Weak Antiferromagnetic Coupling via a Superexchange Interaction between Mn(II)–Mn(II) Ions: A QM/MM Study of the Active Site of Human Cytosolic X‑Propyl Aminopeptidase P
We investigate the dinuclear manganese, Mn(II)–Mn(II), active site of human cytosolic X-propyl aminopeptidase (XPNPEP1) by employing the QM/MM method. The optimized structure supports two manganese atoms at the active site and excludes the possibility of a single Mn(II) atom or another combination o...
Gespeichert in:
| Veröffentlicht in: | J. Phys. Chem. Lett 2012-08, Vol.3 (16), p.2293-2297 |
|---|---|
| Hauptverfasser: | , , , |
| Format: | Artikel |
| Sprache: | eng |
| Schlagworte: | |
| Online-Zugang: | Volltext |
| Tags: |
Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
|
| container_end_page | 2297 |
|---|---|
| container_issue | 16 |
| container_start_page | 2293 |
| container_title | J. Phys. Chem. Lett |
| container_volume | 3 |
| creator | Wu, Sangwook Liu, Shubin Sim, Sooyeon Pedersen, Lee G |
| description | We investigate the dinuclear manganese, Mn(II)–Mn(II), active site of human cytosolic X-propyl aminopeptidase (XPNPEP1) by employing the QM/MM method. The optimized structure supports two manganese atoms at the active site and excludes the possibility of a single Mn(II) atom or another combination of divalent metal ions, Ca(II), Fe(II), an Mg(II). A broken-symmetry solution verifies an antiferromagnetically coupled state between the Mn(II)–Mn(II) pair, which is the ground state. From the energy difference between the high spin state (HS) and the broken-symmetry state (BS), we estimate the exchange coupling constant, J, to be 5.15 cm–1. Also, we observe multiple bridges (p orbitals) from the solvent and two carboxylates linking to the Mn(II)–Mn(II), which leads to the weakly antiferromagnetic interaction of d5–d5 electrons through superexchange coupling. |
| doi_str_mv | 10.1021/jz300768g |
| format | Article |
| fullrecord | <record><control><sourceid>acs_osti_</sourceid><recordid>TN_cdi_crossref_primary_10_1021_jz300768g</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>e87906095</sourcerecordid><originalsourceid>FETCH-LOGICAL-a387t-5276513f700b93bb199a899663f9ac646b4e39f6af3ca2c584471a8ef8afc5ec3</originalsourceid><addsrcrecordid>eNptkU1qHDEQhRvjQGwni9ygMBjixcTS9J-UXTP4p8FDbCYh2TXVcmlG4xmpkdS2xytfIeQcuZRPkjZjQhZZ1aP4XtWDlyQfOPvE2ZifLB9TxspCzHeSPS4zMSq5yHf_0W-T_RCWjBWSiXIv-f2d8BYqG40m790a55aiUTBxfbcydg53BgFh1nfk6UEt0M4JahvJo4rGWWgp3hNZmNqPdX38_PRrK6B2NnyGCq6nJ9MpzGJ_swGnIS4IqsF5RzAzkV5WF_0aLUw20QW3Gl7_eH76eeVdt1lBtTbWddRFc4OB4Opd8kbjKtD713mQfDs7_Tq5GF1-Oa8n1eUIU1HGUT4ui5ynumSslWnbcilRSFkUqZaoiqxoM0qlLlCnCscqF1lWchSkBWqVk0oPksPtXReiaYIakqqFctaSig1ngpUiH6DjLaS8C8GTbjpv1ug3A9G8lNH8LWNgj7YsqtAsXe_tEP8_3B9Q54sz</addsrcrecordid><sourcetype>Open Access Repository</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype></control><display><type>article</type><title>Weak Antiferromagnetic Coupling via a Superexchange Interaction between Mn(II)–Mn(II) Ions: A QM/MM Study of the Active Site of Human Cytosolic X‑Propyl Aminopeptidase P</title><source>ACS Publications</source><creator>Wu, Sangwook ; Liu, Shubin ; Sim, Sooyeon ; Pedersen, Lee G</creator><creatorcontrib>Wu, Sangwook ; Liu, Shubin ; Sim, Sooyeon ; Pedersen, Lee G ; Energy Frontier Research Centers (EFRC) ; Center for Solar Fuels (UNC EFRC)</creatorcontrib><description>We investigate the dinuclear manganese, Mn(II)–Mn(II), active site of human cytosolic X-propyl aminopeptidase (XPNPEP1) by employing the QM/MM method. The optimized structure supports two manganese atoms at the active site and excludes the possibility of a single Mn(II) atom or another combination of divalent metal ions, Ca(II), Fe(II), an Mg(II). A broken-symmetry solution verifies an antiferromagnetically coupled state between the Mn(II)–Mn(II) pair, which is the ground state. From the energy difference between the high spin state (HS) and the broken-symmetry state (BS), we estimate the exchange coupling constant, J, to be 5.15 cm–1. Also, we observe multiple bridges (p orbitals) from the solvent and two carboxylates linking to the Mn(II)–Mn(II), which leads to the weakly antiferromagnetic interaction of d5–d5 electrons through superexchange coupling.</description><identifier>ISSN: 1948-7185</identifier><identifier>EISSN: 1948-7185</identifier><identifier>DOI: 10.1021/jz300768g</identifier><language>eng</language><publisher>United States: American Chemical Society</publisher><subject>catalysis (homogeneous), catalysis (heterogeneous), solar (photovoltaic), solar (fuels), photosynthesis (natural and artificial), hydrogen and fuel cells, electrodes - solar, charge transport, materials and chemistry by design, synthesis (novel materials), synthesis (self-assembly) ; Molecular Structure, Quantum Chemistry, and General Theory</subject><ispartof>J. Phys. Chem. Lett, 2012-08, Vol.3 (16), p.2293-2297</ispartof><rights>Copyright © 2012 American Chemical Society</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a387t-5276513f700b93bb199a899663f9ac646b4e39f6af3ca2c584471a8ef8afc5ec3</citedby><cites>FETCH-LOGICAL-a387t-5276513f700b93bb199a899663f9ac646b4e39f6af3ca2c584471a8ef8afc5ec3</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/jz300768g$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/jz300768g$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>314,777,781,882,2752,27057,27905,27906,56719,56769</link.rule.ids><backlink>$$Uhttps://www.osti.gov/biblio/1080785$$D View this record in Osti.gov$$Hfree_for_read</backlink></links><search><creatorcontrib>Wu, Sangwook</creatorcontrib><creatorcontrib>Liu, Shubin</creatorcontrib><creatorcontrib>Sim, Sooyeon</creatorcontrib><creatorcontrib>Pedersen, Lee G</creatorcontrib><creatorcontrib>Energy Frontier Research Centers (EFRC)</creatorcontrib><creatorcontrib>Center for Solar Fuels (UNC EFRC)</creatorcontrib><title>Weak Antiferromagnetic Coupling via a Superexchange Interaction between Mn(II)–Mn(II) Ions: A QM/MM Study of the Active Site of Human Cytosolic X‑Propyl Aminopeptidase P</title><title>J. Phys. Chem. Lett</title><addtitle>J. Phys. Chem. Lett</addtitle><description>We investigate the dinuclear manganese, Mn(II)–Mn(II), active site of human cytosolic X-propyl aminopeptidase (XPNPEP1) by employing the QM/MM method. The optimized structure supports two manganese atoms at the active site and excludes the possibility of a single Mn(II) atom or another combination of divalent metal ions, Ca(II), Fe(II), an Mg(II). A broken-symmetry solution verifies an antiferromagnetically coupled state between the Mn(II)–Mn(II) pair, which is the ground state. From the energy difference between the high spin state (HS) and the broken-symmetry state (BS), we estimate the exchange coupling constant, J, to be 5.15 cm–1. Also, we observe multiple bridges (p orbitals) from the solvent and two carboxylates linking to the Mn(II)–Mn(II), which leads to the weakly antiferromagnetic interaction of d5–d5 electrons through superexchange coupling.</description><subject>catalysis (homogeneous), catalysis (heterogeneous), solar (photovoltaic), solar (fuels), photosynthesis (natural and artificial), hydrogen and fuel cells, electrodes - solar, charge transport, materials and chemistry by design, synthesis (novel materials), synthesis (self-assembly)</subject><subject>Molecular Structure, Quantum Chemistry, and General Theory</subject><issn>1948-7185</issn><issn>1948-7185</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2012</creationdate><recordtype>article</recordtype><recordid>eNptkU1qHDEQhRvjQGwni9ygMBjixcTS9J-UXTP4p8FDbCYh2TXVcmlG4xmpkdS2xytfIeQcuZRPkjZjQhZZ1aP4XtWDlyQfOPvE2ZifLB9TxspCzHeSPS4zMSq5yHf_0W-T_RCWjBWSiXIv-f2d8BYqG40m790a55aiUTBxfbcydg53BgFh1nfk6UEt0M4JahvJo4rGWWgp3hNZmNqPdX38_PRrK6B2NnyGCq6nJ9MpzGJ_swGnIS4IqsF5RzAzkV5WF_0aLUw20QW3Gl7_eH76eeVdt1lBtTbWddRFc4OB4Opd8kbjKtD713mQfDs7_Tq5GF1-Oa8n1eUIU1HGUT4ui5ynumSslWnbcilRSFkUqZaoiqxoM0qlLlCnCscqF1lWchSkBWqVk0oPksPtXReiaYIakqqFctaSig1ngpUiH6DjLaS8C8GTbjpv1ug3A9G8lNH8LWNgj7YsqtAsXe_tEP8_3B9Q54sz</recordid><startdate>20120816</startdate><enddate>20120816</enddate><creator>Wu, Sangwook</creator><creator>Liu, Shubin</creator><creator>Sim, Sooyeon</creator><creator>Pedersen, Lee G</creator><general>American Chemical Society</general><scope>AAYXX</scope><scope>CITATION</scope><scope>OTOTI</scope></search><sort><creationdate>20120816</creationdate><title>Weak Antiferromagnetic Coupling via a Superexchange Interaction between Mn(II)–Mn(II) Ions: A QM/MM Study of the Active Site of Human Cytosolic X‑Propyl Aminopeptidase P</title><author>Wu, Sangwook ; Liu, Shubin ; Sim, Sooyeon ; Pedersen, Lee G</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a387t-5276513f700b93bb199a899663f9ac646b4e39f6af3ca2c584471a8ef8afc5ec3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2012</creationdate><topic>catalysis (homogeneous), catalysis (heterogeneous), solar (photovoltaic), solar (fuels), photosynthesis (natural and artificial), hydrogen and fuel cells, electrodes - solar, charge transport, materials and chemistry by design, synthesis (novel materials), synthesis (self-assembly)</topic><topic>Molecular Structure, Quantum Chemistry, and General Theory</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Wu, Sangwook</creatorcontrib><creatorcontrib>Liu, Shubin</creatorcontrib><creatorcontrib>Sim, Sooyeon</creatorcontrib><creatorcontrib>Pedersen, Lee G</creatorcontrib><creatorcontrib>Energy Frontier Research Centers (EFRC)</creatorcontrib><creatorcontrib>Center for Solar Fuels (UNC EFRC)</creatorcontrib><collection>CrossRef</collection><collection>OSTI.GOV</collection><jtitle>J. Phys. Chem. Lett</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Wu, Sangwook</au><au>Liu, Shubin</au><au>Sim, Sooyeon</au><au>Pedersen, Lee G</au><aucorp>Energy Frontier Research Centers (EFRC)</aucorp><aucorp>Center for Solar Fuels (UNC EFRC)</aucorp><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Weak Antiferromagnetic Coupling via a Superexchange Interaction between Mn(II)–Mn(II) Ions: A QM/MM Study of the Active Site of Human Cytosolic X‑Propyl Aminopeptidase P</atitle><jtitle>J. Phys. Chem. Lett</jtitle><addtitle>J. Phys. Chem. Lett</addtitle><date>2012-08-16</date><risdate>2012</risdate><volume>3</volume><issue>16</issue><spage>2293</spage><epage>2297</epage><pages>2293-2297</pages><issn>1948-7185</issn><eissn>1948-7185</eissn><abstract>We investigate the dinuclear manganese, Mn(II)–Mn(II), active site of human cytosolic X-propyl aminopeptidase (XPNPEP1) by employing the QM/MM method. The optimized structure supports two manganese atoms at the active site and excludes the possibility of a single Mn(II) atom or another combination of divalent metal ions, Ca(II), Fe(II), an Mg(II). A broken-symmetry solution verifies an antiferromagnetically coupled state between the Mn(II)–Mn(II) pair, which is the ground state. From the energy difference between the high spin state (HS) and the broken-symmetry state (BS), we estimate the exchange coupling constant, J, to be 5.15 cm–1. Also, we observe multiple bridges (p orbitals) from the solvent and two carboxylates linking to the Mn(II)–Mn(II), which leads to the weakly antiferromagnetic interaction of d5–d5 electrons through superexchange coupling.</abstract><cop>United States</cop><pub>American Chemical Society</pub><doi>10.1021/jz300768g</doi><tpages>5</tpages><oa>free_for_read</oa></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 1948-7185 |
| ispartof | J. Phys. Chem. Lett, 2012-08, Vol.3 (16), p.2293-2297 |
| issn | 1948-7185 1948-7185 |
| language | eng |
| recordid | cdi_crossref_primary_10_1021_jz300768g |
| source | ACS Publications |
| subjects | catalysis (homogeneous), catalysis (heterogeneous), solar (photovoltaic), solar (fuels), photosynthesis (natural and artificial), hydrogen and fuel cells, electrodes - solar, charge transport, materials and chemistry by design, synthesis (novel materials), synthesis (self-assembly) Molecular Structure, Quantum Chemistry, and General Theory |
| title | Weak Antiferromagnetic Coupling via a Superexchange Interaction between Mn(II)–Mn(II) Ions: A QM/MM Study of the Active Site of Human Cytosolic X‑Propyl Aminopeptidase P |
| url | https://sfx.bib-bvb.de/sfx_tum?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2025-01-18T01%3A55%3A57IST&url_ver=Z39.88-2004&url_ctx_fmt=infofi/fmt:kev:mtx:ctx&rfr_id=info:sid/primo.exlibrisgroup.com:primo3-Article-acs_osti_&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.genre=article&rft.atitle=Weak%20Antiferromagnetic%20Coupling%20via%20a%20Superexchange%20Interaction%20between%20Mn(II)%E2%80%93Mn(II)%20Ions:%20A%20QM/MM%20Study%20of%20the%20Active%20Site%20of%20Human%20Cytosolic%20X%E2%80%91Propyl%20Aminopeptidase%20P&rft.jtitle=J.%20Phys.%20Chem.%20Lett&rft.au=Wu,%20Sangwook&rft.aucorp=Energy%20Frontier%20Research%20Centers%20(EFRC)&rft.date=2012-08-16&rft.volume=3&rft.issue=16&rft.spage=2293&rft.epage=2297&rft.pages=2293-2297&rft.issn=1948-7185&rft.eissn=1948-7185&rft_id=info:doi/10.1021/jz300768g&rft_dat=%3Cacs_osti_%3Ee87906095%3C/acs_osti_%3E%3Curl%3E%3C/url%3E&disable_directlink=true&sfx.directlink=off&sfx.report_link=0&rft_id=info:oai/&rft_id=info:pmid/&rfr_iscdi=true |