Metalloenzyme-like catalyzed isomerizations of sugars by Lewis acid zeolites
Creators
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1.
California Institute of Technology
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2.
Argonne National Laboratory
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3.
Northwestern University
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4.
Wayne State University
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5.
Instituto de Tecnología Química
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6.
Massachusetts Institute of Technology
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7.
University of Delaware
Abstract
Isomerization of sugars is used in a variety of industrially relevant processes and in glycolysis. Here, we show that hydrophobic zeolite beta with framework tin or titanium Lewis acid centers isomerizes sugars, e.g., glucose, via reaction pathways that are analogous to those of metalloenzymes. Specifically, experimental and theoretical investigations reveal that glucose partitions into the zeolite in the pyranose form, ring opens to the acyclic form in the presence of the Lewis acid center, isomerizes into the acyclic form of fructose, and finally ring closes to yield the furanose product. The zeolite catalysts provide processing advantages over metalloenzymes such as an ability to work at higher temperatures and in acidic conditions that allow for the isomerization reaction to be coupled with other important conversions.
Additional Information
© 2012 National Academy of Sciences. Freely available online through the PNAS open access option. Contributed by Mark E. Davis, April 23, 2012 (sent for review April 4, 2012. The work at Caltech and the University of Delaware was financially supported as part of the Catalysis Center for Energy Innovation, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award DE-SC0001004. M.M acknowledges the Fundación Ramón Areces Postdoctoral Research Fellowship Program and the "Subprograma Ramon y Cajal" for Contract RYC-2011-08972 for financial support. R.B.D. acknowledges the Obra Social "la Caixa" for a graduate fellowship. A.P. acknowledges the Caltech Summer Undergraduate Research Fellowship program(SURF) for financial support. The computational studies for this workwere supported by the U.S. Department of Energy under Contract DE-AC0206CH11357 and this material is based upon work supported as part of the Institute for Atom-efficient Chemical Transformations (IACT), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, and Office of Basic Energy Sciences. We gratefully acknowledge grants of computer time from the ANL Laboratory Computing Resource Center (LCRC), and the ANL Center for Nanoscale Materials. This research used resources of the National Energy Research Scientific Computing Center, which is supported by the Office of Sciences of the U.S. Department of Energy under Contract DE-AC02-05CH11231. Author contributions: R.B.-D., R.S.A., Y.R.-L., R.F.L., L.A.C., and M.E.D. designed research; R.B.-D., R.S.A., E.N., M.M., S.-J.H., A.P., and D.S. performed research; R.B.-D., R.S.A., Y.R.-L., S.-J.H., R.F.L., L.A.C., and M.E.D. analyzed data; and R.B.-D., R.S.A., Y.R.-L., L.A.C., and M.E.D. wrote the paper. The authors declare no conflict of interest. This article contains supporting information online at www.pnas.org/lookup/suppl/doi:10.1073/pnas.1206708109/-/DCSupplemental.Attached Files
Published - BermejoDeval2012p18876P_Natl_Acad_Sci_Usa.pdf
Supplemental Material - Appendix.pdf
Files
Appendix.pdf
Additional details
Identifiers
- PMCID
- PMC3382492
- Eprint ID
- 32649
- Resolver ID
- CaltechAUTHORS:20120723-125206829
Funding
- Department of Energy (DOE)
- DE-SC0001004
- Fundación Ramón Areces
- Ramon y Cajal
- RYC-2001-08972
- Obra Social "la Caixa"
- Caltech Summer Undergraduate Research Fellowship (SURF)
Dates
- Created
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2012-07-23Created from EPrint's datestamp field
- Updated
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2021-11-09Created from EPrint's last_modified field