S ‐Adenosyl‐ l ‐ethionine is a Catalytically Competent Analog of S ‐Adenosyl‐ l ‐methionine (SAM) in the Radical SAM Enzyme HydG
Abstract
Abstract Radical S ‐adenosyl‐ l ‐methionine (SAM) enzymes initiate biological radical reactions with the 5′‐deoxyadenosyl radical (5′‐dAdo . ). A [4Fe‐4S] + cluster reductively cleaves SAM to form the Ω organometallic intermediate in which the 5′‐deoxyadenosyl moiety is directly bound to the unique iron of the [4Fe‐4S] cluster, with subsequent liberation of 5′‐dAdo . . We present synthesis of the SAM analog S ‐adenosyl‐ l ‐ethionine (SAE) and show SAE is a mechanistically equivalent SAM‐alternative for HydG, both supporting enzymatic turnover of substrate tyrosine and forming the organometallic intermediate Ω. Photolysis of SAE‐bound HydG forms an ethyl radical trapped in the active site. The ethyl radical withstands prolonged storage at 77 K and its EPR signal is only partially lost upon annealing at 100 K, making it significantly less reactive than the methyl radical formed by SAM photolysis. Upon annealing above 77 K, the ethyl radical adds to the [4Fe‐4S] 2+ cluster, generating an ethyl‐[4Fe‐4S] 3+ organometallic species termed Ω E .
- Authors:
-
[1];
[2];
[1];
[1];
[1];
[1];
[2];
[1]
- Department of Chemistry &, Biochemistry Montana State University Bozeman MT 59717 USA
- Department of Chemistry Northwestern University Evanston IL 60208 USA
- Publication Date:
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1786119
- Resource Type:
- Publisher's Accepted Manuscript
- Journal Name:
- Angewandte Chemie
- Additional Journal Information:
- Journal Name: Angewandte Chemie Journal Volume: 133 Journal Issue: 9; Journal ID: ISSN 0044-8249
- Publisher:
- Wiley Blackwell (John Wiley & Sons)
- Country of Publication:
- Germany
- Language:
- English
Citation Formats
Impano, Stella, Yang, Hao, Shepard, Eric M., Swimley, Ryan, Pagnier, Adrien, Broderick, William E., Hoffman, Brian M., and Broderick, Joan B. S ‐Adenosyl‐ l ‐ethionine is a Catalytically Competent Analog of S ‐Adenosyl‐ l ‐methionine (SAM) in the Radical SAM Enzyme HydG. Germany: N. p., 2021.
Web. doi:10.1002/ange.202014337.
Impano, Stella, Yang, Hao, Shepard, Eric M., Swimley, Ryan, Pagnier, Adrien, Broderick, William E., Hoffman, Brian M., & Broderick, Joan B. S ‐Adenosyl‐ l ‐ethionine is a Catalytically Competent Analog of S ‐Adenosyl‐ l ‐methionine (SAM) in the Radical SAM Enzyme HydG. Germany. https://doi.org/10.1002/ange.202014337
Impano, Stella, Yang, Hao, Shepard, Eric M., Swimley, Ryan, Pagnier, Adrien, Broderick, William E., Hoffman, Brian M., and Broderick, Joan B. Mon .
"S ‐Adenosyl‐ l ‐ethionine is a Catalytically Competent Analog of S ‐Adenosyl‐ l ‐methionine (SAM) in the Radical SAM Enzyme HydG". Germany. https://doi.org/10.1002/ange.202014337.
@article{osti_1786119,
title = {S ‐Adenosyl‐ l ‐ethionine is a Catalytically Competent Analog of S ‐Adenosyl‐ l ‐methionine (SAM) in the Radical SAM Enzyme HydG},
author = {Impano, Stella and Yang, Hao and Shepard, Eric M. and Swimley, Ryan and Pagnier, Adrien and Broderick, William E. and Hoffman, Brian M. and Broderick, Joan B.},
abstractNote = {Abstract Radical S ‐adenosyl‐ l ‐methionine (SAM) enzymes initiate biological radical reactions with the 5′‐deoxyadenosyl radical (5′‐dAdo . ). A [4Fe‐4S] + cluster reductively cleaves SAM to form the Ω organometallic intermediate in which the 5′‐deoxyadenosyl moiety is directly bound to the unique iron of the [4Fe‐4S] cluster, with subsequent liberation of 5′‐dAdo . . We present synthesis of the SAM analog S ‐adenosyl‐ l ‐ethionine (SAE) and show SAE is a mechanistically equivalent SAM‐alternative for HydG, both supporting enzymatic turnover of substrate tyrosine and forming the organometallic intermediate Ω. Photolysis of SAE‐bound HydG forms an ethyl radical trapped in the active site. The ethyl radical withstands prolonged storage at 77 K and its EPR signal is only partially lost upon annealing at 100 K, making it significantly less reactive than the methyl radical formed by SAM photolysis. Upon annealing above 77 K, the ethyl radical adds to the [4Fe‐4S] 2+ cluster, generating an ethyl‐[4Fe‐4S] 3+ organometallic species termed Ω E .},
doi = {10.1002/ange.202014337},
journal = {Angewandte Chemie},
number = 9,
volume = 133,
place = {Germany},
year = {Mon Jan 18 00:00:00 EST 2021},
month = {Mon Jan 18 00:00:00 EST 2021}
}
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