Formation of 2,5-Dihydroxybenzoic acid during the reaction between 1O2 and salicylic acid: Analysis by ESR oximetry and HPLC with electrochemical detection

B. Kalyanaraman, Sujatha Ramanujam, Ravinder Jit Singh, Joy Joseph, Jimmy B. Feix

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Abstract

The oxygen consumption, vis-a-vis 1O2 production during irradiation of dyes such as rose bengal, merocyanine-540, and aluminum phthalocyaninetetrasulfonate, in the presence of salicylic acid was measured by electron spin resonance (ESR) oximetry. Concomitantly, formation of 2,5-dihydroxybenzoic acid (2,5-DHBA) in the same sample was analyzed by HPLC-EC. Both O2 consumption and 2,5-DHBA formation were stimulated by D2O, quenched by azide, unaffected in the presence of catalase, superoxide dismutase, and hydroxyl radical scavengers (ethanol, formate, etc.), and vastly diminished under N2. The stoichiometry between 1O2 consumption and 2,5-DHBA formation was determined to be ca. 0.5. On the basis of experiments using histidine, the chemical rate constant for the reaction between 1O2 and salicylic acid was determined to be 0.20 × 106 M-1 s-1. Furthermore, 1O2 generated from the thermal decomposition of the water-soluble endoperoxide of 3,3′-(1,4-naphthylidene)dipropionate (NDPO2) was shown to react with salicylic acid to form 2,5-DHBA as the major product. We conclude that exclusive formation of 2,5-DHBA is highly diagnostic of 1O2 intermediacy in photochemical systems and in biochemical systems lacking metabolic activity. HPLC-EC is thus a valuable adjunct to ESR oximetry in the characterization of 1O2 and may, on the basis of the selectivity of this reaction, provide a sensitive analytical method for detecting 1O2 intermediacy.

Original languageEnglish (US)
Pages (from-to)4007-4012
Number of pages6
JournalJournal of the American Chemical Society
Volume115
Issue number10
StatePublished - May 19 1993

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Salicylic acid
Oximetry
Salicylic Acid
Electron Spin Resonance Spectroscopy
Paramagnetic resonance
High Pressure Liquid Chromatography
Acids
formic acid
Rose Bengal
Azides
Aluminum
Histidine
Oxygen Consumption
Superoxides
Stoichiometry
Hydroxyl Radical
Catalase
Superoxide Dismutase
Rate constants
Pyrolysis

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Formation of 2,5-Dihydroxybenzoic acid during the reaction between 1O2 and salicylic acid : Analysis by ESR oximetry and HPLC with electrochemical detection. / Kalyanaraman, B.; Ramanujam, Sujatha; Singh, Ravinder Jit; Joseph, Joy; Feix, Jimmy B.

In: Journal of the American Chemical Society, Vol. 115, No. 10, 19.05.1993, p. 4007-4012.

Research output: Contribution to journalArticle

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abstract = "The oxygen consumption, vis-a-vis 1O2 production during irradiation of dyes such as rose bengal, merocyanine-540, and aluminum phthalocyaninetetrasulfonate, in the presence of salicylic acid was measured by electron spin resonance (ESR) oximetry. Concomitantly, formation of 2,5-dihydroxybenzoic acid (2,5-DHBA) in the same sample was analyzed by HPLC-EC. Both O2 consumption and 2,5-DHBA formation were stimulated by D2O, quenched by azide, unaffected in the presence of catalase, superoxide dismutase, and hydroxyl radical scavengers (ethanol, formate, etc.), and vastly diminished under N2. The stoichiometry between 1O2 consumption and 2,5-DHBA formation was determined to be ca. 0.5. On the basis of experiments using histidine, the chemical rate constant for the reaction between 1O2 and salicylic acid was determined to be 0.20 × 106 M-1 s-1. Furthermore, 1O2 generated from the thermal decomposition of the water-soluble endoperoxide of 3,3′-(1,4-naphthylidene)dipropionate (NDPO2) was shown to react with salicylic acid to form 2,5-DHBA as the major product. We conclude that exclusive formation of 2,5-DHBA is highly diagnostic of 1O2 intermediacy in photochemical systems and in biochemical systems lacking metabolic activity. HPLC-EC is thus a valuable adjunct to ESR oximetry in the characterization of 1O2 and may, on the basis of the selectivity of this reaction, provide a sensitive analytical method for detecting 1O2 intermediacy.",
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