School of Materials Science and Engineering, Tianjin Key Laboratory of Composite and Functional Materials, Tianjin University, Tianjin, 300350, China.
School of Pharmacy, Health Science Center, Xi'an Jiaotong University, Xi'an, 710061, China.
Adv Mater. 2021 Apr;33(16):e2008395. doi: 10.1002/adma.202008395. Epub 2021 Mar 18.
The intermolecular H-bonding density heavily influences the gelation and rheological behavior of hydrogen-bonded supramolecular polymer hydrogels, thus offering a delicate pathway to tailor their physicochemical properties for meeting a specific biomedical application. Herein, one methylene spacer between two amides in the side chain of N-acryloyl glycinamide (NAGA) is introduced to generate a variant monomer, N-acryloyl alaninamide (NAAA). Polymerization of NAAA in aqueous solution affords an unprecedented ultrasoft and highly swollen supramolecular polymer hydrogel due to weakened H-bonds caused by an extra methylene spacer, which is verified by variable-temperature Fourier transform infrared (FTIR) spectroscopy and simulation calculation. Intriguingly, poly(N-acryloyl alaninamide) (PNAAA) hydrogel can be tuned to form a transient network with a self-fused and excellent antifouling capability that results from the weakened dual amide H-bonding interactions and enhanced water-amide H-bonding interactions. This self-fused PNAAA hydrogel can completely inhibit postoperative abdominal adhesion and recurrent adhesion after adhesiolysis in vivo. This transient hydrogel network allows for its disintegration and excretion from the body. The molecular mechanism studies reveal the signal pathway of PNAAA hydrogel in inhibiting inflammatory response and regulating fibrinolytic system balance. This self-fused, antifouling ultrasoft supramolecular hydrogel is promising as a barrier biomaterial for completely preventing postoperative tissue adhesion.
分子间氢键密度强烈影响氢键超分子聚合物水凝胶的凝胶化和流变行为，从而为调整其物理化学性质以满足特定的生物医学应用提供了一种精细的途径。在此，在 N-丙烯酰基甘氨酸酰胺（NAGA）侧链中的酰胺之间引入一个亚甲基间隔基，生成变体单体 N-丙烯酰基丙氨酸酰胺（NAAA）。NAAA 在水溶液中的聚合由于额外的亚甲基间隔基导致氢键减弱，从而得到了前所未有的超软和高溶胀的超分子聚合物水凝胶，这通过变温傅里叶变换红外（FTIR）光谱和模拟计算得到了验证。有趣的是，聚（N-丙烯酰基丙氨酸酰胺）（PNAAA）水凝胶可以通过减弱的双重酰胺氢键相互作用和增强的水-酰胺氢键相互作用，调谐形成具有自融合和出色抗污染能力的瞬变网络。这种自融合的 PNAAA 水凝胶可以完全抑制体内手术后的腹部粘连和粘连松解后的复发性粘连。这种瞬态水凝胶网络允许其从体内分解和排泄。分子机制研究揭示了 PNAAA 水凝胶在抑制炎症反应和调节纤维蛋白溶解系统平衡方面的信号通路。这种自融合、抗污染的超软超分子水凝胶有望成为一种完全防止术后组织粘连的屏障生物材料。
