X-ray Magnetic Circular Dichroism of Pseudomonas aeruginosa Nickel(II) Azurin
We show that X-ray magnetic circular dichroism (XMCD) can be employed to probe the oxidation states and other electronic structural features of nickel active sites in proteins. As a calibration standard, we have measured XMCD and X-ray absorption (XAS) spectra for the nickel(II) derivative of Pseudo...
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| Veröffentlicht in: | Journal of the American Chemical Society 2004-05, Vol.126 (18), p.5859-5866 |
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| container_title | Journal of the American Chemical Society |
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| creator | Funk, Tobias Kennepohl, Pierre Di Bilio, Angel J Wehbi, William A Young, Anthony T Friedrich, Stephan Arenholz, Elke Gray, Harry B Cramer, Stephen P |
| description | We show that X-ray magnetic circular dichroism (XMCD) can be employed to probe the oxidation states and other electronic structural features of nickel active sites in proteins. As a calibration standard, we have measured XMCD and X-ray absorption (XAS) spectra for the nickel(II) derivative of Pseudomonas aeruginosa azurin (NiAz). Our analysis of these spectra confirms that the electronic ground state of NiAz is high-spin (S = 1); we also find that the L3-centroid energy is 853.1(1) eV, the branching ratio is 0.722(4), and the magnetic moment is 1.9(4) μB. Density functional theory (DFT) calculations on model NiAz structures establish that orbitals 3d x 2 - y 2 and 3d z 2 are the two valence holes in the high-spin Ni(II) ground state, and in accord with the experimentally determined orbital magnetic moment, the DFT results also demonstrate that both holes are highly delocalized, with 3d x 2 - y 2 having much greater ligand character. |
| doi_str_mv | 10.1021/ja036218d |
| format | Article |
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As a calibration standard, we have measured XMCD and X-ray absorption (XAS) spectra for the nickel(II) derivative of Pseudomonas aeruginosa azurin (NiAz). Our analysis of these spectra confirms that the electronic ground state of NiAz is high-spin (S = 1); we also find that the L3-centroid energy is 853.1(1) eV, the branching ratio is 0.722(4), and the magnetic moment is 1.9(4) μB. Density functional theory (DFT) calculations on model NiAz structures establish that orbitals 3d x 2 - y 2 and 3d z 2 are the two valence holes in the high-spin Ni(II) ground state, and in accord with the experimentally determined orbital magnetic moment, the DFT results also demonstrate that both holes are highly delocalized, with 3d x 2 - y 2 having much greater ligand character.</description><identifier>ISSN: 0002-7863</identifier><identifier>EISSN: 1520-5126</identifier><identifier>DOI: 10.1021/ja036218d</identifier><identifier>PMID: 15125678</identifier><identifier>CODEN: JACSAT</identifier><language>eng</language><publisher>Washington, DC: American Chemical Society</publisher><subject>Azurin - chemistry ; Biological and medical sciences ; Circular Dichroism - methods ; Copper - chemistry ; Crystallography, X-Ray ; Electronic structure ; Fundamental and applied biological sciences. Psychology ; Ligands ; Magnetics ; Models, Molecular ; Molecular biophysics ; Molecular Conformation ; Nickel - chemistry ; Pseudomonas aeruginosa - chemistry ; Structure in molecular biology ; X-Rays</subject><ispartof>Journal of the American Chemical Society, 2004-05, Vol.126 (18), p.5859-5866</ispartof><rights>Copyright © 2004 American Chemical Society</rights><rights>2004 INIST-CNRS</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a414t-6fa1e95c79832c7af87683d2a40f42c6f915eb65e17302781cf7d33fed7465eb3</citedby><cites>FETCH-LOGICAL-a414t-6fa1e95c79832c7af87683d2a40f42c6f915eb65e17302781cf7d33fed7465eb3</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://pubs.acs.org/doi/pdf/10.1021/ja036218d$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/ja036218d$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>314,780,784,2765,27076,27924,27925,56738,56788</link.rule.ids><backlink>$$Uhttp://pascal-francis.inist.fr/vibad/index.php?action=getRecordDetail&idt=15752702$$DView record in Pascal Francis$$Hfree_for_read</backlink><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/15125678$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Funk, Tobias</creatorcontrib><creatorcontrib>Kennepohl, Pierre</creatorcontrib><creatorcontrib>Di Bilio, Angel J</creatorcontrib><creatorcontrib>Wehbi, William A</creatorcontrib><creatorcontrib>Young, Anthony T</creatorcontrib><creatorcontrib>Friedrich, Stephan</creatorcontrib><creatorcontrib>Arenholz, Elke</creatorcontrib><creatorcontrib>Gray, Harry B</creatorcontrib><creatorcontrib>Cramer, Stephen P</creatorcontrib><title>X-ray Magnetic Circular Dichroism of Pseudomonas aeruginosa Nickel(II) Azurin</title><title>Journal of the American Chemical Society</title><addtitle>J. Am. Chem. Soc</addtitle><description>We show that X-ray magnetic circular dichroism (XMCD) can be employed to probe the oxidation states and other electronic structural features of nickel active sites in proteins. As a calibration standard, we have measured XMCD and X-ray absorption (XAS) spectra for the nickel(II) derivative of Pseudomonas aeruginosa azurin (NiAz). Our analysis of these spectra confirms that the electronic ground state of NiAz is high-spin (S = 1); we also find that the L3-centroid energy is 853.1(1) eV, the branching ratio is 0.722(4), and the magnetic moment is 1.9(4) μB. Density functional theory (DFT) calculations on model NiAz structures establish that orbitals 3d x 2 - y 2 and 3d z 2 are the two valence holes in the high-spin Ni(II) ground state, and in accord with the experimentally determined orbital magnetic moment, the DFT results also demonstrate that both holes are highly delocalized, with 3d x 2 - y 2 having much greater ligand character.</description><subject>Azurin - chemistry</subject><subject>Biological and medical sciences</subject><subject>Circular Dichroism - methods</subject><subject>Copper - chemistry</subject><subject>Crystallography, X-Ray</subject><subject>Electronic structure</subject><subject>Fundamental and applied biological sciences. Psychology</subject><subject>Ligands</subject><subject>Magnetics</subject><subject>Models, Molecular</subject><subject>Molecular biophysics</subject><subject>Molecular Conformation</subject><subject>Nickel - chemistry</subject><subject>Pseudomonas aeruginosa - chemistry</subject><subject>Structure in molecular biology</subject><subject>X-Rays</subject><issn>0002-7863</issn><issn>1520-5126</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2004</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNpt0MtKAzEUBuAgitbqwheQ2Si6GM1tkumy1FvVakUFd-E0k2jqzESTDlif3pEWdeEqnJyPn8OP0A7BRwRTcjwFzAQlebGCOiSjOM0IFauogzGmqcwF20CbMU7bkdOcrKMN0oJMyLyDRk9pgHkygufazJxOBi7opoSQnDj9EryLVeJtMo6mKXzla4gJmNA8u9pHSG6cfjXlwXB4mPQ_m-DqLbRmoYxme_l20ePZ6cPgIr2-PR8O-tcpcMJnqbBATC_TspczqiXYXIqcFRQ4tpxqYXskMxORGSIZpjIn2sqCMWsKydvfCeui_UXuW_DvjYkzVbmoTVlCbXwTlSQ9TATnLTxcQB18jMFY9RZcBWGuCFbf3amf7lq7uwxtJpUpfuWyrBbsLQFEDaUNUGsX_ziZUYlp69KFc3FmPn72EF6VkExm6mF8r57wiI8v767U6DcXdFRT34S67e6fA78AOHuQLg</recordid><startdate>20040512</startdate><enddate>20040512</enddate><creator>Funk, Tobias</creator><creator>Kennepohl, Pierre</creator><creator>Di Bilio, Angel J</creator><creator>Wehbi, William A</creator><creator>Young, Anthony T</creator><creator>Friedrich, Stephan</creator><creator>Arenholz, Elke</creator><creator>Gray, Harry B</creator><creator>Cramer, Stephen P</creator><general>American Chemical Society</general><scope>BSCLL</scope><scope>IQODW</scope><scope>CGR</scope><scope>CUY</scope><scope>CVF</scope><scope>ECM</scope><scope>EIF</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope></search><sort><creationdate>20040512</creationdate><title>X-ray Magnetic Circular Dichroism of Pseudomonas aeruginosa Nickel(II) Azurin</title><author>Funk, Tobias ; Kennepohl, Pierre ; Di Bilio, Angel J ; Wehbi, William A ; Young, Anthony T ; Friedrich, Stephan ; Arenholz, Elke ; Gray, Harry B ; Cramer, Stephen P</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a414t-6fa1e95c79832c7af87683d2a40f42c6f915eb65e17302781cf7d33fed7465eb3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2004</creationdate><topic>Azurin - chemistry</topic><topic>Biological and medical sciences</topic><topic>Circular Dichroism - methods</topic><topic>Copper - chemistry</topic><topic>Crystallography, X-Ray</topic><topic>Electronic structure</topic><topic>Fundamental and applied biological sciences. Psychology</topic><topic>Ligands</topic><topic>Magnetics</topic><topic>Models, Molecular</topic><topic>Molecular biophysics</topic><topic>Molecular Conformation</topic><topic>Nickel - chemistry</topic><topic>Pseudomonas aeruginosa - chemistry</topic><topic>Structure in molecular biology</topic><topic>X-Rays</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Funk, Tobias</creatorcontrib><creatorcontrib>Kennepohl, Pierre</creatorcontrib><creatorcontrib>Di Bilio, Angel J</creatorcontrib><creatorcontrib>Wehbi, William A</creatorcontrib><creatorcontrib>Young, Anthony T</creatorcontrib><creatorcontrib>Friedrich, Stephan</creatorcontrib><creatorcontrib>Arenholz, Elke</creatorcontrib><creatorcontrib>Gray, Harry B</creatorcontrib><creatorcontrib>Cramer, Stephen P</creatorcontrib><collection>Istex</collection><collection>Pascal-Francis</collection><collection>Medline</collection><collection>MEDLINE</collection><collection>MEDLINE (Ovid)</collection><collection>MEDLINE</collection><collection>MEDLINE</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><jtitle>Journal of the American Chemical Society</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Funk, Tobias</au><au>Kennepohl, Pierre</au><au>Di Bilio, Angel J</au><au>Wehbi, William A</au><au>Young, Anthony T</au><au>Friedrich, Stephan</au><au>Arenholz, Elke</au><au>Gray, Harry B</au><au>Cramer, Stephen P</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>X-ray Magnetic Circular Dichroism of Pseudomonas aeruginosa Nickel(II) Azurin</atitle><jtitle>Journal of the American Chemical Society</jtitle><addtitle>J. Am. Chem. Soc</addtitle><date>2004-05-12</date><risdate>2004</risdate><volume>126</volume><issue>18</issue><spage>5859</spage><epage>5866</epage><pages>5859-5866</pages><issn>0002-7863</issn><eissn>1520-5126</eissn><coden>JACSAT</coden><abstract>We show that X-ray magnetic circular dichroism (XMCD) can be employed to probe the oxidation states and other electronic structural features of nickel active sites in proteins. As a calibration standard, we have measured XMCD and X-ray absorption (XAS) spectra for the nickel(II) derivative of Pseudomonas aeruginosa azurin (NiAz). Our analysis of these spectra confirms that the electronic ground state of NiAz is high-spin (S = 1); we also find that the L3-centroid energy is 853.1(1) eV, the branching ratio is 0.722(4), and the magnetic moment is 1.9(4) μB. Density functional theory (DFT) calculations on model NiAz structures establish that orbitals 3d x 2 - y 2 and 3d z 2 are the two valence holes in the high-spin Ni(II) ground state, and in accord with the experimentally determined orbital magnetic moment, the DFT results also demonstrate that both holes are highly delocalized, with 3d x 2 - y 2 having much greater ligand character.</abstract><cop>Washington, DC</cop><pub>American Chemical Society</pub><pmid>15125678</pmid><doi>10.1021/ja036218d</doi><tpages>8</tpages><oa>free_for_read</oa></addata></record> |
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| subjects | Azurin - chemistry Biological and medical sciences Circular Dichroism - methods Copper - chemistry Crystallography, X-Ray Electronic structure Fundamental and applied biological sciences. Psychology Ligands Magnetics Models, Molecular Molecular biophysics Molecular Conformation Nickel - chemistry Pseudomonas aeruginosa - chemistry Structure in molecular biology X-Rays |
| title | X-ray Magnetic Circular Dichroism of Pseudomonas aeruginosa Nickel(II) Azurin |
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