Balima Maeva, Morfin Isabelle, Sudre Guillaume, Montembault Alexandra
Université Claude Bernard Lyon 1, INSA Lyon, Université Jean Monnet, CNRS, UMR 5223, Ingénierie des Matériaux Polymères, F-69622 Villeurbanne Cédex, France.
Univ Grenoble Alpes, CNRS, LiPhy, F-38000 Grenoble, France.
Carbohydr Polym. 2024 Sep 1;339:122265. doi: 10.1016/j.carbpol.2024.122265. Epub 2024 May 12.
In this work, we propose the formation of stretchable hydrogels at neutral pH from the physical crosslinking of chitosan (CS) and hyaluronic acid (HA) by polyelectrolyte complexation. A mixture of CS (M ≈ 600 kg/mol, degree of acetylation ≈ 50 %) solution and HA (M ≈ 77 kg/mol) solution was prepared with an excess of salts screening the electrostatic interactions CS/HA. In a controlled manner, the polyelectrolyte complexation was induced through the progressive dialysis of the salted polymer mixture against a sodium acetate solution (AcONa, 0.01 M) for 7 days. Depending on [HA], various materials were obtained: viscous solutions at [HA] = 0.75 % (w/v); hydrogels at [HA] = 1.50-2.24 % (w/v) with Young modulus of 14 kPa and stretchable to 200 %. The small angle X-ray scattering characterization of the hydrogels revealed a multiscale organization related to the conformation of the polymers induced by the physical interactions. The dialysis process with AcONa was optimized by adding a dialysis step against a zinc acetate solution containing Zn. The combination of polyelectrolyte complexation between CS/HA and metal complexation between Zn and the polymers led to an enhancement of the hydrogel stretchability up to 400 %.
在这项工作中，我们提出通过壳聚糖（CS）和透明质酸（HA）在中性pH下通过聚电解质络合进行物理交联来形成可拉伸水凝胶。制备了CS（M≈600 kg/mol，乙酰化度≈50%）溶液和HA（M≈77 kg/mol）溶液的混合物，其中过量的盐屏蔽了CS/HA的静电相互作用。以可控的方式，通过将加盐的聚合物混合物对醋酸钠溶液（AcONa，0.01 M）进行7天的逐步透析来诱导聚电解质络合。根据[HA]的不同，获得了各种材料：[HA]=0.75%（w/v）时为粘性溶液；[HA]=1.50 - 2.24%（w/v）时为水凝胶，杨氏模量为14 kPa，可拉伸至200%。水凝胶的小角X射线散射表征揭示了与物理相互作用诱导的聚合物构象相关联的多尺度结构。通过增加对含锌醋酸锌溶液的透析步骤，优化了用AcONa的透析过程。CS/HA之间的聚电解质络合与锌和聚合物之间的金属络合相结合，使水凝胶的拉伸性提高到400%。
