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Synthesis of pH-cleavable poly(trimethylene carbonate)-based block copolymers via ROP and RAFT polymerization†
Polymer Chemistry ( IF 4.1 ) Pub Date : 2018-05-24 00:00:00 , DOI: 10.1039/c8py00606g Jingjiang Sun 1, 2, 3, 4 , Stefan Fransen 1, 2, 3, 4 , Xiaoqian Yu 1, 2, 3, 4 , Dirk Kuckling 1, 2, 3, 4
Polymer Chemistry ( IF 4.1 ) Pub Date : 2018-05-24 00:00:00 , DOI: 10.1039/c8py00606g Jingjiang Sun 1, 2, 3, 4 , Stefan Fransen 1, 2, 3, 4 , Xiaoqian Yu 1, 2, 3, 4 , Dirk Kuckling 1, 2, 3, 4
Affiliation
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In this work, poly(dimethylacrylamide)-b-poly(trimethylene carbonate) (PDMAAm-b-PTMC) block copolymers containing a pH-sensitive imine linkage were successfully synthesized by combination of ring-opening polymerization (ROP) and reversible addition–fragmentation chain transfer (RAFT) polymerization. A variety of vanillin terminated PTMC block copolymers were prepared by ROP of trimethylene carbonate (TMC) initiated by modified vanillin in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) as an organo-catalyst. The analysis of the resultant homopolymers by 1H NMR spectroscopy, size exclusion chromatography (SEC) and ESI-ToF masspectrometry (ESI-ToF-MS) revealed the excellent control of molar masses (Mn up to 14 000 g mol−1), dispersities (ĐM < 1.15) and end groups. The PTMC homopolymer was subsequently end-capped with an amino functionalized RAFT-agent leading to a macroinitiator containing imine group. Using this macroinitiator, PDMAAm-b-PTMC block copolymers with various molar masses were successfully prepared. In aqueous solution at pH 7.4, micelles could be formed by self-assembly of the amphiphilic block copolymer using a dialysis method. The hydrodynamic diameter (Dh) of the micelles was 76.3 ± 2.4 nm with a polydispersity index (PDI) of 0.179 ± 0.002. Under weak acidic conditions (pH 6.0), the hydrophilic PDMAAm block could be cleaved from micelles by hydrolysis of the imine linkage, while PTMC nanoparticles formed in situ with an average size of 149.8 ± 4.5 nm (PDI = 0.287 ± 0.007). Based on our strategy, these pH-cleavable PTMC-based amphiphilic block copolymers will expand the range of biodegradable synthetic polymers available for potential biomedical applications, such as controlled drug and gene delivery.
中文翻译：
通过ROP和RAFT聚合 合成pH可裂解的聚碳酸三亚甲基酯基嵌段共聚物†
在这项工作中，通过开环聚合（ROP）和可逆加成-断裂结合，成功合成了具有pH敏感亚胺键的聚（二甲基丙烯酰胺）-b-聚碳酸三亚甲基酯（PDMAAm- b- PTMC）嵌段共聚物。链转移（RAFT）聚合。在1,8-二氮杂双环[5.4.0]十一碳-7-烯（DBU）作为有机催化剂的存在下，通过改性香草醛引发的碳酸亚丙酯（TMC）的ROP制备了多种香草醛封端的PTMC嵌段共聚物。通过1 H NMR光谱，尺寸排阻色谱（SEC）和ESI-ToF质谱（ESI-ToF-MS）对所得均聚物进行分析，结果显示，摩尔质量（M n多达14000克摩尔-1），分散度（Đ中号<1.15）和端基。PTMC均聚物随后用氨基官能化的RAFT-试剂封端，得到含有亚胺基的大分子引发剂。使用这种大分子引发剂，PDMAAm- b成功制备各种摩尔质量-PTMC嵌段共聚物。在pH 7.4的水溶液中，通过渗析法可通过两亲嵌段共聚物的自组装形成胶束。流体动力直径（D h）的胶束为76.3±2.4 nm，多分散指数（PDI）为0.179±0.002。在弱酸性条件下（pH 6.0），可通过亚胺键的水解将亲水性PDMAAm嵌段从微团上裂解下来，而PTMC纳米颗粒原位形成，平均尺寸为149.8±4.5 nm（PDI = 0.287±0.007）。根据我们的策略，这些基于pH值可裂解的PTMC的两亲嵌段共聚物将扩大可生物降解的合成聚合物的范围，这些聚合物可用于潜在的生物医学应用，例如受控药物和基因传递。
更新日期：2018-05-24
中文翻译：
通过ROP和RAFT聚合 合成pH可裂解的聚碳酸三亚甲基酯基嵌段共聚物†
在这项工作中，通过开环聚合（ROP）和可逆加成-断裂结合，成功合成了具有pH敏感亚胺键的聚（二甲基丙烯酰胺）-b-聚碳酸三亚甲基酯（PDMAAm- b- PTMC）嵌段共聚物。链转移（RAFT）聚合。在1,8-二氮杂双环[5.4.0]十一碳-7-烯（DBU）作为有机催化剂的存在下，通过改性香草醛引发的碳酸亚丙酯（TMC）的ROP制备了多种香草醛封端的PTMC嵌段共聚物。通过1 H NMR光谱，尺寸排阻色谱（SEC）和ESI-ToF质谱（ESI-ToF-MS）对所得均聚物进行分析，结果显示，摩尔质量（M n多达14000克摩尔-1），分散度（Đ中号<1.15）和端基。PTMC均聚物随后用氨基官能化的RAFT-试剂封端，得到含有亚胺基的大分子引发剂。使用这种大分子引发剂，PDMAAm- b成功制备各种摩尔质量-PTMC嵌段共聚物。在pH 7.4的水溶液中，通过渗析法可通过两亲嵌段共聚物的自组装形成胶束。流体动力直径（D h）的胶束为76.3±2.4 nm，多分散指数（PDI）为0.179±0.002。在弱酸性条件下（pH 6.0），可通过亚胺键的水解将亲水性PDMAAm嵌段从微团上裂解下来，而PTMC纳米颗粒原位形成，平均尺寸为149.8±4.5 nm（PDI = 0.287±0.007）。根据我们的策略，这些基于pH值可裂解的PTMC的两亲嵌段共聚物将扩大可生物降解的合成聚合物的范围，这些聚合物可用于潜在的生物医学应用，例如受控药物和基因传递。
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