Abstract Well-defined homopolymers of 2-deoxy-2-methacrylamido- d -glucose (MAG) were synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization using 4-cyanopentanoic acid-4-dithiobenzoate as chain transfer agent (CTA) and 2,2′-azobisisobutyronitrile (AIBN) as initiator. The effect of polymerization conditions such as molar ratio of RAFT agent to initiator and monomer to RAFT agent on conversion and molecular mass characteristics of prepared polymers was estimated. Kinetics of the polymerization under various reaction conditions was studied as a function of time and conversion using in situ 1H NMR spectroscopy. The living character of polymerization was demonstrated by carriyng out the further chain extension experiments using isolated PMAG-CTA as a macroRAFT agent. For that, the PMAG with higher molecular weight, as well as block copolymer with acrylic acid were synthesized and characterized using 1H NMR and SEC analysis. A novel amphiphilic copolymer representing a hybrid of glycopolymer and polypeptide fragments was synthesized using RAFT and ring-opening polymerization (ROP). In this case, dithiobenzoate end-group of PMAG was transformed via simultaneous reduction and in situ thiol capping reaction by cysteamine hydrochloride into amino functionality suitable for polymerization of N-carboxyanhydrides (NCA). Two block copolymers of MAG with poly- l -phenylalanine (PPhe) differed with hydrophobic block length were synthesized, characterized and used for preparation of particles via copolymer self-assembly. The hydrodynamic diameter, morphology and cytotoxicity of polymer particles based on PMAG-b-PPhe were evaluated using DLS, TEM and MTT-assay, respectively. Moreover, the encapsulation of model compound (fluorescent dye rhodamine 6G) inside PMAG-b-PPhe micelles, as well as its release, were also tested.

中文翻译：

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通过 RAFT 和 ROP 聚合合成和表征明确的聚（2-脱氧-2-甲基丙烯酰胺-D-葡萄糖）及其生物电势嵌段共聚物

摘要 以 4-氰基戊酸-4-二硫代苯甲酸酯为链转移剂 (CTA)，通过可逆加成-断裂链转移 (RAFT) 聚合合成了 2-脱氧-2-甲基丙烯酰胺-d-葡萄糖 (MAG) 的均聚物和2,2'-偶氮二异丁腈（AIBN）作为引发剂。评估了聚合条件如 RAFT 剂与引发剂和单体与 RAFT 剂的摩尔比对制备的聚合物的转化率和分子量特性的影响。使用原位 1 H NMR 光谱研究了在各种反应条件下的聚合动力学作为时间和转化率的函数。通过使用分离的 PMAG-CTA 作为macroRAFT 试剂进行进一步的扩链实验，证明了聚合的活性特性。为此，具有较高分子量的 PMAG，以及与丙烯酸的嵌段共聚物被合成并使用 1H NMR 和 SEC 分析表征。使用 RAFT 和开环聚合 (ROP) 合成了一种新型的两亲性共聚物，该共聚物代表了糖聚合物和多肽片段的混合体。在这种情况下，PMAG 的二硫代苯甲酸酯端基通过半胱胺盐酸盐的同时还原和原位硫醇封端反应转化为适合 N-羧酸酐 (NCA) 聚合的氨基官能团。合成了两种不同疏水嵌段长度的MAG与聚-l-苯丙氨酸(PPhe)的嵌段共聚物，表征并用于通过共聚物自组装制备颗粒。使用 DLS、TEM 和 MTT 测定法评估基于 PMAG-b-PPhe 的聚合物颗粒的流体动力学直径、形态和细胞毒性，分别。此外，还测试了模型化合物（荧光染料罗丹明 6G）在 PMAG-b-PPhe 胶束中的封装及其释放。