Cui Yang, Zhang Mei, Du Fu-Sheng, Li Zi-Chen
Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Polymer Chemistry and Physics of Ministry of Education, Department of Polymer Science and Engineering, College of Chemistry and Molecular Engineering, Center for Soft Matter Science and Engineering, Peking University, Beijing 100871, China.
ACS Macro Lett. 2017 Jan 17;6(1):11-15. doi: 10.1021/acsmacrolett.6b00833. Epub 2016 Dec 14.
We report the straightforward synthesis of two types of HO-cleavable poly(ester-amide)s ( and ) via the Passerini multicomponent polymerization (P-MCP) of 4-formylbenzeneboronic acid pinacol ester with 1,6-diisocyanohexane and 1,6-hexanedioic acid or a polyethylene glycol (PEG) dicarboxylic acid. The HO-cleavable phenylboronic acid ester was integrated into the polymer backbone by the in situ formed benzyl ester bond. GPC and H NMR confirmed the complete HO-triggered degradation of these polymers in aqueous medium by a mechanism of sequential oxidation of phenylboronic acid ester and self-immolative elimination. Compared with the hydrophobic polymer , the PEG-based water-soluble polymer degraded much faster even at a lower HO concentration. Cytocompatible nanoparticles of polymer loaded with fluorescent Nile red were fabricated, and controlled release of Nile red in response to HO was achieved, thus, demonstrating the utility of these polymers as potential HO-responsive delivery vehicles.
我们报道了通过4-甲酰基苯硼酸频哪醇酯与1,6-二异氰基己烷和1,6-己二酸或聚乙二醇（PEG）二羧酸的Passerini多组分聚合（P-MCP）直接合成两种类型的可被HO裂解的聚（酯-酰胺）（ 和 ）。可被HO裂解的苯基硼酸酯通过原位形成的苄酯键整合到聚合物主链中。凝胶渗透色谱（GPC）和核磁共振氢谱（H NMR）证实了这些聚合物在水性介质中通过苯基硼酸酯的顺序氧化和自牺牲消除机制完全由HO引发降解。与疏水性聚合物 相比，基于PEG的水溶性聚合物 即使在较低的HO浓度下也降解得更快。制备了负载荧光尼罗红的聚合物 的细胞相容性纳米颗粒，并实现了尼罗红对HO的响应性控释，因此，证明了这些聚合物作为潜在的HO响应性递送载体的实用性。
