DOI: 10.1111/j.1432-1033.1988.tb13792.x. Higher oxidation states of prostaglandin H synthase

Higher oxidation states of prostaglandin H synthase

10.1111/j.1432-1033.1988.tb13792.x

Crossref journal-article

Wiley

European Journal of Biochemistry (311)

Abstract

Purified prostaglandin H synthase (EC 1.14.99.1), reconstituted with hemin, was reacted with substrates of the cyclooxygenase and peroxidase reaction. The resulting EPR spectra were measured below 90 K. Arachidonic acid, added under anaerobic conditions, did not change the EPR spectrum of the native enzyme due to high‐spin ferric heme. Arachidonic acid with O2, as well as prostaglandin G2 or H2O2, decreased the spectrum of the native enzyme and concomitantly a doublet signal at g= 2.005 was formed with maximal intensity of 0.35 spins/enzyme and a half‐life of less than 20 s at ‐12 °C. From the conditions for the formation and the effect of inhibitors, this doublet signal was assigned to an enzyme intermediate of the peroxidase reaction, namely a higher oxidation state.The doublet signal with characteristic hyperfine structure was nearly identical to the signal of the tyrosyl radical in ribonucleotide reductase (EC 1.17.4.1). Hence the signal of prostaglandin H synthase was assigned to a tyrosyl radical. Electronic spectra as well as decreased power saturation of the tyrosyl radical signal indicated heme in its ferryl state which coupled to the tyrosyl radical weakly. [FeIVO(protoporphyrin IX)]…Tyr+· was suggested as the structure of this two‐electron oxidized state of the enzyme.A hypothetical role for the tyrosyl radical could be the abstraction of a hydrogen at C‐13 of arachidonic acid which is assumed to be the initial step of the cyclooxygenase reaction.

Bibliography

KARTHEIN, R., DIETZ, R., NASTAINCZYK, W., & RUF, H. H. (1988). Higher oxidation states of prostaglandin H synthase. European Journal of Biochemistry, 171(1â2), 313â320. Portico.

Authors 4

Rainer KARTHEIN (first)
Reiner DIETZ (additional)
Wolfgang NASTAINCZYK (additional)
Hans Heinrich RUF (additional)

References 50 Referenced 247

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Dates

Type	When
Created	20 years, 5 months ago (March 3, 2005, 8:49 p.m.)
Deposited	1 year, 11 months ago (Aug. 31, 2023, 7:22 a.m.)
Indexed	1 month, 3 weeks ago (July 3, 2025, 9:28 p.m.)
Issued	37 years, 7 months ago (Jan. 1, 1988)
Published	37 years, 7 months ago (Jan. 1, 1988)
Published Online	20 years, 5 months ago (March 3, 2005)
Published Print	37 years, 7 months ago (Jan. 1, 1988)

Funders 0

None

BibTeX

@article{KARTHEIN_1988, title={Higher oxidation states of prostaglandin H synthase: EPR study of a transient tyrosyl radical in the enzyme during the peroxidase reaction}, volume={171}, ISSN={1432-1033}, url={http://dx.doi.org/10.1111/j.1432-1033.1988.tb13792.x}, DOI={10.1111/j.1432-1033.1988.tb13792.x}, number={1–2}, journal={European Journal of Biochemistry}, publisher={Wiley}, author={KARTHEIN, Rainer and DIETZ, Reiner and NASTAINCZYK, Wolfgang and RUF, Hans Heinrich}, year={1988}, month=jan, pages={313–320} }

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    "date-parts": [
      [
        1988,
        1
      ]
    ]
  },
  "references-count": 50,
  "journal-issue": {
    "issue": "1-2",
    "published-print": {
      "date-parts": [
        [
          1988,
          1
        ]
      ]
    }
  },
  "alternative-id": [
    "10.1111/j.1432-1033.1988.tb13792.x"
  ],
  "URL": "http://dx.doi.org/10.1111/j.1432-1033.1988.tb13792.x",
  "relation": {},
  "ISSN": [
    "0014-2956",
    "1432-1033"
  ],
  "subject": [],
  "container-title-short": "European Journal of Biochemistry",
  "published": {
    "date-parts": [
      [
        1988,
        1
      ]
    ]
  }
}