Redox and ligand exchange reactions of potential gold(I) and gold(III)-cyanide metabolites under biomimetic conditions
Biomimetic pathways for the oxidation of [Au(CN) 2] −, a gold metabolite, and further cyanation of the gold(III) products to form Au(CN) 4 − were investigated using 13C NMR and UV–Visible spectroscopic methods. Hypochlorite ion, an oxidant released during the oxidative burst of immune cells, was emp...
Gespeichert in:
| Veröffentlicht in: | Journal of inorganic biochemistry 2001-05, Vol.85 (1), p.67-76 |
|---|---|
| Hauptverfasser: | , , , , |
| Format: | Artikel |
| Sprache: | eng |
| Schlagworte: | |
| Online-Zugang: | Volltext |
| Tags: |
Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
|
| container_end_page | 76 |
|---|---|
| container_issue | 1 |
| container_start_page | 67 |
| container_title | Journal of inorganic biochemistry |
| container_volume | 85 |
| creator | Canumalla, Annapurna J Al-Zamil, Norah Phillips, Matthew Isab, Anvarhusein A Shaw III, C.Frank |
| description | Biomimetic pathways for the oxidation of [Au(CN)
2]
−, a gold metabolite, and further cyanation of the gold(III) products to form Au(CN)
4
− were investigated using
13C NMR and UV–Visible spectroscopic methods. Hypochlorite ion, an oxidant released during the oxidative burst of immune cells, was employed. The reaction generates mixed dicyanoaurate(III) complexes,
trans-[Au(CN)
2X
2]
−, where X
− represents equilibrating hydroxide and chloride ligands, and establishes the chemical feasibility of dicyanoaurate oxidation by OCl
− to gold(III) species. This oxidation reaction suggests a new procedure for synthesis of H[Au(CN)
2Cl
2]. Reaction of
trans-[Au(CN)
2X
2]
− (X
−=Cl
− and Br
−) or [AuCl
4]
− with HCN in aqueous solution at pH 7.4 leads directly to [Au(CN)
4]
− without detection of the anticipated [Au(CN)
x
X
4−
x
]
−intermediates, which is attributed to the
cis- and
trans-accelerating effects of the cyanides. The reduction of [Au(CN)
4]
− by glutathione and other thiols is a complex, pH-dependent process that proceeds through two intermediates and ultimately generates [Au(CN)
2]
−. These studies provide further insight into the possible mechanisms of an immunogenically generated gold(I)/gold(III) redox cycle in vivo. |
| doi_str_mv | 10.1016/S0162-0134(00)00224-5 |
| format | Article |
| fullrecord | <record><control><sourceid>proquest_cross</sourceid><recordid>TN_cdi_proquest_miscellaneous_70892045</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><els_id>S0162013400002245</els_id><sourcerecordid>70892045</sourcerecordid><originalsourceid>FETCH-LOGICAL-c361t-b2083e77fad688cadd3859fc03d5846887fbc7625671e8bcd743957878df09583</originalsourceid><addsrcrecordid>eNqFkE1r3DAQhkVpaLZpf0KKTiV7cDKyLEs-lRLaZCEQSNqzkKXxRsWWtpJ3yf77eD9IjrloxPC8M8xDyDmDSwasvnqcnrIAxqsLgDlAWVaF-EBmTElecF5VH8nsFTkln3P-BwBCVPITOWWMS1k3ckY2D-jiMzXB0d4vdwWf7ZMJS6QJjR19DJnGjq7iiGH0pqfL2LuLxXwfOfwXi3lhtyZ4h3TA0bSx9yNmug4OE219HPzU9pbaGJzfj_xCTjrTZ_x6rGfk7-9ff65vi7v7m8X1z7vC8pqNRVuC4ihlZ1ytlDXOcSWazgJ3QlVTS3atlXUpaslQtdbJijdCKqlcB41Q_Ix8P8xdpfh_jXnUg88W-94EjOusJaimhEpMoDiANsWcE3Z6lfxg0lYz0Dvhei9c72xqAL0Xrne5b8cF63ZA95Y6Gp6AHwcApzM3HpPO1mOw6HxCO2oX_TsrXgBJb5A-</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>70892045</pqid></control><display><type>article</type><title>Redox and ligand exchange reactions of potential gold(I) and gold(III)-cyanide metabolites under biomimetic conditions</title><source>MEDLINE</source><source>Elsevier ScienceDirect Journals</source><creator>Canumalla, Annapurna J ; Al-Zamil, Norah ; Phillips, Matthew ; Isab, Anvarhusein A ; Shaw III, C.Frank</creator><creatorcontrib>Canumalla, Annapurna J ; Al-Zamil, Norah ; Phillips, Matthew ; Isab, Anvarhusein A ; Shaw III, C.Frank</creatorcontrib><description>Biomimetic pathways for the oxidation of [Au(CN)
2]
−, a gold metabolite, and further cyanation of the gold(III) products to form Au(CN)
4
− were investigated using
13C NMR and UV–Visible spectroscopic methods. Hypochlorite ion, an oxidant released during the oxidative burst of immune cells, was employed. The reaction generates mixed dicyanoaurate(III) complexes,
trans-[Au(CN)
2X
2]
−, where X
− represents equilibrating hydroxide and chloride ligands, and establishes the chemical feasibility of dicyanoaurate oxidation by OCl
− to gold(III) species. This oxidation reaction suggests a new procedure for synthesis of H[Au(CN)
2Cl
2]. Reaction of
trans-[Au(CN)
2X
2]
− (X
−=Cl
− and Br
−) or [AuCl
4]
− with HCN in aqueous solution at pH 7.4 leads directly to [Au(CN)
4]
− without detection of the anticipated [Au(CN)
x
X
4−
x
]
−intermediates, which is attributed to the
cis- and
trans-accelerating effects of the cyanides. The reduction of [Au(CN)
4]
− by glutathione and other thiols is a complex, pH-dependent process that proceeds through two intermediates and ultimately generates [Au(CN)
2]
−. These studies provide further insight into the possible mechanisms of an immunogenically generated gold(I)/gold(III) redox cycle in vivo.</description><identifier>ISSN: 0162-0134</identifier><identifier>EISSN: 1873-3344</identifier><identifier>DOI: 10.1016/S0162-0134(00)00224-5</identifier><identifier>PMID: 11377697</identifier><language>eng</language><publisher>United States: Elsevier Inc</publisher><subject>Auricyanide ; Aurocyanide ; Biological redox reactions ; Cis effects ; Cyanates ; Cyanides - chemistry ; Cyanides - metabolism ; Glutathione - metabolism ; Gold ; Gold - chemistry ; Gold - metabolism ; Gold Compounds - chemistry ; Gold Compounds - metabolism ; Hydrogen-Ion Concentration ; Hypochlorite ; Magnetic Resonance Spectroscopy ; Oxidation-Reduction ; Spectrophotometry, Ultraviolet ; Thermodynamics ; Trans effects</subject><ispartof>Journal of inorganic biochemistry, 2001-05, Vol.85 (1), p.67-76</ispartof><rights>2001 Elsevier Science B.V.</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c361t-b2083e77fad688cadd3859fc03d5846887fbc7625671e8bcd743957878df09583</citedby><cites>FETCH-LOGICAL-c361t-b2083e77fad688cadd3859fc03d5846887fbc7625671e8bcd743957878df09583</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktohtml>$$Uhttps://www.sciencedirect.com/science/article/pii/S0162013400002245$$EHTML$$P50$$Gelsevier$$H</linktohtml><link.rule.ids>314,776,780,3536,27903,27904,65309</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/11377697$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Canumalla, Annapurna J</creatorcontrib><creatorcontrib>Al-Zamil, Norah</creatorcontrib><creatorcontrib>Phillips, Matthew</creatorcontrib><creatorcontrib>Isab, Anvarhusein A</creatorcontrib><creatorcontrib>Shaw III, C.Frank</creatorcontrib><title>Redox and ligand exchange reactions of potential gold(I) and gold(III)-cyanide metabolites under biomimetic conditions</title><title>Journal of inorganic biochemistry</title><addtitle>J Inorg Biochem</addtitle><description>Biomimetic pathways for the oxidation of [Au(CN)
2]
−, a gold metabolite, and further cyanation of the gold(III) products to form Au(CN)
4
− were investigated using
13C NMR and UV–Visible spectroscopic methods. Hypochlorite ion, an oxidant released during the oxidative burst of immune cells, was employed. The reaction generates mixed dicyanoaurate(III) complexes,
trans-[Au(CN)
2X
2]
−, where X
− represents equilibrating hydroxide and chloride ligands, and establishes the chemical feasibility of dicyanoaurate oxidation by OCl
− to gold(III) species. This oxidation reaction suggests a new procedure for synthesis of H[Au(CN)
2Cl
2]. Reaction of
trans-[Au(CN)
2X
2]
− (X
−=Cl
− and Br
−) or [AuCl
4]
− with HCN in aqueous solution at pH 7.4 leads directly to [Au(CN)
4]
− without detection of the anticipated [Au(CN)
x
X
4−
x
]
−intermediates, which is attributed to the
cis- and
trans-accelerating effects of the cyanides. The reduction of [Au(CN)
4]
− by glutathione and other thiols is a complex, pH-dependent process that proceeds through two intermediates and ultimately generates [Au(CN)
2]
−. These studies provide further insight into the possible mechanisms of an immunogenically generated gold(I)/gold(III) redox cycle in vivo.</description><subject>Auricyanide</subject><subject>Aurocyanide</subject><subject>Biological redox reactions</subject><subject>Cis effects</subject><subject>Cyanates</subject><subject>Cyanides - chemistry</subject><subject>Cyanides - metabolism</subject><subject>Glutathione - metabolism</subject><subject>Gold</subject><subject>Gold - chemistry</subject><subject>Gold - metabolism</subject><subject>Gold Compounds - chemistry</subject><subject>Gold Compounds - metabolism</subject><subject>Hydrogen-Ion Concentration</subject><subject>Hypochlorite</subject><subject>Magnetic Resonance Spectroscopy</subject><subject>Oxidation-Reduction</subject><subject>Spectrophotometry, Ultraviolet</subject><subject>Thermodynamics</subject><subject>Trans effects</subject><issn>0162-0134</issn><issn>1873-3344</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2001</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNqFkE1r3DAQhkVpaLZpf0KKTiV7cDKyLEs-lRLaZCEQSNqzkKXxRsWWtpJ3yf77eD9IjrloxPC8M8xDyDmDSwasvnqcnrIAxqsLgDlAWVaF-EBmTElecF5VH8nsFTkln3P-BwBCVPITOWWMS1k3ckY2D-jiMzXB0d4vdwWf7ZMJS6QJjR19DJnGjq7iiGH0pqfL2LuLxXwfOfwXi3lhtyZ4h3TA0bSx9yNmug4OE219HPzU9pbaGJzfj_xCTjrTZ_x6rGfk7-9ff65vi7v7m8X1z7vC8pqNRVuC4ihlZ1ytlDXOcSWazgJ3QlVTS3atlXUpaslQtdbJijdCKqlcB41Q_Ix8P8xdpfh_jXnUg88W-94EjOusJaimhEpMoDiANsWcE3Z6lfxg0lYz0Dvhei9c72xqAL0Xrne5b8cF63ZA95Y6Gp6AHwcApzM3HpPO1mOw6HxCO2oX_TsrXgBJb5A-</recordid><startdate>20010501</startdate><enddate>20010501</enddate><creator>Canumalla, Annapurna J</creator><creator>Al-Zamil, Norah</creator><creator>Phillips, Matthew</creator><creator>Isab, Anvarhusein A</creator><creator>Shaw III, C.Frank</creator><general>Elsevier Inc</general><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>20010501</creationdate><title>Redox and ligand exchange reactions of potential gold(I) and gold(III)-cyanide metabolites under biomimetic conditions</title><author>Canumalla, Annapurna J ; Al-Zamil, Norah ; Phillips, Matthew ; Isab, Anvarhusein A ; Shaw III, C.Frank</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c361t-b2083e77fad688cadd3859fc03d5846887fbc7625671e8bcd743957878df09583</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2001</creationdate><topic>Auricyanide</topic><topic>Aurocyanide</topic><topic>Biological redox reactions</topic><topic>Cis effects</topic><topic>Cyanates</topic><topic>Cyanides - chemistry</topic><topic>Cyanides - metabolism</topic><topic>Glutathione - metabolism</topic><topic>Gold</topic><topic>Gold - chemistry</topic><topic>Gold - metabolism</topic><topic>Gold Compounds - chemistry</topic><topic>Gold Compounds - metabolism</topic><topic>Hydrogen-Ion Concentration</topic><topic>Hypochlorite</topic><topic>Magnetic Resonance Spectroscopy</topic><topic>Oxidation-Reduction</topic><topic>Spectrophotometry, Ultraviolet</topic><topic>Thermodynamics</topic><topic>Trans effects</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Canumalla, Annapurna J</creatorcontrib><creatorcontrib>Al-Zamil, Norah</creatorcontrib><creatorcontrib>Phillips, Matthew</creatorcontrib><creatorcontrib>Isab, Anvarhusein A</creatorcontrib><creatorcontrib>Shaw III, C.Frank</creatorcontrib><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 inorganic biochemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Canumalla, Annapurna J</au><au>Al-Zamil, Norah</au><au>Phillips, Matthew</au><au>Isab, Anvarhusein A</au><au>Shaw III, C.Frank</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Redox and ligand exchange reactions of potential gold(I) and gold(III)-cyanide metabolites under biomimetic conditions</atitle><jtitle>Journal of inorganic biochemistry</jtitle><addtitle>J Inorg Biochem</addtitle><date>2001-05-01</date><risdate>2001</risdate><volume>85</volume><issue>1</issue><spage>67</spage><epage>76</epage><pages>67-76</pages><issn>0162-0134</issn><eissn>1873-3344</eissn><abstract>Biomimetic pathways for the oxidation of [Au(CN)
2]
−, a gold metabolite, and further cyanation of the gold(III) products to form Au(CN)
4
− were investigated using
13C NMR and UV–Visible spectroscopic methods. Hypochlorite ion, an oxidant released during the oxidative burst of immune cells, was employed. The reaction generates mixed dicyanoaurate(III) complexes,
trans-[Au(CN)
2X
2]
−, where X
− represents equilibrating hydroxide and chloride ligands, and establishes the chemical feasibility of dicyanoaurate oxidation by OCl
− to gold(III) species. This oxidation reaction suggests a new procedure for synthesis of H[Au(CN)
2Cl
2]. Reaction of
trans-[Au(CN)
2X
2]
− (X
−=Cl
− and Br
−) or [AuCl
4]
− with HCN in aqueous solution at pH 7.4 leads directly to [Au(CN)
4]
− without detection of the anticipated [Au(CN)
x
X
4−
x
]
−intermediates, which is attributed to the
cis- and
trans-accelerating effects of the cyanides. The reduction of [Au(CN)
4]
− by glutathione and other thiols is a complex, pH-dependent process that proceeds through two intermediates and ultimately generates [Au(CN)
2]
−. These studies provide further insight into the possible mechanisms of an immunogenically generated gold(I)/gold(III) redox cycle in vivo.</abstract><cop>United States</cop><pub>Elsevier Inc</pub><pmid>11377697</pmid><doi>10.1016/S0162-0134(00)00224-5</doi><tpages>10</tpages></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 0162-0134 |
| ispartof | Journal of inorganic biochemistry, 2001-05, Vol.85 (1), p.67-76 |
| issn | 0162-0134 1873-3344 |
| language | eng |
| recordid | cdi_proquest_miscellaneous_70892045 |
| source | MEDLINE; Elsevier ScienceDirect Journals |
| subjects | Auricyanide Aurocyanide Biological redox reactions Cis effects Cyanates Cyanides - chemistry Cyanides - metabolism Glutathione - metabolism Gold Gold - chemistry Gold - metabolism Gold Compounds - chemistry Gold Compounds - metabolism Hydrogen-Ion Concentration Hypochlorite Magnetic Resonance Spectroscopy Oxidation-Reduction Spectrophotometry, Ultraviolet Thermodynamics Trans effects |
| title | Redox and ligand exchange reactions of potential gold(I) and gold(III)-cyanide metabolites under biomimetic conditions |
| url | https://sfx.bib-bvb.de/sfx_tum?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2025-01-23T19%3A15%3A58IST&url_ver=Z39.88-2004&url_ctx_fmt=infofi/fmt:kev:mtx:ctx&rfr_id=info:sid/primo.exlibrisgroup.com:primo3-Article-proquest_cross&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.genre=article&rft.atitle=Redox%20and%20ligand%20exchange%20reactions%20of%20potential%20gold(I)%20and%20gold(III)-cyanide%20metabolites%20under%20biomimetic%20conditions&rft.jtitle=Journal%20of%20inorganic%20biochemistry&rft.au=Canumalla,%20Annapurna%20J&rft.date=2001-05-01&rft.volume=85&rft.issue=1&rft.spage=67&rft.epage=76&rft.pages=67-76&rft.issn=0162-0134&rft.eissn=1873-3344&rft_id=info:doi/10.1016/S0162-0134(00)00224-5&rft_dat=%3Cproquest_cross%3E70892045%3C/proquest_cross%3E%3Curl%3E%3C/url%3E&disable_directlink=true&sfx.directlink=off&sfx.report_link=0&rft_id=info:oai/&rft_pqid=70892045&rft_id=info:pmid/11377697&rft_els_id=S0162013400002245&rfr_iscdi=true |