Synthesis of Dynamic-Covalent Shell Crosslinkable Core–Shell-Corona Nanoparticles with Boronic Ester Linkages: A Potential Carrier for Drug Delivery
Synthesis of Dynamic-Covalent Shell Crosslinkable Core–Shell-Corona Nanoparticles with Boronic Ester Linkages: A Potential Carrier for Drug Delivery
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具有硼酯键的动态共价壳可交联核-壳-电晕纳米颗粒的合成：药物输送的潜在载体
DOI：
10.1166/nnl.2017.2485
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发表时间：
2017-09
影响因子：
--
通讯作者：
Lijian Xu
中科院分区：
文献类型：
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作者：
Jianxiong Xu;Shaowen Xie;Haihu Tan;Na Li;Changfan Zhang;Lijian Xu
采用聚（N，N-二甲基丙烯酰胺）-b-聚（3-丙烯酰胺苯硼酸）三硫代碳酸盐（PDMA-b-PAPBA-TTC）和聚（N，N-二甲基丙烯酰胺）-b-聚（5-乙基-2,2-二甲基-1,3-二恶烷-5-基）丙烯酸甲酯三硫代碳酸盐（PDMA-b-EDMA-TTC）两种大型RAFT试剂，在苯乙烯（St）和苯乙烯（St）的分散可逆加成-破碎链转移（RAFT）聚合中合成了具有硼酯键的动态共价壳交联核-壳-电冕纳米粒子（DCSCNs）随后的pH刺激。聚合形成PDMA-b-PEDMA-PS/PDMA-b-PAPBA-PS多室三嵌段共聚物纳米粒子，其中PDMA嵌段形成电晕，PAPBA和PEDMA混合嵌段形成壳，疏溶剂PS嵌段形成核。由于PEDMA嵌段中的1,3-二氧六环在酸性条件下可水解成二醇基团，因此利用苯硼酸与二醇基团之间的硼酯交联的动态共价性制备dcscn。发现DCSCNs在水中具有ph响应性。因此，在pH值为3.8 ~ 7.0时，形成壳交联的核-壳-电晕纳米颗粒，而当pH值高于7.0或低于3.8时，则发生壳交联。这类DCSCNs在体内传递抗癌药物和基因载体方面具有潜在的应用前景。
Dynamic-covalent shell crosslinkable core–shell-corona nanoparticles (DCSCNs) with boronic ester linkages were synthesized employing two macro-RAFT agents of poly(N,N-dimethylacrylamide)-b-poly(3-acrylamidophenylboronic acid) trithiocarbonate (PDMA-b-PAPBA-TTC) and poly(N,N-dimethylacrylamide)-b-poly(5-Ethyl-2,2-dimethyl-1,3-dioxane-5-yl)methyl acrylate trithiocarbonate (PDMA-b-EDMA-TTC) in dispersion reversible addition-fragmentation chain transfer (RAFT) polymerization of styrene (St) and subsequent pH stimulation. Polymerization led to the formation of PDMA-b-PEDMA-PS/PDMA-b-PAPBA-PS multicompartment triblock copolymer nanoparticles, in which the PDMA block formed the corona, the mixed PAPBA and PEDMA blocks formed the shell, and the solvophobic PS block formed the core. Since the 1,3-dioxane ring in PEDMA block can be hydrolyzed into diol groups under acidic condition, DCSCNs were prepared due to the dynamic-covalent nature of the boronic ester cross-links between the phenylboronic acid and diol groups. It was found that the DCSCNs were pH-responsive in water. Consequently, under the pH value of 3.8 to 7.0, shell crosslinked core–shell-corona nanoparticles were formed, while when the pH value was above 7.0 or below 3.8, decrosslinking of the shell happened. This kind of DCSCNs had potential application as in vivo delivery of anticancer drugs and gene vectors.