Cobalt Release from a Nanoscale Multiphase Lithiated Cobalt Phosphate Dominates Interaction with Shewanella oneidensis MR-1 and Bacillus subtilis SB491

Abstract

Cobalt phosphate engineered nanomaterials (ENMs) are an important class of materials that are used as lithium ion battery cathodes, catalysts, and potentially as super capacitors. As production of these nanomaterials increases, so does the likelihood of their environmental release; however, to date, there are relatively few investigations of the impact of nanoscale metal phosphates on biological systems. Furthermore, nanomaterials used in commercial applications are often multiphase materials, and analysis of the toxic potential of mixtures of nanomaterials has been rare. In this work, we studied the interactions of two model environmental bacteria, Shewanella oneidensis MR-1 and Bacillus subtilis, with a multiphase lithiated cobalt phosphate (mLCP) nanomaterial. Using a growth-based viability assay, we found that mLCP was toxic to both bacteria used in this study. To understand the observed toxicity, we screened for production of reactive oxygen species (ROS) and release of Co 2+ from mLCP using three abiotic fluorophores. We also used Newport Green DCF dye to show that cobalt was taken up by the bacteria after mLCP exposure. Using transmission electron microscopy, we noted that the mLCP was not associated with the bacterial cell surface. In order for us to further probe the mechanism of interaction of mLCP, the bacteria were exposed to an equivalent dose of cobalt ions that dissolved from mLCP, which recapitulated the changes in viability when the bacteria were exposed to mLCP, and it also recapitulated the observed bacterial uptake of cobalt. Taken together, this implicates the release of cobalt ions and their subsequent uptake by the bacteria as the major toxicity mechanism of mLCP. The properties of the ENM govern the release rate of cobalt, but the toxicity does not arise from nanospecific effectsand importantly, the chemical composition of the ENM may dictate the oxidation state of the metal centers and thus limit ROS production.

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“…In fact, we have already applied this dye to measure the uptake of cobalt in S. oneidensis upon exposure to nanoscale multiphase lithiated cobalt phosphate. 47 To validate the dye, we exposed bacterial cells pre-loaded with NPG-Ac to both Ni(II) and Co(II) ions (Fig. S5 †).…”

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Review—Nanomaterials Green Synthesis for High-Performance Secondary Rechargeable Batteries: Approaches, Challenges, and Perspectives

“…263 Cathode materials developed using biomaterials are believed to offer a new way to design low cost, high specific capacity, and potential carbonaceous materials for rechargeable secondary batteries. Various natural biomaterials, including viruses, 340 yeast, 341 bacteria, 342 fungi, 269 plant extract, 280 small biomolecules, and peptides, can be developed as building blocks or bio-templates applied for energy storage by assembling into nanostructures with an inorganic material.…”