Characteristic oxidation behavior of β-cyclocitral from the cyanobacterium Microcystis

Abstract

The cyanobacterium Microcystis produces volatile organic compounds such as β-cyclocitral and 3-methyl-1-butanol. The lysis of cyanobacteria involving the blue color formation has been occasionally observed in a natural environment. In this study, we focused on the oxidation behavior of β-cyclocitral that contributed to the blue color formation in a natural environment and compared β-cyclocitral with a structurally related compound concerning its oxidation, acidification, and lytic behavior. The oxidation products of β-cyclocitral were identified by the addition of β-cyclocitral in water, in which 2,2,6-trimethylcyclohex-1-ene-1-yl formate and 2,2,6-trimethylcyclohexanone were structurally characterized. That is, β-cyclocitral was easily oxidized to produce the corresponding carboxylic acid and the enol ester in water without an oxidizing reagent, suggesting that this oxidation proceeded according to the Baeyer-Villiger oxidation. The oxidation behavior of β-cyclocitral in a laboratory was different from that in the natural environment, in which 2,2,6- trimethylcyclohexanone was detected at the highest amount in the natural environment, whereas the highest amount in the laboratory was β-cyclocitric acid. A comparison of β-cyclocitral with structurally similar aldehydes concerning the lytic behavior of a Microcystis strain and the acidification process indicated that only β-cyclocitral was easily oxidized. Furthermore, it was found that a blue color formation occurred between pH 5.5 and 6.5, suggesting that chlorophyll a and β-carotene are unstable and decomposed, whereas phycocyanin was stable to some extent in this range. The obtained results of the characteristic oxidation behavior of β-cyclocitral would contribute to a better understanding of the cyanobacterial life cycle.

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Acknowledgments

We acknowledge Drs. Atsushi Miyachi and Andrea Roxanne J. Anas and Mr. Kohei Kawai for measurement of the high-resolution mass spectral data, NMR measurement, and technical assistance, respectively, in this study.

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Correspondence to Koji Tomita.

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Responsible editor: Philippe Garrigues

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Tomita, K., Hasegawa, M., Arii, S. et al. Characteristic oxidation behavior of β-cyclocitral from the cyanobacterium Microcystis . Environ Sci Pollut Res 23, 11998–12006 (2016). https://doi.org/10.1007/s11356-016-6369-y

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Keywords

  • β-cyclocitral
  • Oxidation
  • Acidification
  • Cyanobacteria
  • Blue color formation
  • Lysis