Peng Xiaobin, Komatsu Naoki, Kimura Takahide, Osuka Atsuhiro
Department of Chemistry, Shiga University of Medical Science, Seta, Otsu 520-2192, Japan.
ACS Nano. 2008 Oct 28;2(10):2045-50. doi: 10.1021/nn800462s.
Since structural control of single-walled carbon nanotubes (SWNTs) leads to control of their physical properties, isolation and synthesis of specific (n,m) structures of SWNTs have been extensively investigated in view of their technological applications. In this context, we developed a novel method for separating SWNTs through molecular recognition with chiral gable-type diporphyrins designated as "nanotweezers". The method allowed us to obtain optically active SWNTs, namely, the chiral SWNTs enriched in either left- or right-handed helical form, for the first time. In this paper, we describe prominent optical enrichment of (7,5)-SWNTs through preferential extraction with chiral 3,6-carbazolylene-bridged nanotweezers as well as simultaneous enrichment of the abundance of (7,5)- and (8,4)-SWNTs. The (n,m) enrichment through this extraction is considered to result from the diameter differentiation of the nanotweezers, suggested by the complex structures in the theoretical calculations. That is, carbazolylene-bridged nanotweezers encapsulate a SWNT deeply enough to recognize the diameter of (7,5)-SWNTs. The deep contact is considered to realize the discrimination of the small diameter difference even less than 0.10 nm. This is a significant progress toward the separation of single species of SWNTs consisting of single (n,m) structure with one helicity.
由于单壁碳纳米管(SWNTs)的结构控制会导致其物理性质的控制,鉴于其技术应用,SWNTs特定(n,m)结构的分离和合成已得到广泛研究。在此背景下,我们开发了一种通过与称为“纳米镊子”的手性山墙型双卟啉进行分子识别来分离SWNTs的新方法。该方法首次使我们能够获得光学活性的SWNTs,即富含左手或右手螺旋形式的手性SWNTs。在本文中,我们描述了通过用手性3,6-咔唑亚基桥连的纳米镊子进行优先萃取,(7,5)-SWNTs显著的光学富集以及(7,5)-和(8,4)-SWNTs丰度的同时富集。理论计算中的复杂结构表明,通过这种萃取实现的(n,m)富集被认为是由于纳米镊子的直径差异所致。也就是说,咔唑亚基桥连的纳米镊子对SWNT的包封深度足以识别(7,5)-SWNTs的直径。这种深度接触被认为能够实现对小于0.10 nm的小直径差异的区分。这是朝着分离由单一(n,m)结构和一种螺旋度组成的单种SWNTs迈出的重要一步。