Structural basis for catalysis by human lipoyl synthase

Abstract Lipoic acid is an essential cofactor in five mitochondrial multiprotein complexes. In each complex, it is tethered in an amide linkage to the side chain of a conserved lysyl residue on a lipoyl carrier protein or lipoyl domain to afford the lipoyl cofactor. Lipoyl synthase catalyzes the las...

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Main Authors: Olga A. Esakova, Douglas M. Warui, Syam Sundar Neti, John N. Alumasa, Squire J. Booker
Format: Article
Language:English
Published: Nature Portfolio 2025-07-01
Series:Nature Communications
Online Access:https://doi.org/10.1038/s41467-025-61393-x
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author Olga A. Esakova
Douglas M. Warui
Syam Sundar Neti
John N. Alumasa
Squire J. Booker
author_facet Olga A. Esakova
Douglas M. Warui
Syam Sundar Neti
John N. Alumasa
Squire J. Booker
author_sort Olga A. Esakova
collection DOAJ
description Abstract Lipoic acid is an essential cofactor in five mitochondrial multiprotein complexes. In each complex, it is tethered in an amide linkage to the side chain of a conserved lysyl residue on a lipoyl carrier protein or lipoyl domain to afford the lipoyl cofactor. Lipoyl synthase catalyzes the last step in the biosynthesis of the lipoyl cofactor, the addition of two sulfur atoms to carbons 6 and 8 of an octanoyllysyl residue of the H protein, the lipoyl carrier protein of the glycine cleavage system. Lipoyl synthase, a member of the radical S-adenosylmethionine superfamily, contains two [Fe4S4] clusters, one of which is sacrificed during catalysis to supply the appended sulfur atoms. Herein, we use X-ray crystallography to characterize several stages in lipoyl synthase catalysis and present a structure of an intermediate wherein the enzyme is cross-linked to the H protein substrate through a 6-mercaptooctanoyl ligand to a [Fe3S4] cluster.
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institution Kabale University
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publishDate 2025-07-01
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spelling doaj-art-3c483ea04efd4cd6b07d760d1cd2d1f32025-08-20T03:43:10ZengNature PortfolioNature Communications2041-17232025-07-0116111210.1038/s41467-025-61393-xStructural basis for catalysis by human lipoyl synthaseOlga A. Esakova0Douglas M. Warui1Syam Sundar Neti2John N. Alumasa3Squire J. Booker4Department of Chemistry, The Pennsylvania State UniversityDepartment of Chemistry, The Pennsylvania State UniversityDepartment of Chemistry, The Pennsylvania State UniversityDepartment of Chemistry, The Pennsylvania State UniversityDepartment of Chemistry, The Pennsylvania State UniversityAbstract Lipoic acid is an essential cofactor in five mitochondrial multiprotein complexes. In each complex, it is tethered in an amide linkage to the side chain of a conserved lysyl residue on a lipoyl carrier protein or lipoyl domain to afford the lipoyl cofactor. Lipoyl synthase catalyzes the last step in the biosynthesis of the lipoyl cofactor, the addition of two sulfur atoms to carbons 6 and 8 of an octanoyllysyl residue of the H protein, the lipoyl carrier protein of the glycine cleavage system. Lipoyl synthase, a member of the radical S-adenosylmethionine superfamily, contains two [Fe4S4] clusters, one of which is sacrificed during catalysis to supply the appended sulfur atoms. Herein, we use X-ray crystallography to characterize several stages in lipoyl synthase catalysis and present a structure of an intermediate wherein the enzyme is cross-linked to the H protein substrate through a 6-mercaptooctanoyl ligand to a [Fe3S4] cluster.https://doi.org/10.1038/s41467-025-61393-x
spellingShingle Olga A. Esakova
Douglas M. Warui
Syam Sundar Neti
John N. Alumasa
Squire J. Booker
Structural basis for catalysis by human lipoyl synthase
Nature Communications
title Structural basis for catalysis by human lipoyl synthase
title_full Structural basis for catalysis by human lipoyl synthase
title_fullStr Structural basis for catalysis by human lipoyl synthase
title_full_unstemmed Structural basis for catalysis by human lipoyl synthase
title_short Structural basis for catalysis by human lipoyl synthase
title_sort structural basis for catalysis by human lipoyl synthase
url https://doi.org/10.1038/s41467-025-61393-x
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