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Hierarchical architectures by synergy between dynamical template self-assembly and biomineralization

Nature Materials volume 6, pages 434–439 (2007)Cite this article

Abstract

Diatoms, shells, bones and teeth are exquisite examples of well-defined structures, arranged from nanometre to macroscopic length scale, produced by natural biomineralization using organic templates to control the growth of the inorganic phase1,2,3,4,5,6. Although strategies mimicking Nature have partially succeeded in synthesizing human-designed bio-inorganic composite materials7,8,9,10, our limited understanding of fundamental mechanisms has so far kept the level of hierarchical complexity found in biological organisms out of the chemists’ reach11. In this letter, we report on the synthesis of unprecedented double-walled silica nanotubes with monodisperse diameters that self-organize into highly ordered centimetre-sized fibres. A unique synergistic growth mechanism is elucidated by the combination of light and electron microscopy, synchrotron X-ray diffuse scattering and Raman spectroscopy. Following this growth mechanism, macroscopic bundles of nanotubules result from the kinetic cross-coupling of two molecular processes: a dynamical supramolecular self-assembly and a stabilizing silica mineralization. The feedback actions between the template growth and the inorganic deposition are driven by a mutual electrostatic neutralization. This ‘dynamical template’ concept can be further generalized as a rational preparation scheme for materials with well-defined multiscale architectures and also as a fundamental mechanism for growth processes in biological systems.

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Figure 1: Silica mineralization of lanreotide.
Figure 2: Multiscale organization of silica–lanreotide nanotubes.
Figure 3: Evidence for double-walled silica–lanreotide nanotubes.
Figure 4: Dynamic template model for the growth mechanism of the peptide–silica fibres.

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Acknowledgements

Beaufour-IPSEN is acknowledged for providing the peptide and European Synchrotron Radiation Facility (ESRF) for allocating beam time (SC801). We are thankful to T. Narayanan for her support during preliminary experiments on the ID02 beamline at the ESRF synchrotron. E. Henry is acknowledged for the capillary picture. This work was supported by the Centre National de la Recherche Scientifique (AC Nanosciences–Nanotechnologies), by a research ministry fellowship (E.P.).

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Authors and Affiliations

  1. Groupe Matière Condensée et Matériaux, UMR 6626 CNRS et Université Rennes 1, 263 Avenue du général Leclerc, 35042 Rennes Cedex, France

    Emilie Pouget, Alain Moreac, Anne Renault & Franck Artzner

  2. NanoSciences Group, CEMES UPR 8011 CNRS, BP 94347, 29 r. J. Marvig, 31055 Toulouse Cedex 4, France

    Erik Dujardin

  3. Interactions Cellulaires et Moléculaires, UMR 6026 CNRS et Université Rennes 1, 263 Avenue du général Leclerc, 35042 Rennes Cedex, France

    Annie Cavalier

  4. Ipsen Pharma S.A., Ctra. Laurea Miro 395, 08980-Sant Feliu de Llobregat, Barcelona, Spain

    Céline Valéry

  5. Sciences Chimiques de Rennes, UMR 6226 CNRS et Université Rennes 1, 263 Avenue du général Leclerc, 35042 Rennes Cedex, France

    Valérie Marchi-Artzner

  6. ESRF, 6 rue Jules Horowitz, BP220, 38043 Grenoble Cedex, France

    Thomas Weiss

  7. URA 2096, IBiTechS, CEA-Saclay, F-91191 Gif/Yvette, France

    Maité Paternostre

Authors
  1. Emilie Pouget
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Contributions

F.A. designed the research, with additional contributions from E.D. and M.P. C.V., V.M.-A., M.P. and F.A. initiated the project. E.P., E.D. and A.C. performed TEM experiments. E.P., T.W., A.R. and F.A. performed SAXS experiments. E.P. and A.M. performed Raman experiments. E.P., E.D., M.P. and F.A. analysed data and wrote the paper.

Corresponding author

Correspondence to Franck Artzner.

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The authors declare no competing financial interests.

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Pouget, E., Dujardin, E., Cavalier, A. et al. Hierarchical architectures by synergy between dynamical template self-assembly and biomineralization. Nature Mater 6, 434–439 (2007). https://doi.org/10.1038/nmat1912

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