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A dual cellular–heterogeneous catalyst strategy for the production of olefins from glucose


Living systems provide a promising approach to chemical synthesis, having been optimized by evolution to convert renewable carbon sources, such as glucose, into an enormous range of small molecules. However, a large number of synthetic structures can still be difficult to obtain solely from cells, such as unsubstituted hydrocarbons. In this work, we demonstrate the use of a dual cellular–heterogeneous catalytic strategy to produce olefins from glucose using a selective hydrolase to generate an activated intermediate that is readily deoxygenated. Using a new family of iterative thiolase enzymes, we genetically engineered a microbial strain that produces 4.3 ± 0.4 g l−1 of fatty acid from glucose with 86% captured as 3-hydroxyoctanoic and 3-hydroxydecanoic acids. This 3-hydroxy substituent serves as a leaving group that enables heterogeneous tandem decarboxylation–dehydration routes to olefinic products on Lewis acidic catalysts without the additional redox input required for enzymatic or chemical deoxygenation of simple fatty acids.

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Fig. 1: Biological hydrocarbons.
Fig. 2: Identification of a new biosynthetic PaaJ-like thiolase family.
Fig. 3: In vitro reconstitution of the PaaJ-dependent fatty acid synthesis pathway.
Fig. 4: Production of medium-chain C8–C10 fatty acids in engineered E. coli strains that contained a thiolase-dependent pathway for iterative chain elongation.
Fig. 5: Downstream processing of 3-hydroxy fatty acids to olefins on heterogeneous catalysts.

Data availability

All data generated and analysed during this study are included in the published article, source data files or supporting information files. All plasmids and strains generated in this study are available by request. Source data are provided with this paper.


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This work was funded by the generous support of the National Science Foundation through a CAREER Award (029504-003) to M.C.Y.C. and the Center for Sustainable Polymers, a National Science Foundation-supported Center for Chemical Innovation (CHE-1901635). H.S. acknowledges support from the Camille and Henry Dreyfus Postdoctoral Program in Environmental Chemistry. Z.Q.W. also acknowledges the generous support from the Research Foundation for the State University of New York (71272-ZQW).

Author information




Z.Q.W., H.S., N.H., D.S.P., P.J.D. and M.C.Y.C designed the research, Z.Q.W., H.S., E.J.K., N.H., D.S.P. and Y.M. carried out the experiments, Z.Q.W., H.S., E.J.K., N.H., D.S.P., G.K., P.J.D. and M.C.Y.C analysed the data and Z.Q.W., H.S., G.K., P.J.D. and M.C.Y.C wrote the paper.

Corresponding authors

Correspondence to Zhen Q. Wang or Michelle C. Y. Chang.

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Peer review information Nature Chemistry thanks Stephen Wallace and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Wang, Z.Q., Song, H., Koleski, E.J. et al. A dual cellular–heterogeneous catalyst strategy for the production of olefins from glucose. Nat. Chem. 13, 1178–1185 (2021).

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