Redox and ligand exchange reactions of potential gold(I) and gold(III)-cyanide metabolites under biomimetic conditions

Annapurna J. Canumalla; Norah Al-Zamil; Matthew Phillips; Anvarhusein A. Isab; C. Frank Shaw

doi:10.1016/S0162-0134(00)00224-5

Redox and ligand exchange reactions of potential gold(I) and gold(III)-cyanide metabolites under biomimetic conditions

Annapurna J. Canumalla
, Norah Al-Zamil
, Matthew Phillips
, Anvarhusein A. Isab
, C. Frank Shaw

Research output: Contribution to journal › Article › peer-review

50 Scopus citations

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)₂X₂]^-, 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)₂Cl₂]. Reaction of trans-[Au(CN)₂X₂]^- (X^-=Cl^- and Br^-) or [AuCl₄]^- with HCN in aqueous solution at pH 7.4 leads directly to [Au(CN)₄]^- without detection of the anticipated [Au(CN)_xX_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.

Original language	English
Pages (from-to)	67-76
Number of pages	10
Journal	Journal of Inorganic Biochemistry
Volume	85
Issue number	1
DOIs	https://doi.org/10.1016/S0162-0134(00)00224-5
State	Published - 2001

Keywords

Auricyanide
Aurocyanide
Biological redox reactions
Cis effects
Gold
Hypochlorite
Trans effects

ASJC Scopus subject areas

Biochemistry
Inorganic Chemistry

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10.1016/S0162-0134(00)00224-5

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@article{3607de3c8cb54292a5629b3931c57ae3,

title = "Redox and ligand exchange reactions of potential gold(I) and gold(III)-cyanide metabolites under biomimetic conditions",

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)2X2]-, 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)2Cl2]. Reaction of trans-[Au(CN)2X2]- (X-=Cl- and Br-) or [AuCl4]- with HCN in aqueous solution at pH 7.4 leads directly to [Au(CN)4]- without detection of the anticipated [Au(CN)xX4-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.",

keywords = "Auricyanide, Aurocyanide, Biological redox reactions, Cis effects, Gold, Hypochlorite, Trans effects",

author = "Canumalla, \{Annapurna J.\} and Norah Al-Zamil and Matthew Phillips and Isab, \{Anvarhusein A.\} and Shaw, \{C. Frank\}",

year = "2001",

doi = "10.1016/S0162-0134(00)00224-5",

language = "English",

volume = "85",

pages = "67--76",

journal = "Journal of Inorganic Biochemistry",

issn = "0162-0134",

publisher = "Elsevier Inc.",

number = "1",

}

TY - JOUR

T1 - Redox and ligand exchange reactions of potential gold(I) and gold(III)-cyanide metabolites under biomimetic conditions

AU - Canumalla, Annapurna J.

AU - Al-Zamil, Norah

AU - Phillips, Matthew

AU - Isab, Anvarhusein A.

AU - Shaw, C. Frank

PY - 2001

Y1 - 2001

N2 - 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)2X2]-, 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)2Cl2]. Reaction of trans-[Au(CN)2X2]- (X-=Cl- and Br-) or [AuCl4]- with HCN in aqueous solution at pH 7.4 leads directly to [Au(CN)4]- without detection of the anticipated [Au(CN)xX4-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.

AB - 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)2X2]-, 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)2Cl2]. Reaction of trans-[Au(CN)2X2]- (X-=Cl- and Br-) or [AuCl4]- with HCN in aqueous solution at pH 7.4 leads directly to [Au(CN)4]- without detection of the anticipated [Au(CN)xX4-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.

KW - Auricyanide

KW - Aurocyanide

KW - Biological redox reactions

KW - Cis effects

KW - Gold

KW - Hypochlorite

KW - Trans effects

UR - https://www.scopus.com/pages/publications/0034983253

U2 - 10.1016/S0162-0134(00)00224-5

DO - 10.1016/S0162-0134(00)00224-5

M3 - Article

C2 - 11377697

AN - SCOPUS:0034983253

SN - 0162-0134

VL - 85

SP - 67

EP - 76

JO - Journal of Inorganic Biochemistry

JF - Journal of Inorganic Biochemistry

IS - 1

ER -

Redox and ligand exchange reactions of potential gold(I) and gold(III)-cyanide metabolites under biomimetic conditions

Abstract

Keywords

ASJC Scopus subject areas

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