Mechanism of the cyanide-catalyzed oxidation of α-ketoaldehydes and α-ketoalcohols

Tadahiko Mashino, Irwin Fridovich

Research output: Contribution to journalArticle

17 Citations (Scopus)

Abstract

Cyanide catalyzes the reduction of dioxygen or of ferricytochrome c by dihydroxyacetone phosphate. The rapid initial phase of these reactions, but not the subsequent slow phase, was augmented by incubating the triose phosphate aerobically or anaerobically at pH 9.0 prior to adding the cyanide. The aerobic incubation, which was most effective, was associated with a decline in enediol, whereas the less effective anaerobic incubation was accompanied by an increase in enediol content. This suggested that the α-ketoaldehyde product of autoxidation of the enediol, rather than the enediol itself, was responsible for the rapid phase reaction which followed addition of cyanide. This was confirmed by exploring the cyanide-catalyzed oxidation of the α-ketoaldehyde, phenylglyoxal. The inhibitory effect of the manganese-containing superoxide dismutase indicated that O2- was a kinetically important intermediate of the rapid phase reaction. A reaction mechanism is proposed which is consistent with the results presented.

Original languageEnglish
Pages (from-to)163-170
Number of pages8
JournalArchives of Biochemistry and Biophysics
Volume252
Issue number1
DOIs
Publication statusPublished - 1987
Externally publishedYes

Fingerprint

Cyanides
Oxidation
Phenylglyoxal
Trioses
Dihydroxyacetone Phosphate
Manganese
Cytochromes c
Superoxide Dismutase
Phosphates
Oxygen

ASJC Scopus subject areas

  • Biochemistry
  • Biophysics
  • Molecular Biology

Cite this

Mechanism of the cyanide-catalyzed oxidation of α-ketoaldehydes and α-ketoalcohols. / Mashino, Tadahiko; Fridovich, Irwin.

In: Archives of Biochemistry and Biophysics, Vol. 252, No. 1, 1987, p. 163-170.

Research output: Contribution to journalArticle

@article{1b34d201a5474d32b5c9d37ab0c2b3b1,
title = "Mechanism of the cyanide-catalyzed oxidation of α-ketoaldehydes and α-ketoalcohols",
abstract = "Cyanide catalyzes the reduction of dioxygen or of ferricytochrome c by dihydroxyacetone phosphate. The rapid initial phase of these reactions, but not the subsequent slow phase, was augmented by incubating the triose phosphate aerobically or anaerobically at pH 9.0 prior to adding the cyanide. The aerobic incubation, which was most effective, was associated with a decline in enediol, whereas the less effective anaerobic incubation was accompanied by an increase in enediol content. This suggested that the α-ketoaldehyde product of autoxidation of the enediol, rather than the enediol itself, was responsible for the rapid phase reaction which followed addition of cyanide. This was confirmed by exploring the cyanide-catalyzed oxidation of the α-ketoaldehyde, phenylglyoxal. The inhibitory effect of the manganese-containing superoxide dismutase indicated that O2- was a kinetically important intermediate of the rapid phase reaction. A reaction mechanism is proposed which is consistent with the results presented.",
author = "Tadahiko Mashino and Irwin Fridovich",
year = "1987",
doi = "10.1016/0003-9861(87)90020-8",
language = "English",
volume = "252",
pages = "163--170",
journal = "Archives of Biochemistry and Biophysics",
issn = "0003-9861",
publisher = "Academic Press Inc.",
number = "1",

}

TY - JOUR

T1 - Mechanism of the cyanide-catalyzed oxidation of α-ketoaldehydes and α-ketoalcohols

AU - Mashino, Tadahiko

AU - Fridovich, Irwin

PY - 1987

Y1 - 1987

N2 - Cyanide catalyzes the reduction of dioxygen or of ferricytochrome c by dihydroxyacetone phosphate. The rapid initial phase of these reactions, but not the subsequent slow phase, was augmented by incubating the triose phosphate aerobically or anaerobically at pH 9.0 prior to adding the cyanide. The aerobic incubation, which was most effective, was associated with a decline in enediol, whereas the less effective anaerobic incubation was accompanied by an increase in enediol content. This suggested that the α-ketoaldehyde product of autoxidation of the enediol, rather than the enediol itself, was responsible for the rapid phase reaction which followed addition of cyanide. This was confirmed by exploring the cyanide-catalyzed oxidation of the α-ketoaldehyde, phenylglyoxal. The inhibitory effect of the manganese-containing superoxide dismutase indicated that O2- was a kinetically important intermediate of the rapid phase reaction. A reaction mechanism is proposed which is consistent with the results presented.

AB - Cyanide catalyzes the reduction of dioxygen or of ferricytochrome c by dihydroxyacetone phosphate. The rapid initial phase of these reactions, but not the subsequent slow phase, was augmented by incubating the triose phosphate aerobically or anaerobically at pH 9.0 prior to adding the cyanide. The aerobic incubation, which was most effective, was associated with a decline in enediol, whereas the less effective anaerobic incubation was accompanied by an increase in enediol content. This suggested that the α-ketoaldehyde product of autoxidation of the enediol, rather than the enediol itself, was responsible for the rapid phase reaction which followed addition of cyanide. This was confirmed by exploring the cyanide-catalyzed oxidation of the α-ketoaldehyde, phenylglyoxal. The inhibitory effect of the manganese-containing superoxide dismutase indicated that O2- was a kinetically important intermediate of the rapid phase reaction. A reaction mechanism is proposed which is consistent with the results presented.

UR - http://www.scopus.com/inward/record.url?scp=0023146553&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0023146553&partnerID=8YFLogxK

U2 - 10.1016/0003-9861(87)90020-8

DO - 10.1016/0003-9861(87)90020-8

M3 - Article

VL - 252

SP - 163

EP - 170

JO - Archives of Biochemistry and Biophysics

JF - Archives of Biochemistry and Biophysics

SN - 0003-9861

IS - 1

ER -