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Disproportionation of Nitric Oxide at a Surface-Bound Nickel Porphyrinoid.

ABSTRACT: Uncommon metal oxidation states in porphyrinoid cofactors are responsible for the activity of many enzymes. The F₄₃₀ and P450nor co-factors, with their reduced Ni^I - and Fe^III -containing tetrapyrrolic cores, are prototypical examples of biological systems involved in methane formation and in the reduction of nitric oxide, respectively. Herein, using a comprehensive range of experimental and theoretical methods, we raise evidence that nickel tetraphenyl porphyrins deposited in vacuo on a copper surface are reactive towards nitric oxide disproportionation at room temperature. The interpretation of the measurements is far from being straightforward due to the high reactivity of the different nitrogen oxides species (eventually present in the residual gas background) and of the possible reaction intermediates. The picture is detailed in order to disentangle the challenging complexity of the system, where even a small fraction of contamination can change the scenario.

SUBMITTER: Stredansky M

PROVIDER: S-EPMC9314816 | biostudies-literature | 2022 May

REPOSITORIES: biostudies-literature

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Disproportionation of Nitric Oxide at a Surface-Bound Nickel Porphyrinoid.

Stredansky Matus M Moro Stefania S Corva Manuel M Sturmeit Henning H Mischke Valentin V Janas David D Cojocariu Iulia I Jugovac Matteo M Cossaro Albano A Verdini Alberto A Floreano Luca L Feng Zhijing Z Sala Alessandro A Comelli Giovanni G Windischbacher Andreas A Puschnig Peter P Hohner Chantal C Kettner Miroslav M Libuda Jörg J Cinchetti Mirko M Schneider Claus Michael CM Feyer Vitaliy V Vesselli Erik E Zamborlini Giovanni G

Angewandte Chemie (International ed. in English) 20220321 20

Uncommon metal oxidation states in porphyrinoid cofactors are responsible for the activity of many enzymes. The F430 and P450nor co-factors, with their reduced NiI - and FeIII -containing tetrapyrrolic cores, are prototypical examples of biological systems involved in methane formation and in the reduction of nitric oxide, respectively. Herein, using a comprehensive range of experimental and theoretical methods, we raise evidence that nickel tetraphenyl porphyrin ...[more]

PMID: 35267236

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Project description:It has been previously demonstrated that metal nanoparticles embedded into polymeric materials doped with nitric oxide (NO) donor compounds can accelerate the release rate of NO for therapeutic applications. Despite the advantages of elevated NO surface flux for eradicating opportunistic bacteria in the initial hours of application, metal nanoparticles can often trigger a secondary biocidal effect through leaching that can lead to unfavorable cytotoxic responses from host cells. Alternatively, copper-based metal organic frameworks (MOFs) have been shown to stabilize Cu2+/1+ via coordination while demonstrating longer-term catalytic performance compared to their salt counterparts. Herein, the practical application of MOFs in NO-releasing polymeric substrates with an embedded NO donor compound was investigated for the first time. By developing composite thermoplastic silicon polycarbonate polyurethane (TSPCU) scaffolds, the catalytic effects achievable via intrapolymeric interactions between an MOF and NO donor compound were investigated using the water-stable copper-based MOF H3[(Cu4Cl)3(BTTri)8-(H2O)12]·72H2O (CuBTTri) and the NO donor S-nitroso-N-acetyl-penicillamine (SNAP). By creating a multifunctional triple-layered composite scaffold with CuBTTri and SNAP, the surface flux of NO from catalyzed SNAP decomposition was found tunable based on the variable weight percent CuBTTri incorporation. The tunable NO surface fluxes were found to elicit different cytotoxic responses in human cell lines, enabling application-specific tailoring. Challenging the TSPCU-NO-MOF composites against 24 h bacterial growth models, the enhanced NO release was found to elicit over 99% reduction in adhered and over 95% reduction in planktonic methicillin-resistant Staphylococcus aureus, with similar results observed for Escherichia coli. These results indicate that the combination of embedded MOFs and NO donors can be used as a highly efficacious tool for the early prevention of biofilm formation on medical devices.

Dataset Information

Disproportionation of Nitric Oxide at a Surface-Bound Nickel Porphyrinoid.

Publications

Disproportionation of Nitric Oxide at a Surface-Bound Nickel Porphyrinoid.

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