Kinetic Study of the Quenching Reaction of Singlet Oxygen by Common Synthetic Antioxidants (tert-Butylhydroxyanisol, tert-di-Butylhydroxytoluene, and tert-Butylhydroquinone) as Compared with α-Tocopherol

Authors

  • Ji In Kim,

    1. Author Kim is with Dept. of Biomaterials Science and Engineering, Yonsei Univ., Seoul, Republic of Korea. Authors Lee, Choi, and Jung are with College of Food Science, Woosuk Univ., Samrea-Up, Wanju-Kun, Jeonbuk Province 565-701, Republic of Korea. Authors Won and Park are with Dept. of Biotechnology, Yonsei Univ. 262, Seongsanno, Seodaemun-gu, Seoul 120-749, Republic of Korea. Direct inquiries to author Jung (E-mail: munjung@woosuk.ac.kr).
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  • Jun Hyun Lee,

    1. Author Kim is with Dept. of Biomaterials Science and Engineering, Yonsei Univ., Seoul, Republic of Korea. Authors Lee, Choi, and Jung are with College of Food Science, Woosuk Univ., Samrea-Up, Wanju-Kun, Jeonbuk Province 565-701, Republic of Korea. Authors Won and Park are with Dept. of Biotechnology, Yonsei Univ. 262, Seongsanno, Seodaemun-gu, Seoul 120-749, Republic of Korea. Direct inquiries to author Jung (E-mail: munjung@woosuk.ac.kr).
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  • Dong Seong Choi,

    1. Author Kim is with Dept. of Biomaterials Science and Engineering, Yonsei Univ., Seoul, Republic of Korea. Authors Lee, Choi, and Jung are with College of Food Science, Woosuk Univ., Samrea-Up, Wanju-Kun, Jeonbuk Province 565-701, Republic of Korea. Authors Won and Park are with Dept. of Biotechnology, Yonsei Univ. 262, Seongsanno, Seodaemun-gu, Seoul 120-749, Republic of Korea. Direct inquiries to author Jung (E-mail: munjung@woosuk.ac.kr).
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  • Bo Mi Won,

    1. Author Kim is with Dept. of Biomaterials Science and Engineering, Yonsei Univ., Seoul, Republic of Korea. Authors Lee, Choi, and Jung are with College of Food Science, Woosuk Univ., Samrea-Up, Wanju-Kun, Jeonbuk Province 565-701, Republic of Korea. Authors Won and Park are with Dept. of Biotechnology, Yonsei Univ. 262, Seongsanno, Seodaemun-gu, Seoul 120-749, Republic of Korea. Direct inquiries to author Jung (E-mail: munjung@woosuk.ac.kr).
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  • Mun Yhung Jung,

    1. Author Kim is with Dept. of Biomaterials Science and Engineering, Yonsei Univ., Seoul, Republic of Korea. Authors Lee, Choi, and Jung are with College of Food Science, Woosuk Univ., Samrea-Up, Wanju-Kun, Jeonbuk Province 565-701, Republic of Korea. Authors Won and Park are with Dept. of Biotechnology, Yonsei Univ. 262, Seongsanno, Seodaemun-gu, Seoul 120-749, Republic of Korea. Direct inquiries to author Jung (E-mail: munjung@woosuk.ac.kr).
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  • Jiyong Park

    1. Author Kim is with Dept. of Biomaterials Science and Engineering, Yonsei Univ., Seoul, Republic of Korea. Authors Lee, Choi, and Jung are with College of Food Science, Woosuk Univ., Samrea-Up, Wanju-Kun, Jeonbuk Province 565-701, Republic of Korea. Authors Won and Park are with Dept. of Biotechnology, Yonsei Univ. 262, Seongsanno, Seodaemun-gu, Seoul 120-749, Republic of Korea. Direct inquiries to author Jung (E-mail: munjung@woosuk.ac.kr).
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Abstract

ABSTRACT:  Effects of synthetic phenolic antioxidants (BHA, BHT, and TBHQ) on the methylene blue (MB) sensitized photooxidation of linoleic acid as compared with that of α-tocopherol have been studied. Their antioxidative mechanism was studied by both ESR spectroscopy in a 2,2,6,6-tetramethylpiperidone (TMPD)-methylene blue (MB) system and spectroscopic analysis of rubrene oxidation induced by a chemical source of singlet oxygen. Total singlet oxygen quenching rate constants (kox−Q+kq) were determined using a steady state kinetic equation. TBHQ showed the strongest protective activity against the MB sensitized photooxidation of linoleic acid, followed by BHA and BHT. TBHQ (1 × 10−3 M) exhibited 86.5% and 71.4% inhibition of peroxide and conjugated diene formations, respectively, in linoleic acid photooxidation after 60-min light illumination. The protective activity of TBHQ against the photosensitized oxidation of linoleic acid was almost comparable to that of α-tocopherol. The data obtained from ESR and rubrene oxidation studies clearly showed the strong singlet oxygen quenching ability of TBHQ. The kox−Q+kq of BHA, BHT, and TBHQ were determined to be 3.37 × 107, 4.26 × 106, and 1.67 × 108 M−1 s−1, respectively. The kox−Q+kq of TBHQ was within the same order of magnitude of that of α-tocopherol, a known efficient singlet oxygen quencher. There was a high negative correlation (r2 = −0.991) between log (kox−Q+kq) and reported oxidation potentials for the synthetic antioxidants, indicating their charge-transfer mechanism for singlet oxygen quenching. This is the 1st report on the kinetic study on kox−Q+kq of TBHQ in methanol as compared with other commonly used commercial synthetic antioxidants and α-tocopherol.

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