEGMA-UPy）组成的 ABC 三嵌段共聚物，聚（ε-己内酯-嵌段-羧酸甜菜碱甲基丙烯酸酯-嵌段-[聚（乙二醇）甲基醚甲基丙烯酸酯-co-（α-甲基丙烯酰基-ω-（6-（3-（6-甲基-4-氧代-1,4-二氢嘧啶-2-基）尿嘧啶基）氨甲酰氧基）己基carbamoyloxy）聚（乙二醇））]），被研究以实现多功能抗冻水凝胶。PCL 和 P（PEGMA-UPy）嵌段分别诱导具有包含疏水性 PCL 核和超分子连接的分级纳米结构的物理网络的形成。聚两性离子中嵌段的超亲水性和超分子连接的限制效应增强了抗冻性能，其中大多数水分子在零下温度以下保持过冷。在宽时间尺度上表征的水凝胶弛豫表明，超分子连接的易于动态导致水凝胶的自修复和可注射性。结合可生物降解的 PCL 核，三嵌段共聚物水凝胶的抗冻和流变特性为可用于低温保存和生物可注射药物储存和递送的水凝胶提供了显著的潜力。
