ABSTRACT In plants, lineage-specific metabolites can be created by activities derived from the catalytic promiscuity of ancestral proteins, although examples of recruiting detoxification

systems to biosynthetic pathways are scarce. The ubiquitous glyoxalase (GLX) system scavenges the cytotoxic methylglyoxal, in which GLXI isomerizes the α-hydroxy carbonyl in the

methylglyoxal–glutathione adduct for subsequent hydrolysis. We show that GLXIs across kingdoms are more promiscuous than recognized previously and can act as aromatases without cofactors. In

cotton, a specialized GLXI variant, SPG, has lost its GSH-binding sites and organelle-targeting signal, and evolved to aromatize cyclic sesquiterpenes bearing α-hydroxyketones to synthesize

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BEING VIEWED BY OTHERS INCORPORATION OF NITROGEN IN ANTINUTRITIONAL _SOLANUM_ ALKALOID BIOSYNTHESIS Article Open access 13 September 2024 THE BIOSYNTHETIC PATHWAY OF POTATO SOLANIDANES

DIVERGED FROM THAT OF SPIROSOLANES DUE TO EVOLUTION OF A DIOXYGENASE Article Open access 26 February 2021 DISCOVERY, CHARACTERIZATION AND ENGINEERING OF LIGASES FOR AMIDE SYNTHESIS Article

19 May 2021 DATA AVAILABILITY The authors declare that all relevant data supporting the findings of this study are available within the paper and its Supplementary Information. The FLNC

reads and HiSeq transcriptomic reads generated in this study have been deposited in the NCBI SRA database under accession number PRJNA493958. Moreover, datasets generated and/or analyzed

during the current study are available from the corresponding author upon reasonable request. CODE AVAILABILITY All code used in this study is available from the corresponding author upon

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with GC–MS, NMR and Q-TOF analyses and X. Hao, B. Xu, B. Yang, C. Shi, Y. Hu, Y. Li, L. Chen and K. Zhai for their kind and generous help. We also thank D. Nelson for naming the CYP

protein. The research was supported by grants from the National Natural Science Foundation of China (Nos. 31788103, 31690092 to X.-Y.C. and No. 31700263 to J.X.L.), the Ministry of

Agriculture of China (grant No. 2016ZX08010002-005 to L.J.W.), the Ministry of Science and Technology of China (grant No. 2016YFD0100500 to L.J.W.) and the Chinese Academy of Sciences (grant

Nos. XDB11030000, QYZDY-SSW-SMC026 and 153D31KYSB20160074 to X.-Y.C.). AUTHOR INFORMATION Author notes * These authors contributed equally: Jin-Quan Huang, Xin Fang. AUTHORS AND

AFFILIATIONS * State Key Laboratory of Plant Molecular Genetics, CAS Center for Excellence in Molecular Plant Sciences, Shanghai Institute of Plant Physiology and Ecology, University of CAS,

Chinese Academy of Sciences, Shanghai, China Jin-Quan Huang, Xiu Tian, Ping Chen, Jia-Ling Lin, Xiao-Xiang Guo, Jian-Xu Li, Zhen Fan, Wei-Meng Song, Fang-Yan Chen, Ruzha Ahati, Ling-Jian

Wang & Xiao-Ya Chen * State Key Laboratory of Phytochemistry and Plant Resources in West China, Kunming Institute of Botany, Chinese Academy of Sciences, Kunming, China Xin Fang * School

of Life Science and Technology, ShanghaiTech University, Shanghai, China Jia-Ling Lin & Xiao-Ya Chen * Shanghai Key Laboratory of Plant Functional Genomics and Resources, Shanghai

Chenshan Botanical Garden, Shanghai Chenshan Plant Science Research Center, Chinese Academy of Sciences, Shanghai, China Qing Zhao, Cathie Martin & Xiao-Ya Chen * John Innes Centre,

Norwich, UK Cathie Martin Authors * Jin-Quan Huang View author publications You can also search for this author inPubMed Google Scholar * Xin Fang View author publications You can also

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author publications You can also search for this author inPubMed Google Scholar * Wei-Meng Song View author publications You can also search for this author inPubMed Google Scholar *

Fang-Yan Chen View author publications You can also search for this author inPubMed Google Scholar * Ruzha Ahati View author publications You can also search for this author inPubMed Google

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this author inPubMed Google Scholar CONTRIBUTIONS J.-Q.H., X.F., X.T. and X.-Y.C. designed and managed the study. C.M., X.F., X.T., W.-M.S., Q.Z. and L.-J.W. discussed results and provided

advice. J.-Q.H. isolated genes and characterized enzymes. J.-Q.H., X.T., J.-L.L., X.-X.G., R.A. and F.-Y.C. isolated compounds and performed LC–MS and GC–MS analyses. X.F. and Z.F. analyzed

the NMR data. J.-Q.H., P.C. and Q.Z. performed bioinformatic analysis. J.-X.L. modeled the enzymes. X.-Y.C., J.-Q.H., X.F. and C.M. wrote the manuscript with input from all authors.

CORRESPONDING AUTHOR Correspondence to Xiao-Ya Chen. ETHICS DECLARATIONS COMPETING INTERESTS The authors declare no competing interests. ADDITIONAL INFORMATION PUBLISHER’S NOTE Springer

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products by a specialized detoxification enzyme. _Nat Chem Biol_ 16, 250–256 (2020). https://doi.org/10.1038/s41589-019-0446-8 Download citation * Received: 30 July 2019 * Accepted: 26

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