UC Santa Barbara

This research investigates the unique properties of nanomaterials (NMs) with highly catalytic surfaces that make them ideal for the production of organic molecules but also confer toxic properties of some NMs. Iron-sulphide NMs were used in a hydrothermal reactor that released hydrogen sulphide and other metal ions in the effluent, as analyzed by inductively-coupled plasma (ICP) spectrometry. Using an environmental scanning electron microscope (ESEM), iron sulphide NM surfaces indicate severe weathering as a result of environmental conditions including high pressure (100 bar H2) and moderate temperatures (130°C). The effluent's chemical properties from the reactor experiment generated chimney structures from newly formed iron-sulphide NMs in a ferrous rich `Hadean Ocean' solution. Using ESEM, we show that structural changes occur under different pHs, temperatures, and silicate concentrations. The presence of 5-mer peptides also shows distinct structural differences during the formation of iron-sulphide NM chimneys.

Nano-titanium dioxide NMs (nTiO2) were used to show the toxicity of nTiO2 encrusted Pseudomonas aeruginosa (PA) fed to Tetrahymena thermophila (TT) protozoa under aerobic conditions. The control TT showed limited toxicity when grown in the presence of nTiO2, and scanning transmission electron microscopy (STEM) revealed the initial accumulation of nTiO2 in food vacuoles (FVs) of control TT cells that were not observed in the TT grown with nTiO2-encrusted PA. After 22 h, very little nTiO2 is observed in the control TT FVs as compared with the TT grown with nTiO2-encrusted PA FVs which had about 30% of the FV filled with nTiO2. Toxicity to nTiO2 was observed as reduced growth yields for both the control and the PA fed TT, but also as a reduction in growth rate for TT grown with nTiO2-encrusted PA.

To understand biological weathering of NMs, the use of STEM energy dispersive spectroscopy (EDS) was enhanced to analyze single nano-sized particles. Contamination studies using cadmium selenide (CdSe) and cadmium telluride (CdTe) NMs with PA showed that CdSe weathering occurred in the cytoplasm while CdTe weathering predominantly occurred when associated with the PA cell wall. PA was shown to produce CdSe NMs in the cytoplasm when grown with cadmium and selenite salts as revealed by STEM-EDS. The use of STEM-EDS on embedded samples makes it possible to analyze NM structures while in their experimental location.