Document Detail


Peptide cyclization catalysed by the thioesterase domain of tyrocidine synthetase.
MedLine Citation:
PMID:  11001063     Owner:  NLM     Status:  MEDLINE    
Abstract/OtherAbstract:
In the biosynthesis of many macrocyclic natural products by multidomain megasynthases, a carboxy-terminal thioesterase (TE) domain is involved in cyclization and product release; however, it has not been determined whether TE domains can catalyse macrocyclization (and elongation in the case of symmetric cyclic peptides) independently of upstream domains. The inability to decouple the TE cyclization step from earlier chain assembly steps has precluded determination of TE substrate specificity, which is important for the engineered biosynthesis of new compounds. Here we report that the excised TE domain from tyrocidine synthetase efficiently catalyses cyclization of a decapeptide-thioester to form the antibiotic tyrocidine A, and can catalyse pentapeptide-thioester dimerization followed by cyclization to form the antibiotic gramicidin S. By systematically varying the decapeptide-thioester substrate and comparing cyclization rates, we also show that only two residues (one near each end of the decapeptide) are critical for cyclization. This specificity profile indicates that the tyrocidine synthetase TE, and by analogy many other TE domains, will be able to cyclize and release a broad range of new substrates and products produced by engineered enzymatic assembly lines.
Authors:
J W Trauger; R M Kohli; H D Mootz; M A Marahiel; C T Walsh
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Publication Detail:
Type:  Journal Article; Research Support, Non-U.S. Gov't; Research Support, U.S. Gov't, P.H.S.    
Journal Detail:
Title:  Nature     Volume:  407     ISSN:  0028-0836     ISO Abbreviation:  Nature     Publication Date:  2000 Sep 
Date Detail:
Created Date:  2000-10-19     Completed Date:  2000-10-19     Revised Date:  2006-11-15    
Medline Journal Info:
Nlm Unique ID:  0410462     Medline TA:  Nature     Country:  ENGLAND    
Other Details:
Languages:  eng     Pagination:  215-8     Citation Subset:  IM    
Affiliation:
Department of Biological Chemistry and Molecular Pharmacology, Harvard Medical School, Boston, Massachusetts 02115, USA.
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MeSH Terms
Descriptor/Qualifier:
Bacillus
Catalysis
Cysteamine / analogs & derivatives,  metabolism
Esterases / metabolism*
Gramicidin / metabolism
Mutagenesis
Oligopeptides / metabolism
Peptide Synthases / metabolism*
Peptides / chemical synthesis,  metabolism
Peptides, Cyclic / metabolism*
Protein Structure, Tertiary
Recombinant Proteins
Substrate Specificity
Tyrocidine / metabolism
Chemical
Reg. No./Substance:
0/Oligopeptides; 0/Peptides; 0/Peptides, Cyclic; 0/Recombinant Proteins; 0/Tyrocidine; 1405-97-6/Gramicidin; 60-23-1/Cysteamine; EC 3.1.-/Esterases; EC 6.3.2.-/Peptide Synthases; EC 6.3.2.-/tyrocidine synthetase

From MEDLINE®/PubMed®, a database of the U.S. National Library of Medicine


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