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Volumn 120, Issue 27, 1998, Pages 6704-6714

Activation of molecular oxygen during the reactions of chromium(VI/V/IV) with biological reductants: Implications for chromium-induced genotoxicities

Author keywords

[No Author keywords available]

Indexed keywords

ASCORBIC ACID; CHROMIUM; CYSTEINE; GLUTATHIONE; TROLOX C;

EID: 0032527711     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja974240z     Document Type: Article
Times cited : (128)

References (94)
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    • 2: = 2-ethyl-2-hydroxybutanoic acid; GSH = glutathione (γ-glutamylcysteinylglycine); HEPES = N-[2-hydroxyethyl]-piperazine-N′-[2-ethanesulfonic acid]; Red = reductant; SOD = Superoxide dismutase; Trolox = 6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid.
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    • Generation, stability and UV-visible spectra of Cr(IV)-ehba complexes are described in the following: (a) Ghosh, M. C.; Gould, E. S. Inorg. Chem. 1991, 30, 491-494. (b) Codd, R.; Lay, P. A.; Levina, A. Inorg. Chem. 1997, 36, 5440-5448.
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    • 2) did not change in the presence of 1.0 mM of Cr(VI), Cr(V), or Cr(IV) (pH = 7.0-7.5).
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    • Preliminary kinetic experiments have shown that the rates of Cr(V) reactions with catalase, SOD, or DMPO under the studied conditions were insignificant in comparison with those for the Cr(V) + Cys reaction.
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    • However, autocatalysis was not observed under the conditions used in this work
    • 0 ratios, these reactions possessed autocatalytic behavior: (a) Ghosh, S. K.; Bose, R. N.; Gould, E. S. Inorg. Chem. 1987, 26, 3722-3727. (b) Ghosh, S. K.; Bose, R. N.; Gould, E. S. Inorg. Chem. 1987, 26, 2684-2687. However, autocatalysis was not observed under the conditions used in this work.
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    • 26,31 The simplest kinetic schemes, applied here (Table 2), do not reflect true mechanisms of these reactions. The kinetic data (17-20 in Table 2) are given only for comparison with the reactions in the presence of Red (1-16 in Table 2).
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    • 26b however, application of the stopped-flow technique in the current work allowed to obtain definitive evidence for their existence. The equilibrium (eq 2) is probably achieved within a deadtime of the stopped-flow experiment.
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    • 12 and complexes with Trolox oxidation product, 2-hydroxy-2-methyl-4-(2,5,6-trimethyl-2,4-dioxo-2,5-cyclohexadienyl)butanoic acid (Dalla-Pozza, A.-M. B.Sc. Honours Thesis, University of Sydney, 1996).
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    • Since all the reductants used possess a number of potential donor groups (see Scheme 2), such mixtures of Cr(V/IV) species may be very complex
    • Since all the reductants used possess a number of potential donor groups (see Scheme 2), such mixtures of Cr(V/IV) species may be very complex.
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    • 52,53 This is because the applied kinetic schemes (Table 2) did not take into account the second-order disproportionation reactions of the anionradicals (eq 17 in Scheme 2).
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