Department of Advanced Materials Science, Graduate School of Frontier Sciences, The University of Tokyo, 5-1-5 Kashiwanoha, Kashiwa 277-8561, Japan.
International Center for Materials Nanoarchitectonics (WPI-MANA), National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba 305-0044, Japan.
Int J Mol Sci. 2022 May 13;23(10):5454. doi: 10.3390/ijms23105454.
The simplicity of fullerenes as assembled components provides attractive opportunities for basic understanding in self-assembly research. We applied in situ reactive methods to the self-assembly process of C60 molecules with melamine/ethylenediamine components in solution, resulting in a novel type of fullerene assemblies, micron-sized two-dimensional, amorphous shape-regular objects, fullerene rosettes. ATR−FTIR spectra, XPS, and TGA results suggest that the melamine/ethylenediamine components strongly interact and/or are covalently linked with fullerenes in the fullerene rosettes. The broad peak for layer spacing in the XRD patterns of the fullerene rosettes corresponds roughly to the interdigitated fullerene bilayer or monolayer of modified fullerene molecules. The fullerene rosettes are made from the accumulation of bilayer/monolayer assemblies of hybridized fullerenes in low crystallinity. Prototype sensor systems were fabricated upon immobilization of the fullerene rosettes onto surfaces of a quartz crystal microbalance (QCM), and selective sensing of formic acid was demonstrated as preliminary results for social-demanded toxic material sensing. The QCM sensor with fullerene rosette is categorized as one of the large-response sensors among reported examples. In selectivity to formic acids against basic guests (formic acid/pyridine >30) or aromatic guests (formic acid/toluene >110), the fullerene rosette-based QCM sensor also showed superior performance.
富勒烯作为组装元件的简单性为自组装研究中的基础理解提供了有吸引力的机会。我们将原位反应方法应用于溶液中 C60 分子与三聚氰胺/乙二胺成分的自组装过程中,得到了一种新型的富勒烯组装体,即微米级二维、无定形形状规则的物体,富勒烯蔷薇花。ATR−FTIR 光谱、XPS 和 TGA 结果表明,三聚氰胺/乙二胺成分与富勒烯蔷薇花中的富勒烯强烈相互作用和/或发生共价键合。富勒烯蔷薇花的 XRD 图谱中层间距的宽峰大致对应于交错的富勒烯双层或改性富勒烯分子的单层。富勒烯蔷薇花是由杂交富勒烯的双层/单层组装体在低结晶度下积累而成的。在石英晶体微天平(QCM)表面上固定富勒烯蔷薇花后,构建了原型传感器系统,并初步展示了对甲酸的选择性传感,作为对社会所需有毒物质传感的示范。带有富勒烯蔷薇花的 QCM 传感器被归类为已报道的大响应传感器之一。在对甲酸(甲酸/吡啶>30)或芳香族客体(甲酸/甲苯>110)的选择性方面,基于富勒烯蔷薇花的 QCM 传感器也表现出优异的性能。