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Metal-coordination interactions in the template-mediated synthesis of substrate-selective polymers: recognition of bis(imidazole) substrates by copper(II) iminodiacetate containing polymers

Dhal, Pradeep K. and Arnold, Frances H. (1992) Metal-coordination interactions in the template-mediated synthesis of substrate-selective polymers: recognition of bis(imidazole) substrates by copper(II) iminodiacetate containing polymers. Macromolecules, 25 (25). pp. 7051-7059. ISSN 0024-9297. https://resolver.caltech.edu/CaltechAUTHORS:20180720-124935431

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Abstract

Metal-complexing polymer matrices capable of specific recognition and binding to metal-coordinating substrates have been prepared by template-directed polymerization. The synthesis of these materials involves preorganization of a copper-containing vinyl monomer, copper(II) [N-(4-vinylbenzyl)-imino]diacetic acid (1), with bifunctional bis(imidazole) templates (2-5) of varying geometry and subsequent polymerization with a large excess of ethylene glycol dimethacrylate as the cross-linking agent. Complexation of metal-chelating monomers with the template during polymerization directs the positioning of metal ions in the polymer matrices, while a high degree of cross-linking stabilizes the functional group arrangement. In equilibrium binding experiments with single substrates and selected substrate pairs, the polymers preferentially bind their own templates, with separation factors (α) of 1.17-1.35 and binding constants that range from 1800 to 3800 M^(-1). The capacities and affinities of the polymers for different substrates and ESR spectral analyses of the polymers loaded with substrate suggest a defined arrangement of metal ion sites in the templated materials that is absent in nontemplated polymers. The substrate selectivity likely involves some cooperative two-site coordination of the bis(imidazoles) as well as steric interactions with the binding cavities ("cavity fitting"). This template polymerization strategy is discussed from the viewpoint of designing highly specific abiotic receptors for recognition of delicate and complex biomolecules.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://dx.doi.org/10.1021/ma00051a050DOIArticle
ORCID:
AuthorORCID
Dhal, Pradeep K.0000-0002-7059-855X
Arnold, Frances H.0000-0002-4027-364X
Additional Information:© 1992 American Chemical Society. Received June 8, 1992; Revised Manuscript Received September 2, 1992. This research is supported by a grant from the National Science Foundation (Grant BCS-9108502). F.H.A. gratefully acknowledges a fellowship from the David and Lucile Packard Foundation and a Presidential Young Investigator Award of the National Science Foundation. We wish to thank Prof. Douglas Clark and Mr. Rhett Affleck (U. C. Berkeley) for their kind assistance with the ESR experiments.
Funders:
Funding AgencyGrant Number
NSFBCS-9108502
David and Lucile Packard FoundationUNSPECIFIED
Issue or Number:25
Record Number:CaltechAUTHORS:20180720-124935431
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20180720-124935431
Official Citation:Metal-coordination interactions in the template-mediated synthesis of substrate-selective polymers: recognition of bis(imidazole) substrates by copper(II) iminodiacetate containing polymers Pradeep K. Dhal and Frances H. Arnold Macromolecules 1992 25 (25), 7051-7059 DOI: 10.1021/ma00051a050
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:88065
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:23 Jul 2018 21:05
Last Modified:03 Oct 2019 20:02

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