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Visualizing single-molecule diffusion in mesoporous materials

Nature volume 450, pages 705–708 (2007)Cite this article

Abstract

Periodic mesoporous materials formed through the cooperative self-assembly of surfactants and framework building blocks can assume a variety of structures1,2,3, and their widely tuneable properties make them attractive hosts for numerous applications4,5,6,7. Because the molecular movement in the pore system is the most important and defining characteristic of porous materials8, it is of interest to learn about this behaviour as a function of local structure. Generally, individual fluorescent dye molecules can be used as molecular beacons with which to explore the structure of—and the dynamics within—these porous hosts9,10,11,12,13, and single-molecule fluorescence techniques provide detailed insights into the dynamics of various processes, ranging from biology14,15 to heterogeneous catalysis16. However, optical microscopy methods cannot directly image the mesoporous structure of the host system accommodating the diffusing molecules, whereas transmission electron microscopy provides detailed images of the porous structure17, but no dynamic information. It has therefore not been possible to ‘see’ how molecules diffuse in a real nanoscale pore structure. Here we present a combination of electron microscopic mapping and optical single-molecule tracking experiments to reveal how a single luminescent dye molecule travels through linear or strongly curved sections of a mesoporous channel system. In our approach we directly correlate porous structures detected by transmission electron microscopy with the diffusion dynamics of single molecules detected by optical microscopy. This opens up new ways of understanding the interactions of host and guest.

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Figure 1: Sample systems.
Figure 2: Merging of the single-molecule trajectories and the TEM micrographs.
Figure 3: Structural elements found in real two-dimensional hexagonal mesoporous silica film.
Figure 4: Structural elements and molecular trajectories found in real two-dimensional hexagonal mesoporous silica film.

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Acknowledgements

We thank K. Müllen for providing the TDI dye; Siltronic AG for the silicon wafers; the group of P. Müller-Buschbaum for the 2D-GISAXS measurements; and S. Schmidt and B. Platschek for assistance with electron microscopy. This work was funded by two Collaborative Research Centres (‘Manipulation of matter at the nanometer length scale’ and ‘Dynamics and intermediates of molecular transformations’) of the German Research Foundation (DFG) and by the Nanosystems Initiative Munich (NIM), as well as the Center for Integrated Protein Science Munich (CiPSM).

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Author notes

  1. Andreas Zürner and Johanna Kirstein: These authors contributed equally to this work.

Authors and Affiliations

  1. Department of Chemistry and Biochemistry and Center for NanoScience (CeNS), University of Munich, Butenandtstrasse 5-13 (E), D-81377 Munich, Germany, Munich

    Andreas Zürner, Johanna Kirstein, Markus Döblinger, Christoph Bräuchle & Thomas Bein

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  1. Andreas Zürner
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  2. Johanna Kirstein
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  3. Markus Döblinger
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  4. Christoph Bräuchle
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Corresponding authors

Correspondence to Christoph Bräuchle or Thomas Bein.

Supplementary information

Supplementary Information

This file contains Supplementary Figures 1-2 with Legends, Supplementary Table 1 and Legends for Supplementary Movies 1-3. (PDF 2427 kb)

Supplementary Movie 1

This file contains Supplementary Movie 1 which is a wide-field movie of fluorescent dye molecules diffusing through the porous system. Temporal resolution: 200 ms per frame. Animation with 5x real time. (MOV 6699 kb)

Supplementary Movie 2

This file contains Supplementary Movie 2 which shows the animation of the single particle trajectory superimposed with the porous structure from TEM (see Fig. 4a). The molecule clearly diffuses along the porous structure. Animation with 2x real time. (MOV 2655 kb)

Supplementary Movie 3

This file contains Supplementary Movie 3 which shows the animation of the single particle trajectory superimposed with the porous structure from TEM (see Fig. 4c). The molecule clearly diffuses along the porous structure and bounces back at domain boundaries. Animation with 2x real time. (MOV 4607 kb)

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Zürner, A., Kirstein, J., Döblinger, M. et al. Visualizing single-molecule diffusion in mesoporous materials. Nature 450, 705–708 (2007). https://doi.org/10.1038/nature06398

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