A Mn(II)-Mn(III) EPR signal arises from the interaction of NO with the S1 state of the water-oxidizing complex of photosystem II

Biochemistry
Josephine SarrouV Petrouleas

Abstract

It was shown recently [Goussias, C., Ioannidis, N., and Petrouleas, V. (1997) Biochemistry 36, 9261-9266] that incubation of photosystem II preparations with NO at -30 degrees C in the dark results in the formation of a new intermediate of the water-oxidizing complex. This is characterized by an EPR signal centered at g = 2 with prominent manganese hyperfine structure. We have examined the detailed structure of the signal using difference EPR spectroscopy. This is facilitated by the observations that NO can be completely removed without decrease or modification of the signal, and illumination at 0 degree C eliminates the signal. The signal spans 1600 G and is characterized by sharp hyperfine structure. 14NO and 15NO cw EPR combined with pulsed ENDOR and ESEEM studies show no detectable contributions of the nitrogen nucleus to the spectrum. The spectrum bears similarities to the experimental spectrum of the Mn(II)-Mn(III) catalase [Zheng, M., Khangulov, S. V., Dismukes, G. C., and Barynin, V. V. (1994) Inorg. Chem. 33, 382-387]. Simulations allowing small variations in the catalase-tensor values result in an almost accurate reproduction of the NO-induced signal. This presents strong evidence for the assignment of the latter to a...Continue Reading

References

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Citations

Sep 10, 2011·Chemical Communications : Chem Comm·Evangelia S KoumousiTheocharis C Stamatatos
Nov 20, 2002·Philosophical Transactions of the Royal Society of London. Series B, Biological Sciences·Charilaos GoussiasA William Rutherford
Apr 16, 2014·Nitric Oxide : Biology and Chemistry·Amarendra N MisraEmilia L Apostolova
May 5, 1999·Current Opinion in Chemical Biology·C F Yocum, V L Pecoraro
Apr 22, 2004·Biochimica Et Biophysica Acta·Ron J Pace, Karin A Ahrling
Jul 25, 2000·Journal of Biological Inorganic Chemistry : JBIC : a Publication of the Society of Biological Inorganic Chemistry·N IoannidisV Petrouleas
Sep 9, 2004·Chemical Reviews·Sumitra MukhopadhyayWilliam H Armstrong
Sep 5, 2002·Journal of the American Chemical Society·Keri L ClemensR David Britt
Feb 27, 2010·Langmuir : the ACS Journal of Surfaces and Colloids·Shuichi IshigureMamoru Nango

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