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Synthetic hosts by monomolecular imprinting inside dendrimers

Nature volume 418, pages 399–403 (2002)Cite this article

Abstract

Synthetic host systems capable of selectively binding guest molecules are of interest for applications ranging from separations and chemical or biological sensing to the development of biomedical materials. Such host systems can be efficiently prepared by ‘imprinting’ polymers or inorganic materials with template molecules, which, upon removal, leave behind spatially arranged functional groups that act as recognition sites1,2,3,4. However, molecularly imprinted polymers have limitations, including incomplete template removal, broad guest affinities and selectivities, and slow mass transfer5,6,7,8. An alternative strategy for moulding desired recognition sites uses combinatorial libraries of assemblies that are made of a relatively small number of molecules, interconverting in dynamic equilibrium; upon addition of a target molecule, the library equilibrium shifts towards the best hosts9,10,11. Here we describe the dynamic imprinting of dendritic macromolecules with porphyrin templates to yield synthetic host molecules containing one binding site each. The process is based on our general strategy to prepare cored dendrimers12,13, and involves covalent attachment of dendrons to a porphyrin core, cross-linking of the end-groups of the dendrons, and removal of the porphyrin template by hydrolysis. In contrast to more traditional polymer imprinting, our approach ensures nearly homogeneous binding sites and quantitative template removal. Moreover, the hosts are soluble in common organic solvents and amenable to the incorporation of other functional groups, which should facilitate further development of this system for novel applications.

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Figure 1: Scheme illustrating the preparation of imprinted dendrimer 6.
Figure 2: Structural drawing illustrating structural changes that occur upon hydrolysis of the cross-linked dendrimer 5.
Figure 3: Porphyrins used to study binding properties of imprinted dendrimer 6.
Figure 4: Calculated structure of imprinted dendrimer 6 built by iterative attachment of dendrons to the core porphyrin, minimization and cross-linking of neighbouring double bonds.

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Acknowledgements

We thank W.A. Goddard and T. Cagin for help with dendrimer modelling. This work was funded by the NIH and the US Army Research Office. I.Z. thanks the Arnold and Mabel Beckman Foundation for a Beckman fellowship.

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Authors and Affiliations

  1. Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, 600 S. Mathews Avenue, Illinois, 61801, USA

    Steven C. Zimmerman, Michael S. Wendland, Neal A. Rakow & Kenneth S. Suslick

  2. Beckman Institute for Advanced Science and Technology, University of Illinois at Urbana-Champaign, Urbana, 600 S. Mathews Avenue, Illinois, 61801, USA

    Steven C. Zimmerman, Ilya Zharov & Kenneth S. Suslick

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  1. Steven C. Zimmerman
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  2. Michael S. Wendland
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Correspondence to Steven C. Zimmerman.

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Zimmerman, S., Wendland, M., Rakow, N. et al. Synthetic hosts by monomolecular imprinting inside dendrimers. Nature 418, 399–403 (2002). https://doi.org/10.1038/nature00877

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