Mackiol Tino, Pascouau Chloé, Nagel Manuel, Bizmark Tamara M, Montesel Luca, Fischer-Schuch Jochen, Besenius Pol
Department of Chemistry, Johannes Gutenberg-University Mainz Duesbergweg 10-14 55128 Mainz Germany
Institut für Biotechnologie und Wirkstoff-Forschung gGmbH Hanns-Dieter-Hüsch-Weg 17 55128 Mainz Germany.
Polym Chem. 2025 Jul 3. doi: 10.1039/d5py00522a.
-Acylated poly(amino esters) (PAEs) synthesized organocatalytic ring-opening polymerization (ROP) offer potential for tailored, functional and degradable polymers. In this study, a universal monomer precursor toward -acylated-1,4-oxazepan-7-ones (OxP)s was synthesized using a three-step approach, allowing for the introduction of various functional groups. Two novel oxidation sensitive OxP monomers bearing a double bond and a sulfide group were designed, as well as two monomers with alkyl moieties. The organocatalytic ROP of the OxP monomers using 1,8-diazabicyclo[5.4.0]undec-7-en (DBU) and 1-(3,5-bis(trifluoromethyl)phenyl)-3-cyclohexyl thiourea (TU) as catalysts was investigated. Polymerizations were performed under ambient temperature, affording homopolymers with narrow dispersities ( = 1.09-1.13). As a proof of concept, a post-polymerization thiol-ene functionalization of the allyl functional PAE was performed photo-rheology experiments. Finally, the (bio)degradability of the -acylated poly(amino esters) was evaluated through a series of degradation studies under mild enzymatic catalysis, in neutral phosphate-buffered saline solution and under accelerated conditions.
通过有机催化开环聚合（ROP）合成的酰化聚（氨基酯）（PAE）为定制的、功能性和可降解聚合物提供了潜力。在本研究中，采用三步法合成了一种通用的朝向酰化-1,4-恶唑烷-7-酮（OxP）的单体前体，从而能够引入各种官能团。设计了两种带有双键和硫醚基团的新型氧化敏感型OxP单体，以及两种带有烷基部分的单体。研究了以1,8-二氮杂双环[5.4.0]十一碳-7-烯（DBU）和1-(3,5-双（三氟甲基）苯基)-3-环己基硫脲（TU）作为催化剂的OxP单体的有机催化ROP。聚合反应在室温下进行，得到了具有窄分散度（Đ = 1.09 - 1.13）的均聚物。作为概念验证，通过光流变学实验对烯丙基官能化PAE进行了聚合后硫醇-烯官能化。最后，通过在温和酶催化、中性磷酸盐缓冲盐溶液和加速条件下的一系列降解研究，评估了酰化聚（氨基酯）的（生物）降解性。
