Theoretical examination of the mechanism of aldose-ketose isomerization |
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Authors: | Zheng, Ya-Jun Merz, Kenneth M., Jr Farber, Gregory K. |
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Affiliation: | 152 Davey Laboratory, Department of Chemistry, Pennsylvania State University University Park, PA 16802, USA |
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Abstract: | Two mechanisms for an aldoseketose isomerization havebeen examined using high level ab initio and semiempirical molecularorbital methods. The proton transfer pathway via an enediolintermediate is shown to be favored in the absence of a metalion, while the hydride transfer pathway becomes favored in thepresence of a metal ion. Our calculations explain why the protontransfer pathway is operative in most aldoseketose isomerizationreactions. These calculations also provide further support forthe previously proposed metal ion-mediated hydride transfermechanism for xylose isomerase. |
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Keywords: | computational chemistry/ enzyme mechanism/ metal ion/ sugar/ xylose isomerase |
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