Deciphering Radical Transport in the Large Subunit of Class I Ribonucleotide Reductase
Incorporation of 2,3,6-trifluorotyrosine (F[subscript 3]Y) and a rhenium bipyridine ([Re]) photooxidant into a peptide corresponding to the C-terminus of the β protein (βC19) of Escherichia coli ribonucleotide reductase (RNR) allows for the temporal monitoring of radical transport into the α2 subuni...
| Main Authors: | , , , , |
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| Format: | Article |
| Language: | en_US |
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American Chemical Society (ACS)
2013
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| Online Access: | http://hdl.handle.net/1721.1/82555 https://orcid.org/0000-0001-8076-4489 https://orcid.org/0000-0002-4507-1115 |
| _version_ | 1826214278364921856 |
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| author | Stubbe, JoAnne Nocera, Daniel G. Holder, Patrick Pizano, Arturo Alejandro Anderson, Bryce Lane |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Stubbe, JoAnne Nocera, Daniel G. Holder, Patrick Pizano, Arturo Alejandro Anderson, Bryce Lane |
| author_sort | Stubbe, JoAnne |
| collection | MIT |
| description | Incorporation of 2,3,6-trifluorotyrosine (F[subscript 3]Y) and a rhenium bipyridine ([Re]) photooxidant into a peptide corresponding to the C-terminus of the β protein (βC19) of Escherichia coli ribonucleotide reductase (RNR) allows for the temporal monitoring of radical transport into the α2 subunit of RNR. Injection of the photogenerated F[subscript 3]Y radical from the [Re]–F[subscript 3]Y−βC19 peptide into the surface accessible Y731 of the α2 subunit is only possible when the second Y730 is present. With the Y–Y established, radical transport occurs with a rate constant of 3 × 10[superscript 5] s[superscript –1]. Point mutations that disrupt the Y–Y dyad shut down radical transport. The ability to obviate radical transport by disrupting the hydrogen bonding network of the amino acids composing the colinear proton-coupled electron transfer pathway in α2 suggests a finely tuned evolutionary adaptation of RNR to control the transport of radicals in this enzyme. |
| first_indexed | 2024-09-23T10:40:43Z |
| format | Article |
| id | mit-1721.1/82555 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T10:40:43Z |
| publishDate | 2013 |
| publisher | American Chemical Society (ACS) |
| record_format | dspace |
| spelling | mit-1721.1/825552022-09-27T14:11:34Z Deciphering Radical Transport in the Large Subunit of Class I Ribonucleotide Reductase Stubbe, JoAnne Nocera, Daniel G. Holder, Patrick Pizano, Arturo Alejandro Anderson, Bryce Lane Massachusetts Institute of Technology. Department of Chemistry Holder, Patrick Pizano, Arturo Alejandro Anderson, Bryce Lane Stubbe, JoAnne Nocera, Daniel G. Incorporation of 2,3,6-trifluorotyrosine (F[subscript 3]Y) and a rhenium bipyridine ([Re]) photooxidant into a peptide corresponding to the C-terminus of the β protein (βC19) of Escherichia coli ribonucleotide reductase (RNR) allows for the temporal monitoring of radical transport into the α2 subunit of RNR. Injection of the photogenerated F[subscript 3]Y radical from the [Re]–F[subscript 3]Y−βC19 peptide into the surface accessible Y731 of the α2 subunit is only possible when the second Y730 is present. With the Y–Y established, radical transport occurs with a rate constant of 3 × 10[superscript 5] s[superscript –1]. Point mutations that disrupt the Y–Y dyad shut down radical transport. The ability to obviate radical transport by disrupting the hydrogen bonding network of the amino acids composing the colinear proton-coupled electron transfer pathway in α2 suggests a finely tuned evolutionary adaptation of RNR to control the transport of radicals in this enzyme. National Institutes of Health (GM 47274) National Institutes of Health (GM 29595) National Institutes of Health (Fellowship GM 087034) 2013-11-22T19:00:26Z 2013-11-22T19:00:26Z 2011-11 2011-09 Article http://purl.org/eprint/type/JournalArticle 0002-7863 1520-5126 http://hdl.handle.net/1721.1/82555 Holder, Patrick G., Arturo A. Pizano, Bryce L. Anderson, JoAnne Stubbe, and Daniel G. Nocera. “Deciphering Radical Transport in the Large Subunit of Class I Ribonucleotide Reductase.” Journal of the American Chemical Society 134, no. 2 (January 18, 2012): 1172-1180. https://orcid.org/0000-0001-8076-4489 https://orcid.org/0000-0002-4507-1115 en_US http://dx.doi.org/10.1021/ja209016j Journal of the American Chemical Society Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use. application/pdf American Chemical Society (ACS) PMC |
| spellingShingle | Stubbe, JoAnne Nocera, Daniel G. Holder, Patrick Pizano, Arturo Alejandro Anderson, Bryce Lane Deciphering Radical Transport in the Large Subunit of Class I Ribonucleotide Reductase |
| title | Deciphering Radical Transport in the Large Subunit of Class I Ribonucleotide Reductase |
| title_full | Deciphering Radical Transport in the Large Subunit of Class I Ribonucleotide Reductase |
| title_fullStr | Deciphering Radical Transport in the Large Subunit of Class I Ribonucleotide Reductase |
| title_full_unstemmed | Deciphering Radical Transport in the Large Subunit of Class I Ribonucleotide Reductase |
| title_short | Deciphering Radical Transport in the Large Subunit of Class I Ribonucleotide Reductase |
| title_sort | deciphering radical transport in the large subunit of class i ribonucleotide reductase |
| url | http://hdl.handle.net/1721.1/82555 https://orcid.org/0000-0001-8076-4489 https://orcid.org/0000-0002-4507-1115 |
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