Understanding the reaction mechanisms of nicotinamide adenine dinucleotide (NADH) with lithium cobalt oxide and other metal oxide nanomaterials

• Published in: Environmental science. Nano Vol. 11; no. 2; pp. 518 - 528
• Main Authors: Kruszynski Earl, Catherine E, Henke, Austin H, Laudadio, Elizabeth D, Hamers, Robert J
• Format: Journal Article
• Language: English
• Published: Cambridge Royal Society of Chemistry 16.02.2024
• Subjects: Adenine; Adenosine; Analytical methods; Batteries; Binding; Biomolecules; Cathodes; Cobalt; Cobalt oxides; Electrode materials; Electron transport; Environmental chemistry; Environmental perception; Fluorescence; Fluorescence spectroscopy; Geochemistry; Heavy metals; Lithium; Lithium compounds; Lithium-ion batteries; Mass spectrometry; Mass spectroscopy; Metal ions; Metal oxides; Metals; NAD; NADH; Nanomaterials; Nanoparticles; Nanotechnology; Nicotinamide; Nicotinamide adenine dinucleotide; Oxides; Phosphates; Photoelectron spectroscopy; Photoelectrons; Reaction mechanisms; Rechargeable batteries; Redox properties; Ribose; Spectroscopy; Transition metal oxides; X ray photoelectron spectroscopy
• ISSN: 2051-8153; 2051-8161
• DOI: 10.1039/d3en00351e

High-valent metal oxides such as LiCoO 2 and related materials are of increasing environmental concern due to the large-scale use in lithium-ion batteries and potential for metal ion release into aqueous systems. A key aspect of the environmental chemistry of these materials is the potential role redox chemistry plays in their transformations as well as their influence on the surrounding environment ( i.e. , biomolecules, organisms etc. ). In recent work, we showed that LiCoO 2 (a common lithium-ion battery cathode material) oxidizes nicotinamide adenine dinucleotide (NADH), an essential molecule for electron transport, and enhances Co release from LiCoO 2 . In the present work, we investigated the mechanism of interaction by examining the role of the ribose, phosphate, adenosine, and nicotinamide components of NADH in the transformation of LiCoO 2 nanoparticles. To build an understanding of the interaction mechanism, we used fluorescence spectroscopy to measure the changes in redox state and inductively coupled plasma-mass spectrometry (ICP-MS) to measure the changes in dissolved Co. Our results reveal the importance of surface binding, via the phosphate functionality, in initiating the redox transformation of both LiCoO 2 and NADH. Observations from X-ray photoelectron spectroscopy (XPS) data show that molecules containing phosphate were bound to the surface of the nanoparticles and those without that functionality were not. We further established the generality of the results with LiCoO 2 by examining other high-valent transition metal oxides. This surface binding effect has implications for understanding how other phosphorylated species can be transformed directly in the presence of high-valent metal oxide nanomaterials. Biomolecules that have both redox capability and phosphate functionality undergo direct surface initiated redox with high-valent metal oxide nanoparticles, oxidizing the molecule and increasing Co release from the nanoparticles.