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INSIGHTS INTO THE METAL HANDLING MECHANISMS OF TITANIUM DIOXIDE-BINDING BACTERIA RHODOCOCCUS RUBER

Cobani, Lori
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Thesis/Dissertation
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2024-08
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Chemistry
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http://dx.doi.org/10.34944/dspace/10581
Abstract
Titanium is an abundant element in the Earth’s crust, making up about 0.6% of itscomposition and predominantly occurring as Ti(IV) in slightly soluble mineral oxides. Titanium has a wide range of uses due to its excellent properties such as high strength-to-weight ratio, corrosion resistance, and biocompatibility. Despite its abundance and being readily absorbed by certain organisms, no essential biological function for titanium has been identified. Nonetheless, there is evidence that titanium is bioactive, including in its interactions with microbes. Titanium interacts with specific unicellular organisms and with biomolecules found in them, increasing the likelihood of the potential presence of titanium in microbial metalloproteomes. Understanding titanium’s presence and varied roles across different microbial phyla may eventually lead to the discovery of an essential biological role for this element. Another hydrolysis-prone metal is iron, which unlike titanium, is an essential nutrient for almost all living organisms. While higher organisms obtain it through their diet, some lower organisms have developed sophisticated mechanisms to acquire it. Siderophores are small, metalchelators secreted by bacteria that scavenge iron and bring it to the organism for its metabolic needs. The significance of this class of molecules is that they can be used in the pharmaceutical industry for delivering a drug to its specific target site, including antibiotics. Rhodococcus ruber is a siderophore-producing marine organism, isolated first due to its high affinity for metal oxides, particularly titanium dioxide. R. ruber GIN.1 and DSM 43338 strains were grown under laboratory conditions and a growth media recipe was developed to trigger the secretion of siderophores by these two strains. Here, we present the isolation, purification and structure elucidation of the first siderophore molecule secreted by this species. Similar to other siderophores, it contains two catechol groups and a hydroxamic group. This is supported by genomic analysis of the GIN.1 strain which revealed a similar cluster to some heterobactin structures. UV-Vis spectroscopy data shows that this novel molecule has high affinity for iron, comparable to other siderophores. Understanding the siderophore-iron interaction may help to study the mechanism of how these bacterial cells obtain titanium from the metal oxide particles. Future research will focus on the further characterization of this new siderophore molecule and its potential applications. Other molecules that were investigated from R. ruber were the surface binding proteins that exhibit specific affinity for titanium dioxide (TiO2). Knowing the fact that this bacteria binds strongly and selectively to TiO2 among other metal oxides, the question was raised to identify the molecules in this organism that mediate the affinity for titanium dioxide. After growing the bacteria for the purpose of siderophore production, a separate procedure was developed to isolate the binding proteins. Using mutanolysin treatment, the proteins were released from the bacterial cell walls and subsequently purified. SDS-PAGE analysis, combined with silver stain technique, revealed distinct protein bands, which were further characterized using mass spectrometry and sequencing techniques. The main focus was to identify and elucidate the primary structure of these TiO2-binding proteins. These proteins share similarities with known metal-binding proteins, suggesting specific amino acid motifs responsible for TiO2 affinity. On a different project related to metals in biology, ferritin is a protein that stores iron and releases it as needed by the organism. It plays a crucial role in maintaining iron homeostasis, and has several applications in biotechnology, biomedical research, as well as environmental and industrial uses. The ability to reduce toxic chromate (Cr(VI)) to nontoxic chromium (Cr(III)) is of interest due to the progressively increasing concentrations of chromate in bodies of water due to industrial pollution. The biomineralization process of iron by ferritin proteins plays a significant role in the reduction of toxic chromate compounds, presenting a potential solution to remediate environmental pollution. This study focused on characterizing the biomineralization of iron and the subsequent reduction of chromate by L-chain ferritin, specifically investigating its efficacy compared to conventional ferritin proteins. Iron mineralization of the protein was achieved through an incremental loading procedure, followed by photochemical batch reactions to assess iron release and chromate reduction capabilities under simulated solar radiation. Results indicate that while L-chain ferritin exhibits potential for iron biomineralization, its efficiency in chromate reduction is limited compared to conventional ferritin proteins.
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