Department of Chemical and Materials Engineering, University of Alberta , Edmonton, Alberta T6G 2G6, Canada.
Department of Chemistry, Centennial Centre for Interdisciplinary Science, University of Alberta , Edmonton, Alberta T6G 2G6, Canada.
Biomacromolecules. 2018 Feb 12;19(2):596-605. doi: 10.1021/acs.biomac.7b01679. Epub 2018 Jan 27.
Dynamic hydrogels based on arylboronic esters have been considered as ideal platforms for biomedical applications given their self-healing and injectable characteristics. However, there still exist some critical issues that need to be addressed or improved, including hydrogel biocompatibility, physiological usability, and tunability of mechanical properties. Here, two kinds of phospholipid bioinspired MPC copolymers, one is zwitterionic copolymer (PMB) containing a fixed 15 mol % of benzoxaborole (pK ≈ 7.2) groups and the other is zwitterionic glycopolymers (PMG) with varied ratios of sugar groups (20%, 50%, 80%), were synthesized respectively via one-pot facile reversible addition-fragmentation chain transfer (RAFT) polymerization. PMBG hydrogels were formed spontaneously after mixing 10 wt % of PMB and PMG copolymer solutions because of dynamic benzoxaborole-sugar interactions. The mechanical properties of nine hydrogels (3 × 3) with different sugar contents and pHs (7.4, 8.4, 9.4) were carefully studied by rheological measurements, and hydrogels with higher sugar content and higher pH were found to have higher strength. Moreover, similar to other arylboronic ester-based hydrogels, PMBG hydrogels possessed not only self-healing and injectable properties but also pH/sugar responsiveness. Additionally, in vitro cytotoxicity tests of gel extracts on both normal and cancer cells further confirmed the excellent biocompatibility of the hydrogels, which should be ascribed to the biomimetic nature of phosphorylcholine (PC) and sugar residues of the copolymers. Consequently, the zwitterionic dynamic hydrogels provide promising future for diverse biomedical applications.
基于芳基硼酸酯的动态水凝胶因其自修复和可注射的特性而被认为是生物医学应用的理想平台。然而，仍然存在一些需要解决或改进的关键问题，包括水凝胶的生物相容性、生理可用性和机械性能的可调节性。在这里，我们合成了两种磷脂仿生 MPC 共聚物，一种是含有固定 15 mol %苯并恶唑硼酸酯（pK ≈ 7.2）基团的两性离子共聚物（PMB），另一种是具有不同糖基比例（20%、50%、80%）的两性离子糖基聚合物（PMG），分别通过一锅简便的可逆加成-断裂链转移（RAFT）聚合来合成。PMB 和 PMG 共聚物溶液以 10 wt %混合后可自发形成 PMBG 水凝胶，这是由于动态苯并恶唑-糖相互作用。通过流变学测量仔细研究了具有不同糖含量和 pH 值（7.4、8.4、9.4）的九种水凝胶（3 × 3）的力学性能，发现具有较高糖含量和较高 pH 值的水凝胶具有更高的强度。此外，与其他基于芳基硼酸酯的水凝胶类似，PMBG 水凝胶不仅具有自修复和可注射的特性，还具有 pH/糖响应性。此外，凝胶提取物对正常细胞和癌细胞的体外细胞毒性测试进一步证实了水凝胶的优异生物相容性，这应归因于共聚物中磷酰胆碱（PC）和糖残基的仿生性质。因此，两性离子动态水凝胶为各种生物医学应用提供了广阔的前景。
