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  • 1
    ISSN: 1573-5079
    Keywords: manganese cluster ; multiline signal ; oxygen evolution ; S-states ; water ligation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract A comparative study of X-band EPR and ENDOR of the S2 state of photosystem II membrane fragments and core complexes in the frozen state is presented. The S2 state was generated either by continuous illumination at T=200 K or by a single turn-over light flash at T=273 K yielding entirely the same S2 state EPR signals at 10 K. In membrane fragments and core complex preparations both the multiline and the g=4.1 signals were detected with comparable relative intensity. The absence of the 17 and 23 kDa proteins in the core complex preparation has no effect on the appearance of the EPR signals. 1H-ENDOR experiments performed at two different field positions of the S2 state multiline signal of core complexes permitted the resolution of four hyperfine (hf) splittings. The hf coupling constants obtained are 4.0, 2.3, 1.1 and 0.6 MHz, in good agreement with results that were previously reported (Tang et al. (1993) J Am Chem Soc 115: 2382–2389). The intensities of all four line pairs belonging to these hf couplings are diminished in D2O. A novel model is presented and on the basis of the two largest hfc's distances between the manganese ions and the exchangeable protons are deduced. The interpretation of the ENDOR data indicates that these hf couplings might arise from water which is directly ligated to the manganese of the water oxidizing complex in redox state S2.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 23 (1984), S. 173-194 
    ISSN: 0570-0833
    Keywords: ENDOR spectroscopy ; Spectroscopy ; Free radicals ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The name “ENDOR” has been known since biblical times and denotes a small town close to the Sea of Galilee (ca. 1000 B.C., 1 Sam. 28 : 7 ff). The acronym “ENDOR” (Electron Nuclear DOuble Resonance) characterizes the extension of electron spin resonance to electron-nuclear double resonance spectroscopy, a method that has opened up new dimensions for the investigation of complicated paramagnetic molecules. Only ENDOR spectoscopy, which has achieved technical perfection in the last decade, overcomes the resolution limitations of EPR spectroscopy, thus allowing interesting applications in the field of biochemistry. ENDOR investigations of the primary process of photosynthesis, of the mode of action of derivatives of vitamin E and K, and of the mechanism of the enzymatic catalysis of flavoenzymes in biological redox-chains have opened up new vistas. ENDOR and its extension to the triple resonance experiment TRIPLE offer, for example, the potential for a precise determination of hyperfine coupling constants, including their signs, which are frequently especially interesting. In addition to protons, a multiple of magnetic nuclei can be studied by ENDOR, such as e.g. 2H, 13C, and 14N. The ENDOR techniques is not restricted to monoradicals, but can also be applied to polyradicals in spin states of higher multiplicities (triplet, quartet, or quintet state). The experimental data accessible from ENDOR yield information about spin and charge density distributions, and about the geometrics of radicals and their internal dynamics; they also provide an excellent test for the accuracy of quantum mechanical calculations.
    Additional Material: 23 Ill.
    Type of Medium: Electronic Resource
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