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Exploration of nanostructured channel systems with single-molecule probes

Nature Materials volume 6, pages 303–310 (2007)Cite this article

Abstract

Molecular movement in confined spaces is of broad scientific and technological importance in areas ranging from molecular sieving and membrane separation to active transport through ion channels. Whereas measurements of ensemble diffusion provide information about the overall behaviour of the guest in a porous host, tracking individual molecules provides insight into both the heterogeneity and the mechanistic details of molecular diffusion as well as into the structure of the host. Here, we show how single dye molecules can be used as nanoscale probes to map out the structure of mesoporous silica channel systems prepared as thin films via cooperative self-assembly of surfactant molecules with polymerizable silicate species. The dye molecules act as beacons while they diffuse through the different structural phases of the host: the structure of the trajectories, the diffusivities and the orientation of single molecules are distinctive for molecules travelling in the lamellar and the hexagonal mesophases. These experiments reveal unprecedented details of the host structure, its domains and the accessibility as well as the connectivity of the channel system.

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Figure 1: Sample systems.
Figure 2: Single-molecule images and trajectories of the pure hexagonal and lamellar phases of the mesoporous hosts obtained by wide-field imaging.
Figure 3: Mean-square displacement as a function of time.
Figure 4: Diffusion of single molecules in the phase mixture.
Figure 5: Diffusion analysis of individual trajectories in the hexagonal phase of the mixture.

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Acknowledgements

We would like to thank K. Müllen (MPI für Polymerforschung, Mainz, Germany) for kindly providing the TDI dye, N. Rauhut for the assistance with the measurements and P. Schwaderer for the AFM data. This work was financially supported by the Sonderforschungsbereich SFB-486.

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Authors and Affiliations

  1. Department of Chemistry and Biochemistry, Center for NanoScience (CeNS) and Nanosystems Initiative Munich (NIM), University of Munich, Butenandtstr. 5-13 (E), 81377 Munich, Germany

    Johanna Kirstein, Barbara Platschek, Christophe Jung, Thomas Bein & Christoph Bräuchle

  2. Institut de recherches pluridisciplinaires sur l’environnement et les matériaux, umr 5624 du CNRS et de l’Université de Pau et des pays de l’Adour, avenue Pierre Angot, 64053 PAU Cedex 9, France

    Ross Brown

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Correspondence to Christoph Bräuchle.

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Kirstein, J., Platschek, B., Jung, C. et al. Exploration of nanostructured channel systems with single-molecule probes. Nature Mater 6, 303–310 (2007). https://doi.org/10.1038/nmat1861

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