Probing the Mechanism of Cyanobacterial Aldehyde Decarbonylase Using a Cyclopropyl Aldehyde

Overview

Journal J Am Chem Soc

Publisher American Chemical Society

Specialty Chemistry

Date 2013 Mar 22

PMID 23514600

Citations 28

Authors

Bishwajit Paul

Debasis Das

Benjamin Ellington

E Neil G Marsh

Affiliations

Soon will be listed here.

Abstract

Cyanobacterial aldehyde decarbonylase (cAD) is a non-heme diiron oxygenase that catalyzes the conversion of fatty aldehydes to alkanes and formate. The mechanism of this chemically unusual reaction is poorly understood. We have investigated the mechanism of C1-C2 bond cleavage by cAD using a fatty aldehyde that incorporates a cyclopropyl group, which can act as a radical clock. When reacted with cAD, the cyclopropyl aldehyde produces 1-octadecene as the rearranged product, providing evidence for a radical mechanism for C-C bond scission. In an alternate pathway, the cyclopropyl aldehyde acts as a mechanism-based irreversible inhibitor of cAD through covalent binding of the alkyl chain to the enzyme.

Citing Articles

Incorporation, fate, and turnover of free fatty acids in cyanobacteria.

Kahn A, Oliveira P, Cuau M, Leao P FEMS Microbiol Rev. 2023; 47(2).

PMID: 37061785 PMC: 10114076. DOI: 10.1093/femsre/fuad015.

Recent advances in the improvement of cyanobacterial enzymes for bioalkane production.

Hayashi Y, Arai M Microb Cell Fact. 2022; 21(1):256.

PMID: 36503511 PMC: 9743570. DOI: 10.1186/s12934-022-01981-4.

Utilizing Alcohol for Alkane Biosynthesis by Introducing a Fatty Alcohol Dehydrogenase.

Sui Y, Kishino S, Maruyama S, Ito M, Muramatsu M, Obata S Appl Environ Microbiol. 2022; 88(23):e0126422.

PMID: 36416567 PMC: 9746291. DOI: 10.1128/aem.01264-22.

Fingerprinting cities: differentiating subway microbiome functionality.

Zhu C, Miller M, Lusskin N, Mahlich Y, Wang Y, Zeng Z Biol Direct. 2019; 14(1):19.

PMID: 31666099 PMC: 6822482. DOI: 10.1186/s13062-019-0252-y.

Metal-Free Aryl Cross-Coupling Directed by Traceless Linkers.

Haensch V, Neuwirth T, Steinmetzer J, Kloss F, Beckert R, Grafe S Chemistry. 2019; 25(70):16068-16073.

PMID: 31621964 PMC: 6973076. DOI: 10.1002/chem.201903582.

References

Rude M, Schirmer A . New microbial fuels: a biotech perspective. Curr Opin Microbiol. 2009; 12(3):274-81. DOI: 10.1016/j.mib.2009.04.004. View

Buist P . Exotic biomodification of fatty acids. Nat Prod Rep. 2007; 24(5):1110-27. DOI: 10.1039/b508584p. View

Eser B, Das D, Han J, Jones P, Marsh E . Oxygen-independent alkane formation by non-heme iron-dependent cyanobacterial aldehyde decarbonylase: investigation of kinetics and requirement for an external electron donor. Biochemistry. 2011; 50(49):10743-50. PMC: 3235001. DOI: 10.1021/bi2012417. View

Bourdenx B, Bernard A, Domergue F, Pascal S, Leger A, Roby D . Overexpression of Arabidopsis ECERIFERUM1 promotes wax very-long-chain alkane biosynthesis and influences plant response to biotic and abiotic stresses. Plant Physiol. 2011; 156(1):29-45. PMC: 3091054. DOI: 10.1104/pp.111.172320. View

Cheesbrough T, Kolattukudy P . Microsomal preparation from an animal tissue catalyzes release of carbon monoxide from a fatty aldehyde to generate an alkane. J Biol Chem. 1988; 263(6):2738-43. View

Rowland O, Zheng H, Hepworth S, Lam P, Jetter R, Kunst L . CER4 encodes an alcohol-forming fatty acyl-coenzyme A reductase involved in cuticular wax production in Arabidopsis. Plant Physiol. 2006; 142(3):866-77. PMC: 1630741. DOI: 10.1104/pp.106.086785. View

Aarts M, Keijzer C, Stiekema W, Pereira A . Molecular characterization of the CER1 gene of arabidopsis involved in epicuticular wax biosynthesis and pollen fertility. Plant Cell. 1995; 7(12):2115-27. PMC: 161066. DOI: 10.1105/tpc.7.12.2115. View

Qiu Y, Tittiger C, Wicker-Thomas C, Le Goff G, Young S, Wajnberg E . An insect-specific P450 oxidative decarbonylase for cuticular hydrocarbon biosynthesis. Proc Natl Acad Sci U S A. 2012; 109(37):14858-63. PMC: 3443174. DOI: 10.1073/pnas.1208650109. View

Valentine A, Toy P, Newcomb M, Lippard S . Oxidation of ultrafast radical clock substrate probes by the soluble methane monooxygenase from Methylococcus capsulatus (Bath). J Biol Chem. 1999; 274(16):10771-6. DOI: 10.1074/jbc.274.16.10771. View

10.

Somerville C, Youngs H, Taylor C, Davis S, Long S . Feedstocks for lignocellulosic biofuels. Science. 2010; 329(5993):790-2. DOI: 10.1126/science.1189268. View

11.

Reed J, Vanderwel D, Choi S, Pomonis J, Reitz R, Blomquist G . Unusual mechanism of hydrocarbon formation in the housefly: cytochrome P450 converts aldehyde to the sex pheromone component (Z)-9-tricosene and CO2. Proc Natl Acad Sci U S A. 1994; 91(21):10000-4. PMC: 44945. DOI: 10.1073/pnas.91.21.10000. View

12.

Kunst L, Samuels A . Biosynthesis and secretion of plant cuticular wax. Prog Lipid Res. 2002; 42(1):51-80. DOI: 10.1016/s0163-7827(02)00045-0. View

13.

Li N, Norgaard H, Warui D, Booker S, Krebs C, Bollinger Jr J . Conversion of fatty aldehydes to alka(e)nes and formate by a cyanobacterial aldehyde decarbonylase: cryptic redox by an unusual dimetal oxygenase. J Am Chem Soc. 2011; 133(16):6158-61. PMC: 3113487. DOI: 10.1021/ja2013517. View

14.

Cao F, Chen Y, Cierpicki T, Liu Y, Basrur V, Lei M . An Ash2L/RbBP5 heterodimer stimulates the MLL1 methyltransferase activity through coordinated substrate interactions with the MLL1 SET domain. PLoS One. 2010; 5(11):e14102. PMC: 2990719. DOI: 10.1371/journal.pone.0014102. View

15.

Cheesbrough T, Kolattukudy P . Alkane biosynthesis by decarbonylation of aldehydes catalyzed by a particulate preparation from Pisum sativum. Proc Natl Acad Sci U S A. 1984; 81(21):6613-7. PMC: 391980. DOI: 10.1073/pnas.81.21.6613. View

16.

Souda P, Ryan C, Cramer W, Whitelegge J . Profiling of integral membrane proteins and their post translational modifications using high-resolution mass spectrometry. Methods. 2011; 55(4):330-6. PMC: 3498814. DOI: 10.1016/j.ymeth.2011.09.019. View

17.

Li N, Chang W, Warui D, Booker S, Krebs C, Bollinger Jr J . Evidence for only oxygenative cleavage of aldehydes to alk(a/e)nes and formate by cyanobacterial aldehyde decarbonylases. Biochemistry. 2012; 51(40):7908-16. DOI: 10.1021/bi300912n. View

18.

Wang X, Kolattukudy P . Solubilization and purification of aldehyde-generating fatty acyl-CoA reductase from green alga Botryococcus braunii. FEBS Lett. 1995; 370(1-2):15-8. DOI: 10.1016/0014-5793(95)00781-4. View

19.

Schirmer A, Rude M, Li X, Popova E, del Cardayre S . Microbial biosynthesis of alkanes. Science. 2010; 329(5991):559-62. DOI: 10.1126/science.1187936. View

20.

Huang H, Chang W, Pai P, Romo A, Mansoorabadi S, Russell D . Evidence for radical-mediated catalysis by HppE: a study using cyclopropyl and methylenecyclopropyl substrate analogues. J Am Chem Soc. 2012; 134(39):16171-4. PMC: 3463719. DOI: 10.1021/ja3078126. View