Department of Chemistry and the Centre for Advanced Materials and Biomaterials Research , The University of Western Ontario , 1151 Richmond Street , London , Ontario , Canada N6A 5B7.
Department of Physics and Astronomy and the Centre for Advanced Materials and Biomaterials Research , The University of Western Ontario , 1151 Richmond Street , London , Ontario , Canada N6A 3K7.
Biomacromolecules. 2020 Jan 13;21(1):152-162. doi: 10.1021/acs.biomac.9b01115. Epub 2019 Sep 24.
Polyelectrolyte complexation, the combination of anionically and cationically charged polymers through ionic interactions, can be used to form hydrogel networks. These networks can be used to encapsulate and release cargo, but the release of cargo is typically rapid, occurring over a period of hours to a few days and they often exhibit weak, fluid-like mechanical properties. Here we report the preparation and study of polyelectrolyte complexes (PECs) from sodium hyaluronate (HA) and poly[tris(hydroxypropyl)(4-vinylbenzyl)phosphonium chloride], poly[triphenyl(4-vinylbenzyl)phosphonium chloride], poly[tri(-butyl)(4-vinylbenzyl)phosphonium chloride], or poly[triethyl(4-vinylbenzyl)phosphonium chloride]. The networks were compacted by ultracentrifugation, then their composition, swelling, rheological, and self-healing properties were studied. Their properties depended on the structure of the phosphonium polymer and the salt concentration, but in general, they exhibited predominantly gel-like behavior with relaxation times greater than 40 s and self-healing over 2-18 h. Anionic molecules, including fluorescein, diclofenac, and adenosine-5'-triphosphate, were encapsulated into the PECs with high loading capacities of up to 16 wt %. Fluorescein and diclofenac were slowly released over 60 days, which was attributed to a combination of hydrophobic and ionic interactions with the dense PEC network. The cytotoxicities of the polymers and their corresponding networks with HA to C2C12 mouse myoblast cells was investigated and found to depend on the structure of the polymer and the properties of the network. Overall, this work demonstrates the utility of polyphosphonium-HA networks for the loading and slow release of ionic drugs and that their physical and biological properties can be readily tuned according to the structure of the phosphonium polymer.
聚电解质络合，即通过离子相互作用将阴离子和阳离子带电聚合物结合在一起，可以用于形成水凝胶网络。这些网络可用于封装和释放货物，但货物的释放通常很快，在几小时到几天的时间内发生，而且它们通常表现出较弱的、类似流体的机械性能。在这里，我们报告了通过透明质酸钠 (HA) 和聚[三（羟丙基）（4-乙烯基苄基）氯化膦]、聚[三苯基（4-乙烯基苄基）氯化膦]、聚[三（-丁基）（4-乙烯基苄基）氯化膦]或聚[三乙基（4-乙烯基苄基）氯化膦]制备和研究聚电解质络合物（PECs）。通过超速离心使网络压实，然后研究它们的组成、溶胀、流变和自修复性能。它们的性质取决于磷聚合物的结构和盐浓度，但一般来说，它们表现出主要凝胶状行为，弛豫时间大于 40 s，自修复时间为 2-18 h。包括荧光素、双氯芬酸和腺苷-5'-三磷酸在内的阴离子分子被封装到 PECs 中，装载量高达 16 wt%。荧光素和双氯芬酸在 60 天内缓慢释放，这归因于与致密 PEC 网络的疏水和离子相互作用的结合。研究了聚合物及其与 HA 的相应网络对 C2C12 小鼠成肌细胞的细胞毒性，发现其取决于聚合物的结构和网络的性质。总的来说，这项工作证明了聚磷-HA 网络在负载和缓慢释放离子药物方面的实用性，并且可以根据磷聚合物的结构轻松调节其物理和生物性质。
