A tethered niacin-derived pincer complex with a nickel-carbon bond in lactate racemase
Lactic acid racemization is involved in lactate metabolism and cell wall assembly of many microorganisms. Lactate racemase (Lar) requires nickel, but the nickel-binding site and the role of three accessory proteins required for its activation remain enigmatic. We combined mass spectrometry and x-ray...
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Veröffentlicht in: | Science (American Association for the Advancement of Science) 2015-07, Vol.349 (6243), p.66-69 |
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creator | Desguin, Benoît Zhang, Tuo Soumillion, Patrice Hols, Pascal Hu, Jian Hausinger, Robert P. |
description | Lactic acid racemization is involved in lactate metabolism and cell wall assembly of many microorganisms. Lactate racemase (Lar) requires nickel, but the nickel-binding site and the role of three accessory proteins required for its activation remain enigmatic. We combined mass spectrometry and x-ray crystallography to show that Lar from Lactobacillus plantarum possesses an organometallic nickel-containing prosthetic group. A nicotinic acid mononucleotide derivative is tethered to Lys184 and forms a tridentate pincer complex that coordinates nickel through one metal-carbon and two metal-sulfur bonds, with His200 as another ligand. Although similar complexes have been previously synthesized, there was no prior evidence for the existence of pincer cofactors in enzymes. The wide distribution of the accessory proteins without Lar suggests that it may play a role in other enzymes. |
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(ANL), Argonne, IL (United States). Advanced Photon Source (APS)</creatorcontrib><description>Lactic acid racemization is involved in lactate metabolism and cell wall assembly of many microorganisms. Lactate racemase (Lar) requires nickel, but the nickel-binding site and the role of three accessory proteins required for its activation remain enigmatic. We combined mass spectrometry and x-ray crystallography to show that Lar from Lactobacillus plantarum possesses an organometallic nickel-containing prosthetic group. A nicotinic acid mononucleotide derivative is tethered to Lys184 and forms a tridentate pincer complex that coordinates nickel through one metal-carbon and two metal-sulfur bonds, with His200 as another ligand. Although similar complexes have been previously synthesized, there was no prior evidence for the existence of pincer cofactors in enzymes. The wide distribution of the accessory proteins without Lar suggests that it may play a role in other enzymes.</description><identifier>ISSN: 0036-8075</identifier><identifier>EISSN: 1095-9203</identifier><identifier>DOI: 10.1126/science.aab2272</identifier><identifier>CODEN: SCIEAS</identifier><language>eng</language><publisher>Washington: American Association for the Advancement of Science</publisher><subject>Accessories ; Bacteria ; Bacterial proteins ; Biochemistry ; Bonding ; Chemical bonds ; Derivatives ; Enzymes ; Lactates ; Nickel ; Proteins</subject><ispartof>Science (American Association for the Advancement of Science), 2015-07, Vol.349 (6243), p.66-69</ispartof><rights>Copyright © 2015 American Association for the Advancement of Science</rights><rights>Copyright © 2015, American Association for the Advancement of Science</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c388t-6761a6288aa990bab01b43fbfe93cfc486625361461c6b255d0d72cdd5cb4a863</citedby><cites>FETCH-LOGICAL-c388t-6761a6288aa990bab01b43fbfe93cfc486625361461c6b255d0d72cdd5cb4a863</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://www.jstor.org/stable/pdf/24748438$$EPDF$$P50$$Gjstor$$H</linktopdf><linktohtml>$$Uhttps://www.jstor.org/stable/24748438$$EHTML$$P50$$Gjstor$$H</linktohtml><link.rule.ids>230,314,780,784,803,885,2884,2885,27924,27925,58017,58250</link.rule.ids><backlink>$$Uhttps://www.osti.gov/biblio/1438858$$D View this record in Osti.gov$$Hfree_for_read</backlink></links><search><creatorcontrib>Desguin, Benoît</creatorcontrib><creatorcontrib>Zhang, Tuo</creatorcontrib><creatorcontrib>Soumillion, Patrice</creatorcontrib><creatorcontrib>Hols, Pascal</creatorcontrib><creatorcontrib>Hu, Jian</creatorcontrib><creatorcontrib>Hausinger, Robert P.</creatorcontrib><creatorcontrib>Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)</creatorcontrib><title>A tethered niacin-derived pincer complex with a nickel-carbon bond in lactate racemase</title><title>Science (American Association for the Advancement of Science)</title><description>Lactic acid racemization is involved in lactate metabolism and cell wall assembly of many microorganisms. Lactate racemase (Lar) requires nickel, but the nickel-binding site and the role of three accessory proteins required for its activation remain enigmatic. We combined mass spectrometry and x-ray crystallography to show that Lar from Lactobacillus plantarum possesses an organometallic nickel-containing prosthetic group. A nicotinic acid mononucleotide derivative is tethered to Lys184 and forms a tridentate pincer complex that coordinates nickel through one metal-carbon and two metal-sulfur bonds, with His200 as another ligand. Although similar complexes have been previously synthesized, there was no prior evidence for the existence of pincer cofactors in enzymes. The wide distribution of the accessory proteins without Lar suggests that it may play a role in other enzymes.</description><subject>Accessories</subject><subject>Bacteria</subject><subject>Bacterial proteins</subject><subject>Biochemistry</subject><subject>Bonding</subject><subject>Chemical bonds</subject><subject>Derivatives</subject><subject>Enzymes</subject><subject>Lactates</subject><subject>Nickel</subject><subject>Proteins</subject><issn>0036-8075</issn><issn>1095-9203</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2015</creationdate><recordtype>article</recordtype><recordid>eNpdkcuLFDEQh4MoOI6ePQlBL156N69Op4_LsrrCghf1Gqqrq5mMPcmYZHz890Zm8LCHoijqq-ePsddSXEmp7HXBQBHpCmBSalBP2EaKse9GJfRTthFC286JoX_OXpSyF6LlRr1h3254pbqjTDOPATDEbqYcfrbwGFq7zDEdjiv95r9C3XFoEH6ntUPIU4q82cxD5CtghUo8A9IBCr1kzxZYC726-C37-uHuy-199_D546fbm4cOtXO1s4OVYJVzAOMoJpiEnIxepoVGjQsaZ63qtZXGSrST6vtZzIPCee5xMuCs3rK3576p1ODbCyrhDlOMhNVL04b0rkHvz9Axpx8nKtUfQkFaV4iUTsXLURglRd9-tGXvHqH7dMqxneClHZWT2hrTqOszhTmVkmnxxxwOkP94Kfw_MfxFDH8Ro1W8OVfsS035P67MYFzbUv8FXdCHvw</recordid><startdate>20150703</startdate><enddate>20150703</enddate><creator>Desguin, Benoît</creator><creator>Zhang, Tuo</creator><creator>Soumillion, Patrice</creator><creator>Hols, Pascal</creator><creator>Hu, Jian</creator><creator>Hausinger, Robert P.</creator><general>American Association for the Advancement of Science</general><general>The American Association for the Advancement of Science</general><general>AAAS</general><scope>AAYXX</scope><scope>CITATION</scope><scope>7QF</scope><scope>7QG</scope><scope>7QL</scope><scope>7QP</scope><scope>7QQ</scope><scope>7QR</scope><scope>7SC</scope><scope>7SE</scope><scope>7SN</scope><scope>7SP</scope><scope>7SR</scope><scope>7SS</scope><scope>7T7</scope><scope>7TA</scope><scope>7TB</scope><scope>7TK</scope><scope>7TM</scope><scope>7U5</scope><scope>7U9</scope><scope>8BQ</scope><scope>8FD</scope><scope>C1K</scope><scope>F28</scope><scope>FR3</scope><scope>H8D</scope><scope>H8G</scope><scope>H94</scope><scope>JG9</scope><scope>JQ2</scope><scope>K9.</scope><scope>KR7</scope><scope>L7M</scope><scope>L~C</scope><scope>L~D</scope><scope>M7N</scope><scope>P64</scope><scope>RC3</scope><scope>OTOTI</scope></search><sort><creationdate>20150703</creationdate><title>A tethered niacin-derived pincer complex with a nickel-carbon bond in lactate racemase</title><author>Desguin, Benoît ; Zhang, Tuo ; Soumillion, Patrice ; Hols, Pascal ; Hu, Jian ; Hausinger, Robert P.</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c388t-6761a6288aa990bab01b43fbfe93cfc486625361461c6b255d0d72cdd5cb4a863</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2015</creationdate><topic>Accessories</topic><topic>Bacteria</topic><topic>Bacterial proteins</topic><topic>Biochemistry</topic><topic>Bonding</topic><topic>Chemical bonds</topic><topic>Derivatives</topic><topic>Enzymes</topic><topic>Lactates</topic><topic>Nickel</topic><topic>Proteins</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Desguin, Benoît</creatorcontrib><creatorcontrib>Zhang, Tuo</creatorcontrib><creatorcontrib>Soumillion, Patrice</creatorcontrib><creatorcontrib>Hols, Pascal</creatorcontrib><creatorcontrib>Hu, Jian</creatorcontrib><creatorcontrib>Hausinger, Robert P.</creatorcontrib><creatorcontrib>Argonne National Lab. 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subjects | Accessories Bacteria Bacterial proteins Biochemistry Bonding Chemical bonds Derivatives Enzymes Lactates Nickel Proteins |
title | A tethered niacin-derived pincer complex with a nickel-carbon bond in lactate racemase |
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