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1. Quantitative Mapping of Oxidative Stress Response to Lithium Cobalt Oxide Nanoparticles in Single Cells Using Multiplexed in Situ Gene Expression Analysis

   https://doi.org/10.1021/acs.nanolett.8b05172  

   Cui, Yi ; Melby, Eric S. ; Mensch, Arielle C. ; Laudadio, Elizabeth D. ; Hang, Mimi N. ; Dohnalkova, Alice ; Hu, Dehong ; Hamers, Robert J. ; Orr, Galya ( February 2019 , Nano Letters)
2. Dynamic aqueous transformations of lithium cobalt oxide nanoparticle induce distinct oxidative stress responses of B. subtilis

   https://doi.org/10.1039/D0EN01151G  

   Gari, Metti K. ; Lemke, Paul ; Lu, Kelly H. ; Laudadio, Elizabeth D. ; Henke, Austin H. ; Green, Curtis M. ; Pho, Thomas ; Hoang, Khoi Nguyen ; Murphy, Catherine J. ; Hamers, Robert J. ; et al ( January 2021 , Environmental Science: Nano)

   null (Ed.)

   Lithium cobalt oxide (LiCoO 2 ), an example of nanoscale transition metal oxide and a widely commercialized cathode material in lithium ion batteries, has been shown to induce oxidative stress and generate intracellular reactive oxygen species (ROS) in model organisms. In this study, we aimed to understand the time-dependent roles of abiotic ROS generation and Co ions released in aqueous medium by LiCoO 2 NPs, and examined the induced biological responses in model bacterium, B. subtilis upon exposure. We found that the redox-active LiCoO 2 NPs produced abiotic ROS primarily through H 2 O 2 generation when freshly suspended. Subsequently, the freshly-suspended LiCoO 2 NPs induced additional DNA breakage, and changes in expression of oxidative stress genes in B. subtilis that could not be accounted for by the released Co ions alone. Notably, in 48 hour old LiCoO 2 suspensions, H 2 O 2 generation subsided while higher concentrations of Co ions were released. The biological responses in DNA damage and gene expression to the aged LiCoO 2 NPs recapitulated those induced by the released Co ions. Our results demonstrated oxidative stress mechanisms for bacteria exposed to LiCoO 2 NPs were mediated by the generation of distinct biotic and abiotic ROS species, which depended on the aqueous transformation state of the NPs. This study revealed the interdependent and dynamic nature of NP transformation and their biological consequences where the state of NPs resulted in distinct NP-specific mechanisms of oxidative injury. Our work highlights the need to capture the dynamic transformation of NPs that may activate the multiple routes of oxidative stress responses in cells. 

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3. Energy Starvation in Daphnia magna from Exposure to a Lithium Cobalt Oxide Nanomaterial

   https://doi.org/10.1021/acs.chemrestox.1c00189  

   Niemuth, Nicholas J. ; Curtis, Becky J. ; Laudadio, Elizabeth D. ; Sostare, Elena ; Bennett, Evan A. ; Neureuther, Nicklaus J. ; Mohaimani, Aurash A. ; Schmoldt, Angela ; Ostovich, Eric D. ; Viant, Mark R. ; et al ( January 2021 , Chemical Research in Toxicology)

   null (Ed.)

   Growing evidence across organisms points to altered energy metabolism as an adverse outcome of metal oxide nanomaterial toxicity, with a mechanism of toxicity potentially related to the redox chemistry of processes involved in energy production. Despite this evidence, the significance of this mechanism has gone unrecognized in nanotoxicology due to the field’s focus on oxidative stress as a universal—but non-specific—nanotoxicity mechanism. To further explore metabolic impacts, we determined LCO’s effects on these pathways in the model organism Daphnia magna through global gene expression analysis using RNA-Seq and untargeted metabolomics by direct-injection mass spectrometry. Our results show a sublethal 1 mg/L 48 h exposure of D. magna to LCO nanosheets causes significant impacts on metabolic pathways versus untreated controls, while exposure to ions released over 48 hr does not. Specifically, transcriptomic analysis using DAVID indicated significant enrichment (Benjamini-adjusted p ≤0.0.5) in LCO-exposed animals for changes in pathways involved in the cellular response to starvation (25 genes), mitochondrial function (70 genes), ATP-binding (70 genes), oxidative phosphorylation (53 genes), NADH dehydrogenase activity (12 genes), and protein biosynthesis (40 genes). Metabolomic analysis using MetaboAnalyst indicated significant enrichment (gamma-adjusted p < 0.1) for changes in amino acid metabolism (19 metabolites) and starch, sucrose, and galactose metabolism (7 metabolites). Overlap of significantly impacted pathways by RNA-Seq and metabolomics suggests amino acid breakdown and increased sugar import for energy production. Results indicate that LCO-exposed Daphnia are responding to energy starvation by altering metabolic pathways, both at the gene expression and metabolite level. These results support altered energy production as a sensitive nanotoxicity adverse outcome for LCO exposure and suggest negative impacts on energy metabolism as an important avenue for future studies of nanotoxicity, including for other biological systems and for metal oxide nanomaterials more broadly. 

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4. Impact of Nanoscale Lithium Nickel Manganese Cobalt Oxide (NMC) on the Bacterium Shewanella oneidensis MR-1

   https://doi.org/10.1021/acs.chemmater.5b04505  

   Hang, Mimi N. ; Gunsolus, Ian L. ; Wayland, Hunter ; Melby, Eric S. ; Mensch, Arielle C. ; Hurley, Katie R. ; Pedersen, Joel A. ; Haynes, Christy L. ; Hamers, Robert J. ( February 2016 , Chemistry of Materials)
5. Understanding Reaction Mechanisms of Nicotinamide Adenine Dinucleotide (NADH) with Lithium Cobalt Oxide and Other Metal Oxide Nanomaterials

   https://doi.org/10.1039/D3EN00351E  

   Kruszynski Earl, Catherine E. ; Henke, Austin H. ; Laudadio, Elizabeth D ; Hamers, Robert J. ( January 2023 , Environmental Science: Nano)

   High-valent metal oxides such as LiCoO2 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 LiCoO2(a common lithium-ion battery cathode material) oxidizes nicotinamide adenine dinucleotide (NADH), an essential molecule for electron transport, and enhances Co release from LiCoO2. In the present work, we investigated the mechanism of interaction by examining the role of the ribose, phosphate, adenosine, and the nicotinamide components of NADH in the transformation of LiCoO2 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 the LiCoO2 and the 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 LiCoO2 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. 

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