Dataset Information

Mn2+ concentrations in coastal fish otoliths: understanding environmental and biological influences from EPR.

ABSTRACT: The Mn2+ concentrations in the sagittae otoliths of 12 fish families (and 19 species) that co-occur in a coastal area of southeastern Brazil (~21°S) were quantified using electron paramagnetic resonance (EPR). Inferences were made about the relationship between fish habitat and trace element incorporation. Inferences were made on the relationship between trace element concentration and otolith shape. The differences in Mn2+ concentrations among the species suggest that habitat (and feeding habits) might drive the incorporation of this trace element into fish otoliths, with higher values in bottom-associated fish species than in surface-associated species. In surface-associated fish species, the correlation between trace element concentrations and otolith shape was stronger than in bottom-associated species. Thus, while the Mn bioavailability in a fish's habitat, especially from feeding resources, is a local driving influence of trace element incorporation in sagittae otoliths, species-specific requirements also have an influence. Quantitative EPR is a non-destructive technique that is very useful when the available samples cannot be damaged, like with otolith collections.

SUBMITTER: Di Beneditto APM

PROVIDER: S-EPMC6082802 | biostudies-other | 2018 Sep

REPOSITORIES: biostudies-other

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Mn2+ concentrations in coastal fish otoliths: understanding environmental and biological influences from EPR.

Di Beneditto Ana Paula Madeira APM Franco Roberto Weider de Assis RWA

Journal of biological physics 20180530 3

The Mn2+ concentrations in the sagittae otoliths of 12 fish families (and 19 species) that co-occur in a coastal area of southeastern Brazil (~21°S) were quantified using electron paramagnetic resonance (EPR). Inferences were made about the relationship between fish habitat and trace element incorporation. Inferences were made on the relationship between trace element concentration and otolith shape. The differences in Mn2+ concentrations among the species suggest that habi ...[more]

PMID: 29850983

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Project description:Crystals of Zn2+/Mn2+ yeast enolase with the inhibitor PhAH (phosphonoacetohydroxamate) were grown under conditions with a slight preference for binding of Zn2+ at the higher affinity site, site I. The structure of the Zn2+/Mn2+-PhAH complex was solved at a resolution of 1.54 A, and the two catalytic metal binding sites, I and II, show only subtle displacement compared to that of the corresponding complex with the native Mg2+ ions. Low-temperature echo-detected high-field (W-band, 95 GHz) EPR (electron paramagnetic resonance) and 1H ENDOR (electron-nuclear double resonance) were carried out on a single crystal, and rotation patterns were acquired in two perpendicular planes. Analysis of the rotation patterns resolved a total of six Mn2+ sites, four symmetry-related sites of one type and two out of the four of the other type. The observation of two chemically inequivalent Mn2+ sites shows that Mn2+ ions populate both sites I and II and the zero-field splitting (ZFS) tensors of the Mn2+ in the two sites were determined. The Mn2+ site with the larger D value was assigned to site I based on the 1H ENDOR spectra, which identified the relevant water ligands. This assignment is consistent with the seemingly larger deviation of site I from octahedral symmetry, compared to that of site II. The ENDOR results gave the coordinates of the protons of two water ligands, and adding them to the crystal structure revealed their involvement in a network of H bonds stabilizing the binding of the metal ions and PhAH. Although specific hyperfine interactions with the inhibitor were not determined, the spectroscopic properties of the Mn2+ in the two sites were consistent with the crystal structure. Density functional theory (DFT) calculations carried out on a cluster representing the catalytic site, with Mn2+ in site I and Zn2+ in site II, and vice versa, gave overestimated D values on the order of the experimental ones, although the larger D value was found for Mn2+ in site II rather than in site I. This discrepancy was attributed to the high sensitivity of the ZFS parameters to the Mn-O bond lengths and orientations, such that small, but significant, differences between the optimized and crystal structures alter the ZFS considerably, well above the difference between the two sites.

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Mn2+ concentrations in coastal fish otoliths: understanding environmental and biological influences from EPR.

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Mn<sup>2+</sup> concentrations in coastal fish otoliths: understanding environmental and biological influences from EPR.

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