DC Field | Value | Language |
---|---|---|
dc.contributor.author | Kwak, Yeonju | ko |
dc.contributor.author | Jiang, Wei | ko |
dc.contributor.author | Dassama, Laura M. K. | ko |
dc.contributor.author | Park, Kiyoung | ko |
dc.contributor.author | Bell, Caleb B., III | ko |
dc.contributor.author | Liu, Lei V. | ko |
dc.contributor.author | Wong, Shaun D. | ko |
dc.contributor.author | Saito, Makina | ko |
dc.contributor.author | Kobayashi, Yasuhiro | ko |
dc.contributor.author | Kitao, Shinji | ko |
dc.contributor.author | Seto, Makoto | ko |
dc.contributor.author | Yoda, Yoshitaka | ko |
dc.contributor.author | Alp, E. Ercan | ko |
dc.contributor.author | Zhao, Jiyong | ko |
dc.contributor.author | Bollinger, J. Martin, Jr. | ko |
dc.contributor.author | Krebs, Carsten | ko |
dc.contributor.author | Solomon, Edward I. | ko |
dc.date.accessioned | 2015-11-20T09:13:00Z | - |
dc.date.available | 2015-11-20T09:13:00Z | - |
dc.date.created | 2014-08-05 | - |
dc.date.created | 2014-08-05 | - |
dc.date.created | 2014-08-05 | - |
dc.date.created | 2014-08-05 | - |
dc.date.issued | 2013-11 | - |
dc.identifier.citation | JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, v.135, no.46, pp.17573 - 17584 | - |
dc.identifier.issn | 0002-7863 | - |
dc.identifier.uri | http://hdl.handle.net/10203/201091 | - |
dc.description.abstract | The class Ic ribonucleotide reductase (RNR) from Chlamydia trachomatis (Ct) utilizes a Mn/Fe hetero-binuclear cofactor, rather than the Fe/Fe cofactor found in the beta (R2) subunit of the class Ia enzymes, to react with O-2. This reaction produces a stable (MnFeIII)-Fe-IV cofactor that initiates a radical, which transfers to the adjacent alpha (R1) subunit and reacts with the substrate. We have studied the (MnFeIII)-Fe-IV cofactor using nuclear resonance vibrational spectroscopy (NRVS) and absorption (Abs)/circular dichroism (CD)/magnetic CD (MCD)/variable temperature, variable field (VTVH) MCD spectroscopies to obtain detailed insight into its geometric/electronic structure and to correlate structure with reactivity; NRVS focuses on the Fe-III, whereas MCD reflects the spin-allowed transitions mostly on the Mn-IV. We have evaluated 18 systematically varied structures. Comparison of the simulated NRVS spectra to the experimental data shows that the cofactor has one carboxylate bridge, with Mn-IV at the site proximal to Phe(127). Abs/CD/MCD/VTVH MCD data exhibit 12 transitions that are assigned as d-d and oxo and OH- to metal charge-transfer (CT) transitions. Assignments are based on MCD/Abs intensity ratios, transition energies, polarizations, and derivative-shaped pseudo-A term CT transitions. Correlating these results with TD-DFT calculations defines the (MnFeIII)-Fe-IV cofactor as having a mu-oxo, mu-hydroxo core and a terminal hydroxo ligand on the Mn-IV. From DFT calculations, the Mn-IV at site 1 is necessary to tune the redox potential to a value similar to that of the tyrosine radical in class La RNR, and the OH- terminal ligand on this Mn-IV provides a high proton affinity that could gate radical translocation to the alpha (R1) subunit. | - |
dc.language | English | - |
dc.publisher | AMER CHEMICAL SOC | - |
dc.title | Geometric and Electronic Structure of the Mn(IV)Fe(III) Cofactor in Class Ic Ribonucleotide Reductase: Correlation to the Class la Binuclear Non-Heme Iron Enzyme | - |
dc.type | Article | - |
dc.identifier.wosid | 000327413300048 | - |
dc.identifier.scopusid | 2-s2.0-84888347732 | - |
dc.type.rims | ART | - |
dc.citation.volume | 135 | - |
dc.citation.issue | 46 | - |
dc.citation.beginningpage | 17573 | - |
dc.citation.endingpage | 17584 | - |
dc.citation.publicationname | JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | - |
dc.identifier.doi | 10.1021/ja409510d | - |
dc.contributor.localauthor | Park, Kiyoung | - |
dc.contributor.nonIdAuthor | Kwak, Yeonju | - |
dc.contributor.nonIdAuthor | Jiang, Wei | - |
dc.contributor.nonIdAuthor | Dassama, Laura M. K. | - |
dc.contributor.nonIdAuthor | Bell, Caleb B., III | - |
dc.contributor.nonIdAuthor | Liu, Lei V. | - |
dc.contributor.nonIdAuthor | Wong, Shaun D. | - |
dc.contributor.nonIdAuthor | Saito, Makina | - |
dc.contributor.nonIdAuthor | Kobayashi, Yasuhiro | - |
dc.contributor.nonIdAuthor | Kitao, Shinji | - |
dc.contributor.nonIdAuthor | Seto, Makoto | - |
dc.contributor.nonIdAuthor | Yoda, Yoshitaka | - |
dc.contributor.nonIdAuthor | Alp, E. Ercan | - |
dc.contributor.nonIdAuthor | Zhao, Jiyong | - |
dc.contributor.nonIdAuthor | Bollinger, J. Martin, Jr. | - |
dc.contributor.nonIdAuthor | Krebs, Carsten | - |
dc.contributor.nonIdAuthor | Solomon, Edward I. | - |
dc.description.isOpenAccess | N | - |
dc.type.journalArticle | Article | - |
dc.subject.keywordPlus | RESONANCE VIBRATIONAL SPECTROSCOPY | - |
dc.subject.keywordPlus | DENSITY-FUNCTIONAL THEORY | - |
dc.subject.keywordPlus | TYROSYL RADICAL-DIIRON(III) COFACTOR | - |
dc.subject.keywordPlus | PROTONATED OXYGENIC LIGANDS | - |
dc.subject.keywordPlus | ATOMIC SCREENING CONSTANTS | - |
dc.subject.keywordPlus | CHLAMYDIA-TRACHOMATIS | - |
dc.subject.keywordPlus | INTERMEDIATE-X | - |
dc.subject.keywordPlus | MANGANESE(IV)/IRON(III) COFACTOR | - |
dc.subject.keywordPlus | MODEL COMPLEXES | - |
dc.subject.keywordPlus | DIIRON CLUSTER | - |
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