Noguchi Yuichi, Fujigaya Tsuyohiko, Niidome Yasuro, Nakashima Naotoshi
Department of Applied Chemistry, Graduate School of Engineering, Kyushu University, 744 Motooka, Fukuoka 819-0395 (Japan).
Chemistry. 2008;14(19):5966-73. doi: 10.1002/chem.200800070.
Two different single-walled carbon nanotubes (SWNTs), the so-called HiPco and CoMoCAT, have been individually dissolved in aqueous solutions of double-stranded DNA (dsDNA). Atomic force microscopy (AFM) revealed the fine structures of the dsDNA-wrapped SWNTs. The near-IR absorption and photoluminescence (PL) spectra of aqueous solutions of dsDNA-wrapped SWNTs were recorded and, in pure water, we observed only a single two-dimensional PL spot from (6,5) SWNTs for both HiPco and CoMoCAT. In sharp contrast, when Tris-EDTA (TE) buffer was used in place of pure water, the PL-mapping images of the solutions showed chirality indices of (6,5), (7,5), (7,6), (8,4), (9,4), and (10,2) for HiPco-SWNTs, and (6,5) and (7,5) for CoMoCAT-SWNTs. The first semiconducting bands in the near-IR absorption spectra of solutions of dsDNA-wrapped SWNTs are different. To explain the observed differences in the near-IR absorption and PL behavior we conducted several experiments and found that the near-IR optical properties of the SWNTs can be modulated by changing the pH of the solutions. The pH break-points for near-IR absorption bleaching and PL quenching are different and the phenomena are explained by differences in the numbers of holes generated on the SWNTs. These findings are important from both fundamental and applied viewpoints.
两种不同的单壁碳纳米管(SWNTs),即所谓的HiPco和CoMoCAT,已分别溶解于双链DNA(dsDNA)的水溶液中。原子力显微镜(AFM)揭示了dsDNA包裹的SWNTs的精细结构。记录了dsDNA包裹的SWNTs水溶液的近红外吸收光谱和光致发光(PL)光谱,在纯水中,我们观察到HiPco和CoMoCAT的(6,5)SWNTs均仅产生单个二维PL光斑。与之形成鲜明对比的是,当使用Tris-EDTA(TE)缓冲液代替纯水时,溶液的PL映射图像显示HiPco-SWNTs的手性指数为(6,5)、(7,5)、(7,6)、(8,4)、(9,4)和(10,2),而CoMoCAT-SWNTs的手性指数为(6,5)和(7,5)。dsDNA包裹的SWNTs溶液的近红外吸收光谱中的第一半导体带有所不同。为了解释在近红外吸收和PL行为中观察到的差异,我们进行了多项实验,发现SWNTs的近红外光学性质可通过改变溶液的pH值来调节。近红外吸收漂白和PL猝灭的pH断点不同,这些现象可通过SWNTs上产生的空穴数量差异来解释。从基础和应用的角度来看,这些发现都很重要。