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Selection of carbon nanotubes with specific chiralities using helical assemblies of flavin mononucleotide

Nature Nanotechnology volume 3, pages 356–362 (2008)Cite this article

Abstract

The chirality of single-walled carbon nanotubes affects many of their physical and electronic properties. Current production methods result in nanotubes of mixed chiralities, so facile extraction of specific chiralities of single-walled carbon nanotubes is an important step in their effective utilization. Here we show that the flavin mononucleotide, a common redox cofactor, wraps around single-walled carbon nanotubes in a helical pattern that imparts efficient individualization and chirality selection. The cooperative hydrogen bonding between adjacent flavin moieties results in the formation of a helical ribbon, which organizes around single-walled carbon nanotubes through concentric π–π interactions between the flavin mononucleotide and the underlying graphene wall. The strength of the helical flavin mononucleotide assembly is strongly dependent on nanotube chirality. In the presence of a surfactant, the flavin mononucleotide assembly is disrupted and replaced without precipitation by a surfactant micelle. The significantly higher affinity of the flavin mononucleotide assembly for (8,6)-single-walled carbon nanotubes results in an 85% chirality enrichment from a nanotube sample with broad diameter distribution.

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Figure 1: Photoluminescence emission (PLE) maps of HiPco–SWNT samples.
Figure 2: Helical wrapping motif of FMN around SWNTs.
Figure 3: PLE-assisted determination of FMN replacement by SDBS titration, zooming on (8,6)-SWNT.
Figure 4: Chirality-dependent affinity of FMN-wrapped SWNTs, as determined by SDBS titration.
Figure 5: Chirality, family and modality dependence of FMN-induced ES11 redshift for all PLE-observed nanotubes.
Figure 6: Enrichment of the (8,6) nanotube using (i) selective SDBS replacement of FMN on all but (8,6)-SWNTs, and (ii) addition of NaCl to salt out all SDBS-dispersed nanotubes.

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Acknowledgements

The authors wish to thank Z. Luo, W. Kopcha and C. Badalucco for their help and S. Daniels for valuable discussions. This work has been supported mainly by Air Force Office of Scientific Research (AFOSR) FA9550-06-1-0030, and in part by National Science Foundation (NSF)-Nanoscale Interdisciplinary Research Team (NIRT) DMI-0422724, Army Research Office (ARO)-DAAD-19-02-1-10381, National Institute of Health (NIH)-ES013557 and the U.S. Army Medical Research W81XWH-05-1-0539.

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Authors and Affiliations

  1. Nanomaterials Optoelectronics Laboratory (NOEL), Polymer Program, University of Connecticut, Connecticut, Storrs, 06269-3136, USA

    Sang-Yong Ju, Jonathan Doll & Fotios Papadimitrakopoulos

  2. Department of Chemistry, Institute of Materials Science, University of Connecticut, Storrs, 06269-3136, Connecticut, USA

    Ity Sharma & Fotios Papadimitrakopoulos

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  1. Sang-Yong Ju
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  2. Jonathan Doll
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Contributions

S.J. and F.P. conceived and designed the experiments. S.J. performed sample preparation along with PLE and UV-vis-NIR characterization. J.D. performed HRTEM analysis. S.J. and I.S. performed data analysis. S.J. and F.P. performed the molecular simulation. S.J. and F.P. co-wrote the paper.

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Correspondence to Fotios Papadimitrakopoulos.

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Ju, SY., Doll, J., Sharma, I. et al. Selection of carbon nanotubes with specific chiralities using helical assemblies of flavin mononucleotide. Nature Nanotech 3, 356–362 (2008). https://doi.org/10.1038/nnano.2008.148

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