Quadrupolar Metal Nuclides in Bioinorganic Chemistry: Solid-State NMR Studies

Lipton, Andrew S.; Ellis, Paul D.; Polenova, Tatyana

doi:10.1002/9780470034590.emrstm1082

Cited by 2 publications

(1 citation statement)

References 67 publications

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“…17 O chemical shifts in crystalline amino acids have also been demonstrated to correlate linearly with bond distance and angles [38] and variable-temperature measurements have been used to examine the dynamics and measure 1 H- 17 O couplings allowing for the measurements of O-H bond distances in barium chlorate monohydrate [39]. DFT calculations on bioinorganic complexes can help to correlate the experimental NMR parameters with local coordination environment and geometry of the observed nuclei [40–43]. 17 O NMR spectra of oxygen atoms directly bonded to paramagnetic metal ions have been reported by Kong et al [22] This work is particularly relevant in the context of enzymatic peroxo intermediates which typically have the peroxido moiety is ligated to a paramagnetic metal cofactor.…”

Section: Resultsmentioning

confidence: 99%

Direct detection and characterization of bioinorganic peroxo moieties in a vanadium complex by 17O solid-state NMR and density functional theory

Gupta

Stringer²,

Struppe

et al. 2018

Solid State Nuclear Magnetic Resonance

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Electronic and structural properties of short-lived metal-peroxido complexes, which are key intermediates in many enzymatic reactions, are not fully understood. While detected in various enzymes, their catalytic properties remain elusive because of their transient nature, making them difficult to study spectroscopically. We integrated 17O solid-state NMR and density functional theory (DFT) to directly detect and characterize the peroxido ligand in a bioinorganic V(V) complex mimicking intermediates non-heme vanadium haloperoxidases. 17O chemical shift and quadrupolar tensors, measured by solid-state NMR spectroscopy, probe the electronic structure of the peroxido ligand and its interaction with the metal. DFT analysis reveals the unusually large chemical shift anisotropy arising from the metal orbitals contributing towards the magnetic shielding of the ligand. The results illustrate the power of an integrated approach for studies of oxygen centers in enzyme reaction intermediates.

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Section: Resultsmentioning

confidence: 99%

Direct detection and characterization of bioinorganic peroxo moieties in a vanadium complex by 17O solid-state NMR and density functional theory

Gupta

Stringer²,

Struppe

et al. 2018

Solid State Nuclear Magnetic Resonance

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EMSL Quarterly Highlights Report: 1st Quarter, Fiscal Year 2009

Showalter¹,

Kathmann²,

Manke³

2009

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Using resources at the Department of Energy's EMSL and the Stanford Synchrotron Radiation Lightsource, scientists found that very low concentrations of dissolved metals in seawater may be the energy source microbial communities use to colonize seafloor rocks, presenting insights into how microbial communities thrive in the Earth's crust. These insights into the real-time evolution of the biosphere show how the Earth and its environmental processes function.The current hypothesis is that these communities derive the energy needed to grow by dissolving and oxidizing volcanic-created basalt. The team began with samples of young pillow basalts from the Loihi seamount, an underwater volcano known as the youngest in the Hawaiian chain. They determined the chemical changes that occurred on the basalt surfaces as the microbes colonized and grew.The analyses showed little evidence of basalt dissolution. Rather, biofilm growth was intimately tied to the oxidation of iron and manganese from the seawater, leading to the deposition of highly reactive Fe(III) and Mn(IV) oxide layer on the basalts surfaces. High-resolution imaging at EMSL on polished basalt glasses left near the volcano for a year also showed that volcanic glasses rapidly obtained an iron layer during biofilm growth. Over time, these mineral layers are likely to exert an enormous influence on the environmental chemistry of the seafloor. Microscopy experts at EMSL were significant contributors on the team from the University of Colorado at Boulder, SSRL, Scripps Institution of Oceanography, and the Oregon Health & Sciences University. This study was the first user project to apply EMSL's focused ion beam/scanning electron microscope.

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Quadrupolar Metal Nuclides in Bioinorganic Chemistry: Solid-State NMR Studies

Cited by 2 publications

References 67 publications

Direct detection and characterization of bioinorganic peroxo moieties in a vanadium complex by 17O solid-state NMR and density functional theory

Direct detection and characterization of bioinorganic peroxo moieties in a vanadium complex by 17O solid-state NMR and density functional theory

EMSL Quarterly Highlights Report: 1st Quarter, Fiscal Year 2009

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