A Caltech Library Service

Metalloenzyme-like catalyzed isomerizations of sugars by Lewis acid zeolites

Bermejo-Deval, Ricardo and Assary, Rajeev S. and Nikolla, Eranda and Moliner, Manuel and Román-Leshkov, Yuriy and Hwang, Son-Jong and Palsdottir, Arna and Silverman, Dorothy and Lobo, Raul F. and Curtiss, Larry A. and Davis, Mark E. (2012) Metalloenzyme-like catalyzed isomerizations of sugars by Lewis acid zeolites. Proceedings of the National Academy of Sciences of the United States of America, 109 (25). pp. 9727-9732. ISSN 0027-8424. PMCID PMC3382492. doi:10.1073/pnas.1206708109.

PDF - Published Version
See Usage Policy.

PDF - Supplemental Material
See Usage Policy.


Use this Persistent URL to link to this item:


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.

Item Type:Article
Related URLs:
URLURL TypeDescription CentralArticle
Assary, Rajeev S.0000-0002-9571-3307
Nikolla, Eranda0000-0002-8172-884X
Moliner, Manuel0000-0002-5440-716X
Román-Leshkov, Yuriy0000-0002-0025-4233
Hwang, Son-Jong0000-0002-3210-466X
Curtiss, Larry A.0000-0001-8855-8006
Davis, Mark E.0000-0001-8294-1477
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
Funding AgencyGrant Number
Department of Energy (DOE)DE-SC0001004
Fundación Ramón ArecesUNSPECIFIED
Ramon y CajalRYC-2001-08972
Obra Social "la Caixa"UNSPECIFIED
Caltech Summer Undergraduate Research Fellowship (SURF)UNSPECIFIED
Subject Keywords:glucose isomerization; heterogeneous catalysis; reaction mechanism
Issue or Number:25
PubMed Central ID:PMC3382492
Record Number:CaltechAUTHORS:20120723-125206829
Persistent URL:
Official Citation:Ricardo Bermejo-Deval, Rajeev S. Assary, Eranda Nikolla, Manuel Moliner, Yuriy Román-Leshkov, Son-Jong Hwang, Arna Palsdottir, Dorothy Silverman, Raul F. Lobo, Larry A. Curtiss, and Mark E. Davis Metalloenzyme-like catalyzed isomerizations of sugars by Lewis acid zeolites PNAS 2012 109 (25) 9727-9732; published ahead of print June 4, 2012, doi:10.1073/pnas.1206708109
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:32649
Deposited By: Aucoeur Ngo
Deposited On:23 Jul 2012 21:29
Last Modified:09 Nov 2021 21:28

Repository Staff Only: item control page