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Title: Electron Paramagnetic Resonance Characterization of the Triheme Cytochrome from Geobacter sulfurreducens

Journal Article · · Biochemistry
ORCiD logo [1]; ORCiD logo [1];  [2];  [1];  [1]
  1. Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
  2. Argonne National Lab. (ANL), Argonne, IL (United States). Biosciences Division
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Periplasmic cytochrome A (PpcA) is a representative of a broad class of multiheme cytochromes functioning as protein “nanowires” for storage and extracellular transfer of multiple electrons in the δ-proteobacterium Geobacter sulfurreducens. PpcA contains three bis-His coordinated hemes held in a spatial arrangement that is highly conserved among the multiheme cytochromes c3 and c7 families, carries low potential hemes, and is notable for having one of the lowest number of amino acids utilized to maintain a characteristic protein fold and site-specific heme function. Low temperature X-band electron paramagnetic resonance (EPR) spectroscopy has been used to characterize the electronic configuration of the Fe(III) and the ligation mode for each heme. The three sets of EPR signals are assigned to individual hemes in the three-dimensional crystal structure. The relative energy levels of the Fe(III) 3d orbitals for individual hemes were estimated from the principal g-values. The observed g-tensor anisotropy was used as a probe of electronic structure of each heme, and differences were determined by specifics of axial ligation. To ensure unambiguous assignment of highly anisotropic low-spin (HALS) signal to individual hemes, EPR analyses of iron atom electronic configurations have been supplemented with investigation of porphyrin macrocycles by one-dimensional 1H NMR chemical shift patterns for the methyl substituents. In conclusion, within optimized geometry of hemes in PpcA, the magnetic interactions between hemes were found to be minimal, similar to the c3 family of tetraheme cytochromes.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
1427531
Journal Information:
Biochemistry, Vol. 57, Issue 11; ISSN 0006-2960
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 3 works
Citation information provided by
Web of Science

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Cited By (1)

Examination of abiotic cofactor assembly in photosynthetic biomimetics: site-specific stereoselectivity in the conjugation of a ruthenium(II) tris(bipyridine) photosensitizer to a multi-heme protein journal January 2020

Figures / Tables (9)

Figure 1.(p. 3)figure Figure 1.
Figure 2.(p. 8)figure Figure 2.
Table 1.(p. 9)table Table 1.
Figure 3.(p. 11)figure Figure 3.
Figure 4.(p. 13)figure Figure 4.
Table 2.(p. 13)table Table 2.
Figure 5.(p. 15)figure Figure 5.
Table 3.(p. 17)table Table 3.
Figure 6.(p. 19)figure Figure 6.

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
1H NMR
Geobacter sulfurreducens
Periplasmic cytochrome A
PpcA
X-band EPR
heme coordination
triheme cytochrome