Jurko Lucija, Makuc Damjan, Štern Alja, Plavec Janez, Žegura Bojana, Bošković Perica, Kargl Rupert
Laboratory for Characterization and Processing of Polymers (LCPP), Faculty of Mechanical Engineering, University of Maribor, Smetanova Ulica 17, SI-2000 Maribor, Slovenia.
Slovenian NMR Centre, National Institute of Chemistry, Hajdrihova 19, SI-1000 Ljubljana, Slovenia.
ACS Appl Polym Mater. 2023 Jun 13;5(7):5270-5279. doi: 10.1021/acsapm.3c00691. eCollection 2023 Jul 14.
Cationic charge has been widely used to increase polymer adsorption and flocculation of dispersions or to provide antimicrobial activity. In this work, cationization of hydroxyethyl cellulose (HEC) and polyvinyl alcohol (PVA) was achieved by covalently coupling betaine hydrochloride and choline chloride to the polymer backbones through carbonyl diimidazole (CDI) activation. Two approaches for activation were investigated. CDI in excess was used to activate the polymers' hydroxyls followed by carbonate formation with choline chloride, or CDI was used to activate betaine hydrochloride, followed by ester formation with the polymers' hydroxyls. The first approach led to a more significant cross-linking of PVA, but not of HEC, and the second approach successfully formed ester bonds. Cationic, nitrogen-bearing materials with varying degrees of substitution were obtained in moderate to high yields. These materials were analyzed by Fourier transform infrared spectroscopy, nuclear magnetic resonance, polyelectrolyte titration, and kaolin flocculation. Their dose-dependent effect on the growth of and , and L929 mouse fibroblasts, was investigated. Significant differences were found between the choline- and betaine-containing polymers, and especially, the choline carbonate esters of HEC strongly inhibited the growth of in vitro but were also cytotoxic to fibroblasts. Fibroblast cytotoxicity was also observed for betaine esters of PVA but not for those of HEC. The materials could potentially be used as antimicrobial agents for instance by coating surfaces, but more investigations into the interaction between cells and polysaccharides are necessary to clarify why and how bacterial and human cells are inhibited or killed by these derivatives, especially those containing choline.
阳离子电荷已被广泛用于提高聚合物对分散体的吸附和絮凝能力，或提供抗菌活性。在这项工作中，通过羰基二咪唑（CDI）活化，将盐酸甜菜碱和氯化胆碱共价偶联到聚合物主链上，实现了羟乙基纤维素（HEC）和聚乙烯醇（PVA）的阳离子化。研究了两种活化方法。使用过量的CDI活化聚合物的羟基，然后与氯化胆碱形成碳酸酯；或者使用CDI活化盐酸甜菜碱，然后与聚合物的羟基形成酯。第一种方法导致PVA发生更显著的交联，但HEC没有，第二种方法成功形成了酯键。以中等到高产率获得了具有不同取代度的含氮阳离子材料。通过傅里叶变换红外光谱、核磁共振、聚电解质滴定和高岭土絮凝对这些材料进行了分析。研究了它们对大肠杆菌、金黄色葡萄球菌和L929小鼠成纤维细胞生长的剂量依赖性影响。发现含胆碱和含甜菜碱的聚合物之间存在显著差异，特别是，HEC的碳酸胆碱酯在体外强烈抑制大肠杆菌的生长，但对成纤维细胞也具有细胞毒性。PVA的甜菜碱酯也观察到对成纤维细胞具有细胞毒性，但HEC的甜菜碱酯没有。这些材料有可能用作抗菌剂，例如通过涂覆表面，但需要对细胞与多糖之间的相互作用进行更多研究，以阐明为什么以及这些衍生物，特别是含胆碱的衍生物如何抑制或杀死细菌和人类细胞。
