Nichola M. Kinsinger

Urease-Mediated Room-Temperature Synthesis of Nanocrystalline Titanium Dioxide

Enzymes are an important class of biological molecules whose specific functionalities can be exploited to perform tasks beyond the reach of conventional chemistry. Because they are operational under environmentally friendly, ambient conditions, the adaptation of these biomacromolecules can potentially be used to replace current energy-intensive and environmentally harsh synthesis methods for materials. Here we used a hydrolytic enzyme, urease, to modify the solution environment around a water-soluble and stable TiO(2) precursor to synthesize nanocrystalline titanium dioxide under environmentally benign conditions. This urease-mediated synthesis yields nearly monodisperse TiO(2) nanostructures with high surface area that can be utilized for numerous energy-based applications such as low-cost photovoltaics and photocatalysts.

Understanding the Transformation, Speciation, and Hazard Potential of Copper Particles in a Model Septic Tank System Using Zebrafish to Monitor the Effluent

Although copper-containing nanoparticles are used in commercial products such as fungicides and bactericides, we presently do not understand the environmental impact on other organisms that may be inadvertently exposed. In this study, we used the zebrafish embryo as a screening tool to study the potential impact of two nano Cu-based materials, CuPRO and Kocide, in comparison to nanosized and micron-sized Cu and CuO particles in their pristine form (0-10 ppm) as well as following their transformation in an experimental wastewater treatment system. This was accomplished by construction of a modeled domestic septic tank system from which effluents could be retrieved at different stages following particle introduction (10 ppm). The Cu speciation in the effluent was identified as nondissolvable inorganic Cu(H2PO2)2 and nondiffusible organic Cu by X-ray diffraction, inductively coupled plasma mass spectrometry (ICP-MS), diffusive gradients in thin-films (DGT), and Visual MINTEQ software. While the nanoscale materials, including the commercial particles, were clearly more potent (showing 50% hatching interference above 0.5 ppm) than the micron-scale particulates with no effect on hatching up to 10 ppm, the Cu released from the particles in the septic tank underwent transformation into nonbioavailable species that failed to interfere with the function of the zebrafish embryo hatching enzyme. Moreover, we demonstrate that the addition of humic acid, as an organic carbon component, could lead to a dose-dependent decrease in Cu toxicity in our high content zebrafish embryo screening assay. Thus, the use of zebrafish embryo screening, in combination with the effluents obtained from a modeled exposure environment, enables a bioassay approach to follow the change in the speciation and hazard potential of Cu particles instead of difficult-to-perform direct particle tracking.

Synergistic effect of pH and phase in a nanocrystalline titania photocatalyst.

Titanium dioxide is a semiconducting material that has been studied for many years as a photocatalytic material to degrade organics in water. This study investigated the effect of anatase-rutile mixtures and pH on the photocatalytic degradation of the dye Methylene blue as the target analyte. Anatase-rutile mixtures between 0 and 90% rutile that were synthesized from a water-soluble precursor were suspended at pH 4, 7, and 10. Suspension pH significantly affected the reactivity and efficiency of the photocatalysts because of the particle-particle and sorbate-surface interactions. The highest removal percentage of MB by 240 min at pH 4, 7, and 10 was 35, 99, and 93%, respectively. pH 7 was ideal to observe the affect of percent rutile on the degradation rate, where 91% was removed within 120 min by the material composed of 20% rutile, which is attributed to the synergistic charge transfer of holes from rutile to anatase.

Antimicrobial behavior of novel surfaces generated by electrophoretic deposition and breakdown anodization

Biofilms have devastating impacts on many industries such as increased fuel consumption and damage to surfaces in maritime industries. Ideal biofouling management is inhibition of initial bacterial attachment. The attachment of a model marine bacterium (Halomonas pacfica g) was investigated to evaluate the potential of these new novel surfaces to resist initial bacterial adhesion. Novel engineered surfaces were generated via breakdown anodization or electrophoretic deposition, to modify three parameters: hydrophobicity, surface chemistry, and roughness. Mass transfer rates were determined using a parallel plate flow chamber under relevant solution chemistries. The greatest deposition was observed on the superhydrophilic surface, which had micro- and nano-scale hierarchical structures composed of titanium oxide deposited on a titanium plate. Conversely, one of the hydrophobic surfaces with micro-porous films overlaid with polydimethylsiloxane appeared to be most resistant to cell attachment.

O Antigen Modulates Insect Vector Acquisition of the Bacterial Plant Pathogen Xylella fastidiosa

ABSTRACT Hemipteran insect vectors transmit the majority of plant pathogens. Acquisition of pathogenic bacteria by these piercing/sucking insects requires intimate associations between the bacterial cells and insect surfaces. Lipopolysaccharide (LPS) is the predominant macromolecule displayed on the cell surface of Gram-negative bacteria and thus mediates bacterial interactions with the environment and potential hosts. We hypothesized that bacterial cell surface properties mediated by LPS would be important in modulating vector-pathogen interactions required for acquisition of the bacterial plant pathogen Xylella fastidiosa, the causative agent of Pierces disease of grapevines. Utilizing a mutant that produces truncated O antigen (the terminal portion of the LPS molecule), we present results that link this LPS structural alteration to a significant decrease in the attachment of X. fastidiosa to blue-green sharpshooter foreguts. Scanning electron microscopy confirmed that this defect in initial attachment compromised subsequent biofilm formation within vector foreguts, thus impairing pathogen acquisition. We also establish a relationship between O antigen truncation and significant changes in the physiochemical properties of the cell, which in turn affect the dynamics of X. fastidiosa adhesion to the vector foregut. Lastly, we couple measurements of the physiochemical properties of the cell with hydrodynamic fluid shear rates to produce a Comsol model that predicts primary areas of bacterial colonization within blue-green sharpshooter foreguts, and we present experimental data that support the model. These results demonstrate that, in addition to reported protein adhesin-ligand interactions, O antigen is crucial for vector-pathogen interactions, specifically in the acquisition of this destructive agricultural pathogen.