Dinuclear bisimidazolyl-Cu(II) calix[4]arenes as metalloenzyme models. Synthesis and bifunctional catalysis in phosphate diester transesterification

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Molenveld, Peter and Engbersen, Johan F.J. and Reinhoudt, David N. (1999) Dinuclear bisimidazolyl-Cu(II) calix[4]arenes as metalloenzyme models. Synthesis and bifunctional catalysis in phosphate diester transesterification. Journal of Organic Chemistry, 64 (17). pp. 6337-6341. ISSN 0022-3263

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Abstract:Calix[4]arenes functionalized with two catalytic bisimidazolyl-Cu(II) centers and two additional hydroxymethyl (2-Cu2) or aminomethyl groups (3-Cu2) were synthesized as models for enzymes that cleave phosphate diester bonds. The kinetics of 2-Cu2 and 3-Cu2 in the catalysis of the intramolecular transesterification of the RNA model substrate 2-hydroxypropyl-p-nitrophenyl phosphate were compared with those of the parent calix[4]arene 1-Cu2, lacking the two additional functional groups. Under neutral conditions, all complexes show high rate enhancements due to the cooperative action of the Cu(II) ions. The kinetics indicate for 3-Cu2 bifunctional catalytic effects. At the pH optimum of 7.4 at least one amine is protonated, which can assist as a general acid in the binding and activation of the substrate.
Item Type:Article
Copyright:© 1999 American Chemical Society
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Science and Technology (TNW)
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Link to this item:http://purl.utwente.nl/publications/11813
Official URL:http://dx.doi.org/10.1021/jo9905266
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Metis ID: 106350