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oai:www.ideals.illinois.edu:2142/25419 2023-07-10 col_2142_8859 col_2142_5131 com_2142_8858 com_2142_234 com_2142_5130

Mossbauer photosynthetic reaction centers ubiquinone high-spin ferrous iron o-phenanthroline Mössbauer studies of photsynthetic reaction centers from Rhodopseudomonas sphaeroides R-26 Dissertation / Thesis text Debrunner, Peter G. Boso, Brian 2011-06-16T14:34:08Z 2011-06-16T14:34:08Z 10000-01-01 1982 "Zero field Mossbauer measurements on 57Fe-enriched reaction centers (RCs) differing in ubiquinone content, detergent, oxidation state, or the presence of o-phenanthroline all show a single quadrupole doublet of similar splitting 6EQ, center shift 0, and temperature dependence. The results are indicative of high-spin ferrous iron (Fe+2, S=2) with an approximately invariant first coordination sphere consisting most likely of 6 (or 5) oxygens and nitrogens. The spectra show no evidence for either of the quinones or o-phenanthroline binding directly to the iron. High field (1.0T ~ B < 6.15T) variable temperature (4.2K ~ T < 211K) Mossbauer measurements on native (N) and dithionite reduced (R) RCs yield details concerning the electronic state of the iron. At low temperatures and fields the spectra of Nand R differ; the former consists of a sharp quadrupole doublet, while the lines in the latter are magnetically broadened via the spin-spin interaction with the semiquinone free radical. In high field the spectra of Nand Rare similir, showing broad unresolved doublets at 4.2K, which resolve at higher temperatures. The width of the lower energy line has a minimum near 25K. Analysis of the magnetic data using an empirical model of the internal magnetic field shows that the largest component of the quadrupole tensor, Vzz ' is positive, the asymmetry parameter, n , is 0.3 at 4.2K and 0.6 at 211K, and the quadrupole tensor is rotated with respect to the internal magnetic field. The components of the internal field differ widely in magnitude and temperature dependence.Spi'1 Hamiltonian simulations of the data suggest an unusually small A-tensor at 4.2K, (-9.41T,+1.72T,-10.3T), however, good simulations at other temperatures and fields are obtained if the A-tensor components are allowed to vary. Analysis using a crystal field model with strong electron delocalization can account for the temperature dependence of 6E, and DeltaEq indicates considerable ""unquenched"" <L>. Both the zero field and magnetic measurements suggest the ground state is primarily an <L> orbital and together they suggest that the symmetry at the iron site is lower than rhombic." Submitted by Carolyn Mead (cmead2@illinois.edu) on 2011-06-16T14:34:08Z No. of bitstreams: 1 1982_boso.pdf: 3851603 bytes, checksum: 0bcdb788167d68e0179d300cfffd0ccd (MD5) Made available in DSpace on 2011-06-16T14:34:08Z (GMT). No. of bitstreams: 1 1982_boso.pdf: 3851603 bytes, checksum: 0bcdb788167d68e0179d300cfffd0ccd (MD5) Previous issue date: 1982 Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Carolyn Mead (cmead2@illinois.edu) on 2011-06-16T14:34:08Z Item is restricted indefinitely. Restriction data tranferred 2014-07-01T11:14:08-05:00 Original Data Group with Access UIUC Users [automated] Release Date: none Reason: Thesis Thesis U of I Only 88424 http://hdl.handle.net/2142/25419 en 1982 Brian Boso Physics Physics University of Illinois at Urbana-Champaign Dissertation Ph.D.