AJAC  Vol.5 No.15 , November 2014
The Application of Novel Electrochemical Approach to Antioxidant Activity Assay of Metal Porphyrins with Bulky 3,5-Diisobornyl-4-hydroxyphenyl Moieties
Abstract: The complexes of biogenic metals (Zn2+,Cu2+,Co2+,Mn3+,Fe3+) based on meso-tetra(3,5-diisobor- nyl-4-hydroxyphenyl)porphyrin 1 were synthesized. The electrochemical behavior of these com-pounds was studied using cyclic voltammetry (CV) and rotating disk electrode (RDE) techniques. The antioxidant activity of complexes was estimated by means of the electrochemical assay based on the hydrogen atom transfer reaction to the stable radical 2,2’-diphenyl-1-picrylhydrazyl (DPPH). The RDE method was applied for this process monitoring. It was shown that the efficiency of the metal complexes (Cu2+,Co2+,Mn2+,Ni2+,Fe3+) is practically the same order as that of free base porphyrin 1. However the Zn2+ complex demonstrates significantly higher antioxidant activity, and the stoichiometry of the reaction was determined as σ = 4. The results demonstrate that porphyrin macrocycle can directly affect the antioxidant properties of 2,6-diisobornylphenol.
Cite this paper: Rocheva, T. , Tyurin, V. , Belykh, D. , Moiseeva, А. , Zhang, J. , Buravlev, Е. , Chukicheva, I. , Alexander Kutchin, A. and Milaeva, E. (2014) The Application of Novel Electrochemical Approach to Antioxidant Activity Assay of Metal Porphyrins with Bulky 3,5-Diisobornyl-4-hydroxyphenyl Moieties. American Journal of Analytical Chemistry, 5, 1028-1036. doi: 10.4236/ajac.2014.515109.

[1]   Migliore, L. and Coppedè, F. (2009) Environmental-Induced Oxidative Stress in Neurodegenerative Disorders and Aging. Mutation Research, 674, 73-84.

[2]   Liu, Z.-Q. (2010) Chemical Methods to Evaluate Antioxidant Ability. Chemical Reviews, 110, 5675-5691.

[3]   Niki, E. (2010) Assessment of Antioxidant Capacity in Vitro and in Vivo. Free Radical Biology and Medicine, 49, 503-515.

[4]   Denisov, E.T. (1995) Handbook of Antioxidants: Bond Dissociation Energies, Rate Constants, Activation Energies, and Enthalpies of Reactions. CRC Press, Boca Raton, 174 p.

[5]   Niki, E., Yoshida, Y., Saito, Y. and Noguchi, N. (2005) Lipid Peroxidation: Mechanisms, Inhibition, and Biological Effects. Biochemical and Biophysical Research Communications, 338, 668-676.

[6]   Buravlev, E.V., Chukicheva, I.Yu., Belykh, D.V. and Kuchin, A.V (2007) Simple Synthesis of a Terpenophenol-Chlorin Conjugate with an Amide Bond. Chemistry of Natural Compounds, 43, 678-681.

[7]   Milaeva, E.R. (2011) Metal-Based Antioxidants-Potential Therapeutic Candidates for Prevention the Oxidative Stress-Related Carcinogenesis: Mini-Review. Current Topics in Medicinal Chemistry, 11, 2703-2713.

[8]   Plotnikov, M.B., Chernysheva, G.A., Smol’yakova, V.I., Ivanov, I.S., Kuchin, A.V., Chukicheva, I.Iu. and Krasnov, E.A. (2009) Neuroprotective Effects of Dibornol and Mechanism of Its Action in Rats with Cerebral Ischemia. Vestnik Rossiiskoi Akademii Meditsinskikh Nauk, 11, 12-17. (In Russian)

[9]   Milaeva, E., Shpakovsky, D., Gracheva, Yu., Gerasimova, O., Tyurin, V. and Petrosyan, V. (2003) Oleic Acid Peroxidation in the Presence of Metallo-Porphyrins. Journal of Porphyrins and Phthalocyanines, 7, 719-724.

[10]   Milaeva, E.R., Gerasimova, O.A., Jingwei, Z., Shpakovsky, D.B., Syrbu, S.A., Semeykin, A.S., Koifman, O.I., Kireeva, E.G., Shevtsova, E.F., Bachurin, S.O. and Zefirov, N.S. (2008) Synthesis and Antioxidative Activity of Metalloporphyrins Bearing 2,6-Di-tert-butylphenol pendants. Journal of Inorganic Biochemistry, 102, 1348-1358.

[11]   Tyurin, V.Y., Zhang, J., Moiseeva, A.A., Milaeva, E.R., Belykh, D.V., Buravlev, E.V., Rocheva, T.K., Chukicheva, I.Y. and Kuchin, A.V. (2013) Comparative Study of Redox Characteristics and Antioxidant Activity of Porphyrins with 2,6-Dialkylphenol Groups. Doklady Chemistry, 450, 152-155.

[12]   Rocheva, T.K., Belykh, D.V., Buravlev, E.V., Chukicheva, I.Y., Shevchenko, O.G. and Kutchin, A.V. (2013) Book of Abstracts of the 1st Conference on Medical Chemistry “MedChem Russia-2013”. Moscow, 252. (In Russian)

[13]   Tyurin, V.Y., Meleshonkova, N.N., Dolganov, A.V., Glukhova, A.P. and Milaeva, E.R. (2011) Electrochemical Method in Determination of Antioxidative Activity Using Ferrocene Derivatives as Examples. Russian Chemical Bulletin, 60, 647-655.

[14]   Tyurin, V.Y., Wu, Y., Dolganov, A.V. and Milaeva, E.R. (2011) Antioxidant Activity Assay of 2,6-Di-tert-butylphenols with Phosphonate Groups Using Cyclic Voltammetry. Doklady Chemistry, 436, 31-33.

[15]   Tyurin, V.Y., Zhang, J., Glukhova, A. and Milaeva, E.R. (2011) Electrochemical Antioxidative Activity Assay of Metalloporphyrins Bearing 2,6-Di-tert-butylphenol Groups Based on Electrochemical DPPH-Test. Macroheterocycles, 4, 211-212.

[16]   Belykh, D.V., Rocheva, T.K., Buravlev, E.V., Chukicheva, I.Y. and Kutchin, A.V. (2012) The First Tetra(meso-aryl)porphyrin with Isobornyl Substituents. Macroheterocycles, 5, 121-124.

[17]   Gordon, A.J. and Ford, R.A. (1973) The Chemist’s Companion: A Handbook of Practical Data, Techniques and References. John Wiley and Sons, Inc., New York, 560 p.

[18]   Solon, E. and Bard, A.J. (1964) The Electrochemistry of Diphenylpicrylhydrazyl. Journal of the American Chemical Society, 86, 1926-1928.

[19]   Solon, E. and Bard, A.J. (1964) Coulometric Study of the Reaction of Diphenylpicrylhydrazyl and Bromide Ion. Journal of Physical Chemistry, 68, 1144-1147.

[20]   Galus, Z. (1971) Teoretyczne podstawy elektroanalizy chemicznej: Polarografia, chronowoltamperometria, chronopotencjometria, metoda wirujacego dysku. Państwowe Wydawnictwo Naukowe, Warszawa, 390 p.

[21]   Brand-Williams, W., Cuvelier, M.E. and Berset, C. (1995) Use of a Free Radical Method to Evaluate Antioxidant Activity. LWT, Food Science and Technology, 28, 25-30.

[22]   Bondet, V., Brand-Williams, W. and Berset, C. (1997) Kinetics and Mechanisms of Antioxidant Activity Using the DPPH Free Radical Method. LWT, Food Science and Technology, 30, 609-615.

[23]   Mishra, K., Ojha, H. and Chaudhury, N.K. (2012) Estimation of Antiradical Properties of Antioxidants Using DPPH Assay: A Critical Review and Results. Food Chemistry, 130, 1036-1043.

[24]   Sharma, O.P. and Bhat, T.K. (2009) DPPH Antioxidant Assay Revisited. Food Chemistry, 113, 1202-1205.

[25]   Meleshonkova, N.N., Shpakovsky, D.B., Fionov, A.V., Dolganov, A.V., Magdesieva, T.V. and Milaeva, E.R. (2007) Synthesis and Redox Properties of Novel Ferrocenes with Redox Active 2,6-Di-tert-butylphenol Fragments: The First Example of 2,6-Di-tert-butylphenoxyl Radicals in Ferrocene System. Journal of Organometallic Chemistry, 692, 5339-5344.