Synthesis and characterization of thermoplastic poly(piperazine succinate) metallopolymers coordinated to ruthenium( III ) or iron( III )
Synthesis and characterization of thermoplastic poly(piperazine succinate) metallopolymers coordinated to ruthenium( III ) or iron( III )
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DOI：
10.1002/pol.20220583
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发表时间：
2022-11
影响因子：
3.4
通讯作者：
Jessica K. Schneider;Clarissa A. Ove;R. Pirlo;Justin C. Biffinger
中科院分区：
文献类型：
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作者：
Jessica K. Schneider;Clarissa A. Ove;R. Pirlo;Justin C. Biffinger
含金属聚合物代表了材料科学不断扩展的前沿。在用于产生金属聚合物的众多生物相容性配体中，含哌嗪的聚合物仍处于早期开发阶段，尽管哌嗪是药物设计和生物工程支架元件中的常见官能团。我们报告的第一个合成和表征（与NMR，IR，GPC，紫外可见光谱和热分析）的两个热塑性聚（烷基哌嗪琥珀酸酯）二醇与丙基或己基链桥的哌嗪。这些聚酯二醇然后用二异氰酸酯扩链以产生高度无定形的聚酯氨基甲酸酯热塑性聚合物。然后，Ru（III）或Fe（III）成功地与这些聚合物配位，其中约30%的本体金属聚合物产物变成250倍于含非金属聚合物的分子量。然而，Fe（III）和在较小程度上Ru（III）与这些聚哌嗪的配位加速了聚酯键在水中超过15天的水解。因此，这些新型聚合物是高度可生物降解的，其中Fe（III）金属聚合物比Ru（III）金属聚合物水解得更快，并且聚（哌嗪琥珀酸丙酯）聚合物比聚（哌嗪琥珀酸己酯）聚合物水解得更快。
Metal‐containing polymers represent an ever‐expanding frontier of material science. Of the numerous biocompatible ligands used to create a metallopolymer, piperazine‐containing polymers are still in their early development, even though piperazine is a common functional group in drug design and bioengineering scaffolding elements. We report the first synthesis and characterization (with NMR, IR, GPC, UV–vis spectroscopy, and thermal analysis) of two thermoplastic poly(alkyl piperazine succinate) diols with either propyl or hexyl alkane chains bridging the piperazines. These polyester diols were then chain extended with hexamethylene diisocyanate to create highly amorphous polyester urethane thermoplastic polymers. Ru(III) or Fe(III) was then successfully coordinated with these polymers, with approximately 30% of the bulk metallopolymer product becoming 250x the molecular weight of the non‐metal containing polymers. However, coordination of Fe(III), and to a lesser extent Ru(III), to these polypiperazines accelerated the hydrolysis of the polyester linkage in water over 15 days. Thus, these novel polymers are highly biodegradable with Fe(III) metallopolymers hydrolyzing faster than Ru(III) metallopolymers and poly(propyl piperazine succinate) polymers hydrolyzing faster than poly(hexyl piperazine succinate) polymers.