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• W1991750246 endingPage "1805" @default.
• W1991750246 startingPage "1795" @default.
• W1991750246 abstract "In contrast to high-spin ferrous paramagnetic heme proteins, the chemical shifts of the heme protons are very unusual in the ferrocytochromes c‘. Magnetic susceptibility studies of Rhodobacter capsulatus ferrocytochrome c‘ in frozen solutions have been performed and indicate an S = 2 spin state and a large negative axial (D) zero-field splitting parameter (−18.3 cm-1) as well as a significant rhombic (E) value (−4.9 cm-1). The 1H and 15N resonances have been extensively assigned by TOCSY−HSQC, NOESY−HSQC, and HSQC−NOESY−HSQC 3-D heteronuclear experiments performed on a 8 mM sample labeled with 15N. Based on short-range and medium-range NOEs and HN exchange rates, the secondary structure consists of four helices: helix-1 (3−30), helix-2 (34−49), helix-3 (78−97), and helix-4 (103−117). The 15N, HN, and Hα chemical shifts of the reduced (or ferro) state are compared to those previously assigned for the diamagnetic carbon monoxide complex form. From the chemical shift differences between these redox states, the orientation and the anisotropy of the paramagnetic susceptibility tensor have been determined using the crystallographic coordinates of the ferric state. Values of −23 and −3 cm-1 have been inferred for D and E, and the z-axis of the tensor is tilted approximately 30° from the normal to the heme. The paramagnetic chemical shifts of the heme protons have been determined and split up into Fermi shift and the dipolar shift contributions. The pattern of the contact shifts is very unusual, exhibiting a 2-fold symmetry, and is discussed in terms of molecular orbital interactions between the porphyrin macrocycle and the imidazole ring." @default.
• W1991750246 created "2016-06-24" @default.
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• W1991750246 date "1999-02-19" @default.
• W1991750246 modified "2023-10-09" @default.
• W1991750246 title "Unusual Contact Shifts and Magnetic Tensor Orientation in <i>Rhodobacter</i> <i>capsulatus</i> Ferrocytochrome <i>c</i>‘: NMR, Magnetic Susceptibility, and EPR Studies" @default.
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• W1991750246 doi "https://doi.org/10.1021/ja9820745" @default.
• W1991750246 hasPublicationYear "1999" @default.
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