Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Letter
  • Published:

Molecular imprinting of bulk, microporous silica

Nature volume 403, pages 286–289 (2000)Cite this article

Abstract

Molecular imprinting aims to create solid materials containing chemical functionalities that are spatially organized by covalent1 or non-covalent2 interactions with imprint (or template) molecules during the synthesis process. Subsequent removal of the imprint molecules leaves behind designed sites for the recognition of small molecules, making the material ideally suited for applications such as separations, chemical sensing and catalysis2,3,4,5. Until now, the molecular imprinting of bulk polymers2,3,4,5 and polymer6,7 and silica8,9 surfaces has been reported, but the extension of these methods to a wider range of materials remains problematic. For example, the formation of substrate-specific cavities within bulk silica, while conceptually straightforward10, has been difficult to accomplish experimentally11,12. Here we describe the imprinting of bulk amorphous silicas with single aromatic rings carrying up to three 3-aminopropyltriethoxysilane side groups; this generates and occupies microporosity and attaches functional organic groups to the pore walls in a controlled fashion. The triethoxysilane part of the molecules’ side groups is incorporated into the silica framework during sol–gel synthesis, and subsequent removal of the aromatic core creates a cavity with spatially organized aminopropyl groups covalently anchored to the pore walls. We find that the imprinted silicas act as shape-selective base catalysts. Our strategy can be extended to imprint other functional groups, which should give access to a wide range of functionalized materials.

This is a preview of subscription content, access via your institution

Access options

Buy this article

  • Purchase on Springer Link
  • Instant access to full article PDF
Buy now

Prices may be subject to local taxes which are calculated during checkout

Figure 1: Preparation procedures used to create the imprinted silicas.
Figure 2: Solid-state NMR spectra of the two-point-imprinted material.
Figure 3: Physical adsorption of argon at 77 K.
Figure 4: Infrared and fluorescence spectra from imprinted silicas.

Similar content being viewed by others

References

  1. Whitcombe, M. J., Rodriguez, M. E., Villar, P. & Vulfson,, E. A new method for the introduction of recognition site functionality into polymers prepared by molecular imprinting - Synthesis and characterization of polymer receptors for cholesterol. J. Am. Chem. Soc. 117, 7105–7111 (1995).

    Article  CAS  Google Scholar 

  2. Vlatakis, G., Anderson, L. I., Müller, R. & Mosbach, K. Drug assay using antibody mimics made by molecular imprinting. Nature 361, 645–647 ( 1993).

    Article  ADS  CAS  Google Scholar 

  3. Wulff, G. Molecular imprinting in cross-linked materials with the aid of molecular templates - a way towards artificial antibodies. Angew. Chem. Int. Edn Engl. 34, 1812–1832 ( 1995).

    Article  CAS  Google Scholar 

  4. Davis, M. E., Katz, A. & Ahmad, W. R. Rational catalyst design via imprinted nanostructured materials. Chem. Mater. 8, 1820– 1839 (1996).

    Article  CAS  Google Scholar 

  5. Shea, K. J. Molecular imprinting of synthetic network polymers: the de novo synthesis of macromolecular binding and catalytic sites. Trends Polym. Sci 2, 166–173 ( 1994).

    CAS  Google Scholar 

  6. D'Souza, S. M. et al. Directed nucleation of calcite at a crystal-imprinted polymer surface. Nature 398, 312– 316 (1999).

    Article  ADS  CAS  Google Scholar 

  7. Shi, H., Tsai, W., Garrison, M. D., Ferrari, S. & Ratner,, B. D. Template-imprinted nanostructured surfaces for protein recognition. Nature 398, 593–597 (1999).

    Article  ADS  CAS  PubMed  Google Scholar 

  8. Wulff, G., Heide, B. & Helfmeier, G. Molecular recognition through the exact placement of functional groups on rigid matrices via a template approach. J. Am. Chem. Soc. 108, 1089–1091 (1986).

    Article  CAS  Google Scholar 

  9. Dai, S. et al. Imprint coating: A novel synthesis of selective functionalized ordered mesoporous sorbents. Angew. Chem. Int. Edn Engl. 38 , 1235–1239 (1999).

    Article  CAS  Google Scholar 

  10. Heilmann, J. & Maier,, W. F. Selective catalysis on silicon dioxide with substrate-specific cavities. Angew. Chem. Int. Edn Engl. 33, 471–473 ( 1994).

    Article  Google Scholar 

  11. Ahmad, W. R. & Davis,, M. E. Transesterification on “imprinted” silica. Catal. Lett. 40, 109– 114 (1996).

    Article  CAS  Google Scholar 

  12. Maier, W. F. & Ben Mustapha, W. Transesterification on “imprinted” silica—Reply. Catal. Lett. 46, 137 –140 (1997).

    Article  CAS  Google Scholar 

  13. Katz, A. & Davis, M. E. Investigations into the mechanisms of molecular recognition with imprinted polymers. Macromolecules 32, 4113–4121 ( 1999).

    Article  ADS  CAS  Google Scholar 

  14. Jones, C. W., Tsuji, K. & Davis, M. E. Organic-functionalized molecular sieves as shape-selective catalysts. Nature 393, 52– 54 (1998).

    Article  ADS  CAS  Google Scholar 

  15. Brinker, C. J., Keefer, K. D., Schaefer, D. W. & Ashley,, C. S. Sol-gel transition in simple silicates. J. Non-Cryst. Solids 48, 47–64 (1982).

    Article  ADS  CAS  Google Scholar 

  16. Fuji, K. et al. Visualization of molecular length of α,ω-diamines and temperature by a receptor based on phenolphthalein and crown ether. J. Am. Chem. Soc. 121, 3807–3808 (1999).

    Article  CAS  Google Scholar 

  17. Dunn, D. & Zink, J. I. Probes of pore environment and molecule-matrix interaction in sol-gel materials. Chem. Mater. 4, 2280–2291 (1997).

    Article  Google Scholar 

  18. Houk, J. & Whitesides, G. M. Structure reactivity relations for thiol disulfide interchange. J. Am. Chem. Soc. 109, 6825–6836 (1987).

    Article  CAS  Google Scholar 

Download references

Acknowledgements

A Fannie and John Hertz Foundation Graduate Fellowship to A. K. and a NSF Waterman Award to M. E. D. are gratefully acknowledged. We thank L. W. Beck for assistance with the NMR experiments, and H. Gonzalez and A. G. Myers for discussions.

Author information

Author notes

  1. Alexander Katz

    Present address: Chemical Engineering Department, University of California, Berkeley, California, 94720-1462, USA

Authors and Affiliations

  1. Chemical Engineering, California Institute of Technology, Pasadena, 91125, California, USA

    Alexander Katz & Mark E. Davis

Authors
  1. Alexander Katz
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Mark E. Davis
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Mark E. Davis.

Supplementary information

Supplementary Information

Supplementary Information (PDF 199 kb)

Rights and permissions

Reprints and permissions

About this article

Cite this article

Katz, A., Davis, M. Molecular imprinting of bulk, microporous silica. Nature 403, 286–289 (2000). https://doi.org/10.1038/35002032

Download citation

  • Received:

  • Accepted:

  • Issue Date:

  • DOI: https://doi.org/10.1038/35002032

This article is cited by

Comments

By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.

Search

Advanced search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing