Aggregation Behavior and Antioxidant Properties of Amphiphilic Fullerene C60 Derivatives Cofunctionalized with Cationic and Nonionic Hydrophilic Groups
Aggregation Behavior and Antioxidant Properties of Amphiphilic Fullerene C60 Derivatives Cofunctionalized with Cationic and Nonionic Hydrophilic Groups
复制标题
阳离子和非离子亲水基团共官能化的两亲性富勒烯 C60 衍生物的聚集行为和抗氧化性能
DOI：
10.1021/acs.langmuir.8b03681
复制
发表时间：
2019-05-28
期刊：
影响因子：
3.9
通讯作者：
Hao, Jingcheng
中科院分区：
文献类型：
--
作者：
Chen, Mengjun;Zhou, Shengju;Hao, Jingcheng
富勒烯C-60的两亲性衍生物在超分子化学和生物医学领域具有广泛的应用前景。建立两亲C-60衍生物的分子结构、聚集行为和清除自由基等性质之间的关系是推动这些碳纳米材料真正应用的关键。在本工作中，通过中性前体的一步季胺化反应合成了六个单取代的C-60衍生物，这些C-60衍生物的端基为Percec单枝，末端为低聚(聚氧乙烷)(o-PEO)链(S)。C-60衍生物之间的主要区别在于O-PEO链(S)在Percec Monodendron中的数量和取代位置。含4-取代邻苯二甲酸乙二醇酯的衍生物在水中的溶解度仍然有限。其他具有两条或三条邻PEO链的衍生物在水中表现出更好的溶解性和丰富的聚集行为。研究发现，聚集体的形成既受o-PEO链的数目和取代方式的影响。典型的形貌包括纳米片、纳米线、囊泡、纳米管和纳米棒。虽然C-60衍生物的结构与传统表面活性剂不同，但用临界堆积参数理论也可以很好地解释它们的聚集行为。有趣的是，C-60衍生物清除羟基自由基(OH中心点-)的能力与其在水中的溶解度顺序一致，其中含有三个邻位PEO链的2，3，4-取代的化合物在0.15 mg·mL~(-1)浓度下获得了97.79%的猝灭效率(与0.11 mmoL·L~(-1)相似)。
Amphiphilic derivatives of fullerene C-60 are attractive from viewpoints of supramolecular chemistry and biomedicine. The establishment of relationships among the molecular structure, aggregation behavior and properties such as scavenging radicals of the amphiphilic C-60 derivatives is the key to push these carbon nanomaterials to real applications. In this work, six monosubstituted C-60 derivatives were synthesized by a one-step quaternization of their neutral precursors, which bear Percec monodendrons terminated with oligo(poly(ethylene oxide)) (o-PEO) chain(s). The main difference among the C-60 derivatives lies in the number and substituted position of the o-PEO chain(s) within the Percec monodendron. Derivative with a 4-substitution of the o-PEO chain still showed limited solubility in water. Other derivatives possessing two or three o-PEO chains exhibited much improved solubilities and rich aggregation behavior in water. It was found that the formation of aggregates is regulated both by the number and the substituted pattern of the o-PEO chains. Typical morphologies include nanosheets, nanowires, vesicles, nanotubes, and nanorods. Although the structures of the C-60 derivatives are different from those of traditional surfactants, their aggregation behavior can be also well explained by applying the theory of critical packing parameter. Interestingly, the capabilities of the C-60 derivatives to scavenge the hydroxyl radicals (OH center dot-) followed the same order of their solubility in water, where the compound bearing three o-PEO chains with a 2,3,4-substitution got the champion quenching efficiency of similar to 97.79% at a concentration of 0.15 mg-mL(-1) (similar to 0.11 mmol-L-1).