Activation of molecular oxygen for the oxidation of 2-mercaptoethanol: A kinetic and mechanistic approach

M.Z.A. Rafiquee; Masoom R. Siddiqui; H.N. Haque; M. Shamsul Ola; Hamad A. Al-Lohedan; Z.A. Al-Othman; Saikh M. Wabaidur

Journal of Industrial and Engineering Chemistry, Vol.34, 84-88, February, 2016

DOI10.1016/j.jiec.2015.10.039 Export Citation

Activation of molecular oxygen for the oxidation of 2-mercaptoethanol: A kinetic and mechanistic approach

M.Z.A. Rafiquee^{1, 2, †}, Masoom R. Siddiqui^{3, †}, H.N. Haque^{1, 4}, M. Shamsul Ola⁵, Hamad A. Al-Lohedan^{1, 4}, Z.A. Al-Othman³, and Saikh M. Wabaidur³

¹Surfactant Research Chair, Department of Chemistry, College of Science, King Saud University, Riyadh 11451, Saudi Arabia
²Department of Applied Chemistry, Z.H. College of Engineering and Technology, AMU, Aligarh, UP, India
³Advanced Materials Research Chair, Department of Chemistry, College of Science, King Saud University, Riyadh 11451, Saudi Arabia
⁴, Saudi Arabia
⁵Departments of Biochemistry, College of Science, King Saud University, Riyadh 11451, Saudi Arabia

E-mail:,

Reduction of molecular oxygen by 2-mercaptoethanol in the presence of cobalt(II)histidine is described. Cobalt(II)histidine complex forms dinuclear 2:1 (Co:O2) complex with molecular oxygen (m-dioxyte-trakis(histidinato)dicobalt(II)). The molecular oxygen did not directly react with 2-mercaptoethanol, but, reacted in the form of an adduct with cobalt(II)histidine complex. During the course of the reaction the molecular oxygen is reduced to hydroxide ion while the cobalt(II)histidine complex was oxidized to cobalt(III)histidine while 2-mercaptoethanol is reduced into 2,2'-dithiodiethanol. The decrease in absorbance for the dioxygen complex was monitored spectrophotometrically and was observed that the values of rate constant increased with the increase in [2-mercaptoethanol]. The values of kobs also increased with increasing [NaOH]. Thus, from the results of these studies, mechanism of the reaction has been proposed. In addition, the values of various equilibrium constants and rate constants were also determined using nonlinear least square techniques.

Keywords:2-Mercaptoethanol;Oxidation;Cobalt(II)histidine;Oxygen carrier;Dioxygen

[References]

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Rafiquee MZA, Siddiqui MR, Ali MS, Al-Lohedan HA, Spectroc. Acta Pt. A-Molec. Biomolec. Spectr., 126, 21 (2014)
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[Referenced By]

[1] Nakahara A, Sakutaikagakuto to Seikagakun no Ryoiki (Borderline Field between Biochemistry and Coordination Chemistry), Nankodo, Tokyo, 1967, pp. 221-237.

[2] Otsuka S, Nakamura A, Tatsuno Y, Chem. Commun., http://dx.doi.org/10.1039/C1967000836A., 16, 836a (1967)

[3] Munakata M, Shigematsu T, Bull. Inst. Chem. Res. Kyoto Univ., 49, 297 (1971)

[4] Rafiquee MZA, Siddiqui MR, Ali MS, Al-Lohedan HA, Spectroc. Acta Pt. A-Molec. Biomolec. Spectr., 126, 21 (2014)

[5] Ehrenberg L, Harms-Ringdahl M, Fedorcsak I, Granath F, Acta Chem. Scand., 43, 177 (1989)

[6] Goswami S, Shaikh N, Panja A, Banerjeem P, Int. J. Chem. Kinet., 36, 129 (2004)

[7] Hearon JZ, Burk D, Schade AL, J. Nat. Cancer Inst., 9, 337 (1949)

[8] Earnshaw A, Larkworthy LE, Nature, 192, 1068 (1961)

[9] Sawyer DT, in: Martell AE, Sawyer DT (Eds.), Oxygen Complexes and Oxygen Activation by Transition Metals, Plenum, New York, 1988, p. 131.

[10] Malmstrom BG, Annu. Rev. Biochem., 51, 21 (1982)

[11] Ingraham LL, Meyer DL, Biochemistry of Dioxygen (B), first ed. (1985 edition), Plenum, New York, October 4, 2013 (Softcover reprint of the original).

[12] Hayaishi O, Molecular Mechanisms of Oxygen Activation (B), Academic Press Inc., New York, 1974p. 405.

[13] Tabassum S, Parveen S, Arjmand F, Transition Met. Chem., 30, 196 (2005)

[14] Weschler CJ, Hoffman BM, Basolo F, J. Am. Chem. Soc., 97, 5278 (1975)

[15] Fallab S, Angew. Chem.-Int. Edit., 6, 467 (1967)

[16] Karimi-Maleh H, Tahernejad-Javazmi F, Ensafi AA, Moradi R, Mallakpour S, Beitollahi H, Biosens. Bioelectron., 60, 1 (2014)

[17] Karimi-Maleh H, Biparva P, Hatami M, Biosens. Bioelectron., 48, 270 (2013)

[18] Ensafi AA, Khayamian T, Hasanpour F, J. Pharm. Biomed. Anal., 48, 140 (2008)

[19] Watkins JB, Benz FWC, Science, 199, 1084 (1978)

[20] Wong S, Kirkland JL, Schwanz HA, Simmons AL, Hamilton JA, Corkey BE, Guo W, Life Sci., 107, 32 (2014)

[21] Heidrick ML, Hendricks LC, Cook DE, Mech. Ageing Dev., 27, 341 (1984)

[22] Rafiquee MZA, Siddiqui MR, Ali MS, Al-Lohedan HA, Spectroc. Acta Pt. A-Molec. Biomolec. Spectr., 126, 121 (2014)

[23] Jameson GB, Ibers JA, in: Bertini I (Ed.), Bioinorganic Chemistry, University Science Books, Mill Valley, CA, 1994, p. 167.

[24] Sano Y, Tanabe H, J. Inorg. Nucl. Chem., 25, 11 (1963)

[25] van Streun KH, Belt WJ, Schipper ETWM, Piet P, German AL, J. Mol. Catal., 71, 245 (1992)

[26] Peel JL, Biochem. J., 88, 296 (1963)