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Kinetics of Rapid Covalent Bond Formation of Aniline with Humic Acid: ESR Investigations with Nitroxide Spin Labels

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Abstract

The bioavailability of many soil contaminants depends on their interaction with the soil organic matter. The paper presents a new approach of using stable paramagnetic spin labels for investigating the kinetics of covalent binding of specific xenobiotic functional groups with humic acids, a major organic matter fraction. Leonardite humic acid (LHA) was incubated with the nitroxide spin labels amino-TEMPO (4-amino-2,2,6,6-Tetramethylpiperidin-1-oxyl) and anilino-NO (2,5,5-Trimethyl-2-(3-aminophenyl)pyrrolidin-1-oxyl), respectively, which contain an aliphatic or aromatic functionality susceptible to interaction with LHA. Electron spin resonance spectra of LHA samples without and with the enzyme laccase were recorded at X-band frequency (9.43 GHz) at room temperature and neutral pH. Binding was detected by a pronounced broadening of the spectral lines after incubation of LHA for both spin labels. The development of a broad signal component in the spectrum of anilino-NO indicated the immobilization due to strong binding of the aniline group. The reorientational correlation time of bound anilino-NO is more than two orders of magnitude greater than that of the free label. The ratio of the amount of bound to the unbound species was used to determine the kinetics of the covalent bond formation. Reaction rate constants of 0.16 and 0.01 min−1 were determined corresponding to half-times of 4.3 and 69.3 min, respectively. Treatment of LHA with laccase enhanced the amount of the reacting anilino-NO species by a factor of 7.6, but left the reaction rate unaltered. Oxidative radical coupling was excluded using the spin trap agent n-tert-butyl-alpha-phenylnitrone.

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Acknowledgments

We kindly acknowledge the lab assistance of Elena Bondarenko. Support of the Hungarian National Research Fund OTKA K104956 is greatly acknowledged.

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Authors and Affiliations

  1. Institute of Environmental Systems Research (USF), University of Osnabrück, 49069, Osnabrück, Germany

    Michael Matthies

  2. Physics Department, University of Osnabrück, 49069, Osnabrück, Germany

    Kevin Glinka, Marius Theiling & Heinz-Jürgen Steinhoff

  3. Department of Organic and Medicinal Chemistry, University of Pécs, Szigeti st. 12, 7624, Pécs, Hungary

    Kalman Hideg

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  1. Michael Matthies
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  2. Kevin Glinka
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Correspondence to Michael Matthies.

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Matthies, M., Glinka, K., Theiling, M. et al. Kinetics of Rapid Covalent Bond Formation of Aniline with Humic Acid: ESR Investigations with Nitroxide Spin Labels. Appl Magn Reson 47, 627–641 (2016). https://doi.org/10.1007/s00723-016-0782-8

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  • DOI: https://doi.org/10.1007/s00723-016-0782-8

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