School of Materials Science and Engineering, Nanchang University, Nanchang, Jiangxi 330031, PR China; Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031, PR China.
Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031, PR China.
Mater Sci Eng C Mater Biol Appl. 2020 Jan;106:110157. doi: 10.1016/j.msec.2019.110157. Epub 2019 Sep 3.
Surface modification of carbon nanotubes (CNTs) through controlled living polymerization has demonstrated to be a useful route for preparation of CNTs based polymer composites. However, surface oxidation of CNTs is often required to generate functional groups, which can be further utilized for immobilization of polymerization initiator and grafting polymers. The surface oxidation procedure is rather complex, high energy cost, low efficient and will destroy the structure of CNTs. Therefore, the development of simple and efficient strategies for preparation of CNTs based composites should be of great research interest and raised much attention recently. In this work, a novel mussel inspired strategy that combination of ATRP and ring-opening reaction has been developed for simultaneous preparation of glycosylated and PEGylated CNTs for the first time. CNTs were first coated with polydopamine (PDA) through self-polymerization of dopamine under alkaline aqueous solution. Then polymerization initiator was immobilized on CNT-PDA through simple esterification and amidation reaction to obtain CNT-PDA-Br. The PEGylated CNTs were synthesized through ATRP using CNT-PDA-Br as initiator and polyethylene glycol monoester acrylate and itaconic anhydride (IA) as the monomers. Finally, glucosamine was conjugated with IA via ring-opening reaction. The successful preparation of glycosylated and PEGylated CNTs (CNT-PDA-Poly(PEGMA-co-IA)-Glu) was confirmed by a number of characterization techniques in details. The obtained CNTs based composites showed improved aqueous dispersibility and desirable cytocompatibility, implying their biomedical application potential. As compared with the conventional covalent strategies, the mussel inspired method described in this work will not destroy the structure for introduction functional groups on the surface of CNTs, that can occur under rather mild experimental conditions, including room temperature, short reaction time and aqueous solution. On the other hand, the mussel inspired chemistry can also be used for surface modification of almost any materials regardless of their size, morphology and compositions. Therefore, we believe that the mussel inspired strategy should be a general method for fabrication of various polymer composites for different applications.
通过可控活性聚合对碳纳米管 (CNT) 进行表面改性已被证明是制备基于 CNT 的聚合物复合材料的有效途径。然而，为了产生官能团，通常需要对 CNT 进行表面氧化，这些官能团可以进一步用于固定聚合引发剂和接枝聚合物。表面氧化过程非常复杂，需要高能量成本，效率低，并且会破坏 CNT 的结构。因此，开发简单有效的策略来制备基于 CNT 的复合材料应该是一个非常有研究兴趣的课题，并引起了人们的广泛关注。在这项工作中，我们首次开发了一种新颖的贻贝启发策略，将 ATRP 和开环反应相结合，用于同时制备糖基化和 PEG 化的 CNT。首先，在碱性水溶液中，多巴胺自聚合将聚多巴胺 (PDA) 涂覆在 CNT 上。然后，通过简单的酯化和酰胺化反应将聚合引发剂固定在 CNT-PDA 上，得到 CNT-PDA-Br。通过 ATRP 使用 CNT-PDA-Br 作为引发剂，以聚乙二醇单酯丙烯酸酯和衣康酸酐 (IA) 作为单体合成了 PEG 化的 CNT。最后，通过开环反应将葡萄糖胺与 IA 偶联。通过多种表征技术详细证实了糖基化和 PEG 化 CNT (CNT-PDA-Poly(PEGMA-co-IA)-Glu) 的成功制备。所得到的基于 CNT 的复合材料表现出改善的水分散性和理想的细胞相容性，暗示了它们在生物医学中的应用潜力。与传统的共价策略相比，本文所述的贻贝启发方法不会在相对温和的实验条件下破坏 CNT 表面引入官能团的结构，这些条件包括室温、短反应时间和水溶液。另一方面，贻贝启发化学也可用于表面改性几乎任何材料，无论其尺寸、形态和组成如何。因此，我们相信贻贝启发策略应该是一种通用的方法，用于制备用于不同应用的各种聚合物复合材料。
