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Direct detection and characterization of bioinorganic peroxo moieties in a vanadium complex by 17O solid-state NMR and density functional theory
| Content Provider | Scilit |
|---|---|
| Author | Gupta, Rupal Stringer, John Struppe, Jochem Rehder, Dieter Polenova, Tatyana |
| Copyright Year | 2018 |
| Description | Journal: Solid State Nuclear Magnetic Resonance 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$ ^{17}$O solid-state NMR and density functional theory (DFT) to directly detect and characterize the peroxido ligand in a bioinorganic V(V) complex mimicking intermediates non-heme vanadium haloperoxidases.$ ^{17}$O 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. |
| Related Links | https://manuscript.elsevier.com/S0926204017301510/pdf/S0926204017301510.pdf https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6267778/pdf |
| Ending Page | 20 |
| Page Count | 6 |
| Starting Page | 15 |
| ISSN | 09262040 |
| e-ISSN | 15273326 |
| DOI | 10.1016/j.ssnmr.2018.02.001 |
| Journal | Solid State Nuclear Magnetic Resonance |
| Volume Number | 91 |
| Language | English |
| Publisher | Elsevier BV |
| Publisher Date | 2018-07-01 |
| Access Restriction | Open |
| Subject Keyword | Journal: Solid State Nuclear Magnetic Resonance Atomic, Molecular and Chemical Physics 17o Solid State Nmr Density Functional Theory Calculations Peroxido Ligand Reactive Intermediates |
| Content Type | Text |
| Resource Type | Article |
| Subject | Chemistry Nuclear and High Energy Physics Instrumentation Radiation |
