Thiol oxidation with O in water solutions
Russ.Chem.Bull., Int.Ed., Vol. 52, No. 5, May, 2003
1141
2
reaction in a wide concentration range of reagents. Thus,
the monitoring of the process based on a decrease in the
concentration of a thiol compound imposes limitations
on the latter value, which should be in the range from
4. Z. M. Bacq and P. Alexander, Fundamentals of Radiobiology,
nd ed., Pergamon Press, Oxford, 1961, 432 pp.
2
5
. G. I. Oksengendler, Yady i protivoyadiya [Toxins and Antiꢀ
dotes], Nauka, Leningrad, 1982, 191 pp. (in Russian).
. G. E. Poirier, Langmuir, 1997, 13, 2019.
. J. E. Taylor, E. Y. Jonson, and J. L. Wang, J. Am. Chem.
Soc., 1966, 88, 1663.
6
7
–
4
–3
–1
5
•10 to 5•10 mol L because of low solubility of O2
in aqueous solutions, whereas the concentration of variꢀ
ableꢀvalence metal ions at high oxidation rates of many
thiols can be varied by a factor of no more than 2—3
because of the second order of the reaction with respect to
metal. This range in which the concentrations of the reꢀ
agents can be varied is too narrow to both reliably eluciꢀ
date the characteristic features of catalytic oxidation and
provide conditions for the formation of all kinetically
active forms of complexes of thiol compounds with metal
8
. C. G. Overberger, K. H. Burg, and W. H. Daly, J. Am. Chem.
Soc., 1965, 87, 4125.
9. J. Stauff and F. Nummerfoll, Z. Naturforsch., 1969,
24b, 1009.
0. A. Hanaki and H. Kamide, Chem. Pharm. Bull., 1975,
1
1
1
1
2
3, 1671.
1. D. Cavallini, C. De Marko, and S. Dupre, Arch. Biochem.
Biophys., 1968, 124, 18.
2. R. E. Benesch and R. Benesch, J. Am. Chem. Soc., 1955,
77, 5877.
ions. In addition, if O is reduced only to H O in the
2
2
2
course of the reaction, it is not correct to monitor the
process based on a decrease in the concentration of TC,
because H O that formed additionally oxidizes an equivaꢀ
3. T. J. Wallace, Tetrahedron, 1965, 21, 2271.
14. A. Hanaki, Bull. Chem. Soc. Jpn., 1995, 68, 831.
15. L. Pecci, G. Montefoschi, G. Musci, and D. Cavallini, Amino
Acids, 1997, 13, 355.
2
2
lent amount of the thiol compound and, consequently,
only oneꢀhalf of TC is consumed for catalytic oxidation
of interest. Attempts to determine the degree of reduction
1
6. A. Kachur, C. J. Koch, and J. E. Biaglow, Free Radic. Res.,
999, 31, 23.
1
1
7. G. A. Bagiyan, S. A. Grachev, I. K. Koroleva, and N. V.
Soroka, Zh. Org. Khim., 1975, 11, 900 [J. Org. Chem. USSR,
of O in the course of catalytic oxidation using a known
2
2
1
procedure for analysis of H O in aqueous solutions
2
2
1
975, 11 (Engl. Transl.)].
failed because of the low sensitivity of this procedure. In
rare cases, the presence of H O in a system involving
1
8. G. A. Bagiyan, S. A. Grachev, and N. V. Soroka, Izv. Akad.
Nauk SSSR, Ser. Khim., 1975, 435 [Bull. Acad. Sci. USSR,
Div. Chem. Sci., 1975, 24 (Engl. Transl.)].
2
2
TC, variableꢀvalence metal, and O was only detected
2
qualitatively.
19. G. A. Bagiyan, S. A. Grachev, I. K. Koroleva, and N. V.
Soroka, Zh. Obshch. Khim., 1976, 46, 365 [J. Gen. Chem.
USSR, 1976, 46 (Engl. Transl.)].
To study the stoichiometry and kinetics of catalytic
oxidation of thiol compounds, we developed a sensitive
method of analysis of H O and adapted a known polaroꢀ
2
2
0. G. L. Ellman, Arch. Biochem. Biophys., 1959, 82, 70.
1. J. P. Barton, J. E. Packer, and R. J. Sims, J. Chem. Soc.,
Perkin Trans. 2, 1973, 1547.
2
2
graphic method of analysis of O to solutions containing
2
aggressive TC, which rapidly poison a measuring elecꢀ
trode. The results of studies with the use of these proceꢀ
dures will be published elsewhere.
2
2
2
2. S. A. Grachev and N. V. Soroka, Izv. Akad. Nauk SSSR, Ser.
Khim., 1981, 1756 [Bull. Acad. Sci. USSR, Div. Chem. Sci.,
1
981, 30 (Engl. Transl.)].
3. G. A. Bagiyan, S. A. Grachev, I. K. Koroleva, and N. V.
Soroka, Izv. Akad. Nauk SSSR, Ser. Khim., 1976, 990 [Bull.
Acad. Sci. USSR, Div. Chem. Sci., 1976, 25 (Engl. Transl.)].
4. Yu. I. Skurlatov, G. G. Duka, D. G. Batyr, and S. O. Travin,
Koord. Khim., 1989, 15, 291 [Sov. J. Coord. Chem., 1989, 15
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. H. Beinert, M. C. Kennedy, and C. D. Stout, Chem. Rev.,
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. E. T. Adman, Adv. Protein Chem., 1991, 42, 145.
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Received August 8, 2002;
in revised form January 15, 2003