Numata Munenori, Asai Masayoshi, Kaneko Kenji, Bae Ah-Hyun, Hasegawa Teruaki, Sakurai Kazuo, Shinkai Seiji
Department of Chemistry and Biochemistry, Graduate School of Engineering, Kyushu University, Fukuoka 812-8581, Japan.
J Am Chem Soc. 2005 Apr 27;127(16):5875-84. doi: 10.1021/ja044168m.
We have found that single-chain schizophyllan and curdlan (s-SPG and s-curdlan, respectively) can dissolve as-grown and cut single-walled carbon nanotubes (ag-SWNTs and c-SWNTs, respectively) in aqueous solution. The vis-NIR spectra of the composites suggest that c-SWNTs are dissolved as a bundle, whereas ag-SWNTs exist as one or only a few pieces in the tubular hollow constructed by the helical structure inherent to these beta-1,3-glucans. EDX and CLSM measurements and TEM observation established that the distribution map of these polysaccharides overlaps well with the image of SWNTs, indicating that these two components form a composite. Very interestingly, when c-SWNTs were dissolved with the aid of s-SPG or s-curdlan in water, a clear periodical structure with inclined stripes, as detected by AFM, appeared on the fibrous composite surface. Because this periodical structure has never been recognized for the composites with other water-soluble polymers, one can regard that s-SPG or s-curdlan wraps c-SWNTs constructing a helically twined structure. High-resolution TEM observation of an ag-SWNTs/s-SPG composite gave a clearer image in that two s-SPG chains twine one ag-SWNT and the helical motif is right-handed. When this sample was subjected to the AFM measurement, the composite showed the 2-3 nm height. This height implies that one piece of ag-SWNT is included in the s-SPGs helical structure. As a summary, it has been established that beta-1,3-glucans such as s-SPG and s-curdlan not only dissolve SWNTs but also create a novel superstructure on the surface.
我们发现,单链裂褶多糖和凝胶多糖(分别为s-SPG和s-凝胶多糖)能够在水溶液中溶解生长态和切割后的单壁碳纳米管(分别为ag-SWNTs和c-SWNTs)。复合材料的可见-近红外光谱表明,c-SWNTs以束状形式溶解,而ag-SWNTs以一根或仅几根的形式存在于由这些β-1,3-葡聚糖固有的螺旋结构构建的管状中空结构中。能量色散X射线光谱(EDX)、共聚焦激光扫描显微镜(CLSM)测量以及透射电子显微镜(TEM)观察表明,这些多糖的分布图与SWNTs的图像很好地重叠,表明这两种成分形成了复合材料。非常有趣的是,当c-SWNTs借助s-SPG或s-凝胶多糖在水中溶解时,原子力显微镜(AFM)检测到在纤维状复合材料表面出现了具有倾斜条纹的清晰周期性结构。由于这种周期性结构在与其他水溶性聚合物形成的复合材料中从未被发现,因此可以认为s-SPG或s-凝胶多糖包裹着c-SWNTs构建了一种螺旋缠绕结构。对ag-SWNTs/s-SPG复合材料的高分辨率TEM观察得到了更清晰的图像,即两条s-SPG链缠绕一根ag-SWNT,且螺旋基序为右手螺旋。当对该样品进行AFM测量时,复合材料显示出2 - 3纳米的高度。这个高度意味着一根ag-SWNT包含在s-SPG的螺旋结构中。总之,已经确定s-SPG和s-凝胶多糖等β-1,3-葡聚糖不仅能溶解SWNTs,还能在其表面形成一种新型的超结构。