Binary organocatalytic ring-opening polymerization (ROP) of N-Boc-1,4-oxazepan-7-one (OxP_Boc) is proposed as a versatile method to generate metal-free poly(amine-co-ester)s and the corresponding biodegradable polycationic homo/block (co)polymers. Optimization experiments with different organocatalysts, including 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), DBU/1-(3,5-bis(trifluoromethyl)phenyl)-3-cyclohexylthiourea (TU1), and phosphazene/thiourea, revealed that t-Bu-P₄/TU1 leads to a fast and controlled/living ROP with benzyl alcohol (BnOH) as an initiator and thus allows the formation of well-defined poly(amine-co-ester)s with high molecular mass (M_n,SEC up to 38.8 kg mol^–1) and narrow dispersity. Well-defined poly(N-Boc-1,4-oxazepan-7-one)-based diblock copolymers were also synthesized successfully via the controlled/living ROP, regardless of whether hydrophilic poly(ethylene glycol) (PEG) or hydrophobic polycaprolactone (PCL) was used as a macroinitiator. After treatment with trifluoroacetic acid, the corresponding water-soluble polycationic homopolymer, as well as the hydrophilic (PEG-based copolymer) and amphiphilic (PCL-based copolymer) polycationic diblock copolymers, was obtained. Dynamic light scattering in water and transmission electron microscopy analyses revealed that both polycationic copolymers self-assembled spontaneously to nanostructures; the hydrophilic block copolymer formed spherical nanoparticles, while the amphiphilic one formed rod-shaped nanoparticles.

中文翻译：

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N -Boc-1,4-oxazep​​an-7-one的二元有机催化开环聚合反应制得的聚胺共酯：合成，表征与自组装

N - _Boc -1,4-oxazep​​an-7-one（OxP _Boc）的二元有机催化开环聚合（ROP）被提出作为一种通用的方法来生成无金属的聚（胺-共酯）和相应的可生物降解的聚阳离子均聚物/嵌段（共）聚合物。不同有机催化剂的优化实验，包括1,8-二氮杂双环[5.4.0]十一碳-7-烯（DBU），1,5,7-三氮杂双环[4.4.0] dec-5-烯（TBD），DBU / 1 -（3,5-双（三氟甲基）苯基）-3-环己基硫脲和磷腈/硫脲显示t -Bu-P ₄ / TU1可导致苯甲醇（BnOH）快速且可控制/有效地存在ROP作为引发剂，并因此允许明确定义的聚的形成（胺共-酯）具有高分子量（M _n，SEC最高38.8 kg mol ^–1）并且分散性窄。定义明确的poly（N不管是使用亲水性聚乙二醇（PEG）还是疏水性聚己内酯（PCL），都可以通过受控/活性ROP成功合成基于-Boc-1,4-oxazep​​an-7-one的二嵌段共聚物。宏观引发剂。用三氟乙酸处理后，获得了相应的水溶性聚阳离子均聚物，以及亲水性（基于PEG的共聚物）和两亲性（基于PCL的共聚物）聚阳离子二嵌段共聚物。在水和透射电子显微镜分析中的动态光散射表明，两种聚阳离子共聚物均自发自组装成纳米结构。亲水性嵌段共聚物形成球形纳米颗粒，而两亲性则形成棒状纳米颗粒。