Quantum modeling of bioconjugated nanomaterials

In recent years, the bio-conjugated nanostructured materials have emerged as a new class of materials for the bio-sensing and medical diagnostics applications. In spite of their multi-directional applications, interfacing nanomaterials with bio-molecules has been a challenge due to somewhat limited knowledge about the underlying physics and chemistry behind these interactions and also for the complexity of biomolecules. The main objective of this dissertation is to provide such a detailed knowledge on bioconjugated nanomaterials toward their applications in designing the next generation of sensing devices. Specifically, we investigate the changes in the electronic properties of a boron nitride nanotube (BNNT) due to the adsorption of different bio-molecules, ranging from neutral (DNA/RNA nucleobases) to polar (amino acid molecules). BNNT is a typical member of III-V compounds semiconductors with morphology similar to that of carbon nanotubes (CNTs) but with its own distinct properties. More specifically, the natural affinity of BNNTs toward living cells with no apparent toxicity instigates the applications of BNNTs in drug delivery and cell therapy. Our results predict that the adsorption of DNA/RNA nucleobases on BNNTs amounts to different degrees of modulation in the band gap of BNNTs, which can be exploited for distinguishing these nucleobases from each other. Interestingly, for the polar amino acid molecules, the nature of interaction appeared to vary ranging from Coulombic, van der Waals and covalent depending on the polarity of the individual molecules, each with a different binding strength and amount of charge transfer involved in the interaction. The strong binding of amino acid molecules on the BNNTs explains the observed protein wrapping onto BNNTs without any linkers, unlike carbon nanotubes (CNTs). Additionally, the widely varying binding energies corresponding to different amino acid molecules toward BNNTs indicate to the suitability of BNNTs for the biosensing applications, as compared to the metallic CNTs. The calculated I-V characteristics in these bioconjugated nanotubes predict notable changes in the conductivity of BNNTs due to the physisorption of DNA/RNA nucleobases. This is not the case with metallic CNTs whose transport properties remained unaltered in their conjugated systems with the nucleobases. Collectively, the bioconjugated BNNTs are found to be an excellent system for the next generation sensing devices.

ALTERNATING CURRENT DIELECTROPHORETIC MANIPULATION OF ERYTHROCYTES IN MEDICAL MICRODEVICE TECHNOLOGY

Medical microdevices have gained popularity in the past few decades because they allow the medical laboratory to be taken out into the field and for disease diagnostics to happen with a smaller sample volume, at a lower cost and much faster. Blood is the human body's most readily available and informative diagnostic fluid because of the wealth of information it provides about the body's general health including enzymatic, proteomic and immunological states. The purpose of this project is to optimize operating conditions and study ABO-Rh erythrocytes dielectrophoretic responses to alternating current electric signals. The end goal of this project is the creation of a relatively inexpensive microfluidic device, which can be used for the ABO-Rh typing of a blood sample. This dissertation presents results showing how blood samples of a known ABO- Rh blood type exhibit differing behavior to the same electrical stimulus based on their blood type. The first panel of donors and experiments, presented in Chapter 4 occurred when a sample of known blood type was injected into a microdevice with a T-shaped electrode configuration and the erythorcytes were found to rupture at a rate specific to their ABO-Rh blood type. The second set of experiments, presented in Chapter 5, were originally published in Electrophoresis in 20111. Novel in this work was the discovery that treatment of human erythrocytes with β-galactosidase successfully removed ABO surface antigens such that native A and B blood no longer agglutinated with the proper antibodies. This work was performed in a medium of conductivity 0.9S/m which is close to the measured conductivity of pooled plasma (~1.1S/m). The ability to perform dielectrophoresis experiments at physiological conductivities conditions is advantageous for future portable devices because the device/instrument would not need to store dilution buffers. The final results of this project, presented in Chapter 6, explore the entire dielectrophoretic spectra of the ABO-Rh erythrocytes including the cross-over frequency and the magnitudes of the positive or negative dielectrophoretic response. These were completed at lower medium conductivities of 0.1S/m and 0.01-0.04S/m. These results show that by using the sweep function built into the Agilent alternating current generator it is possible to explore how a single group of blood cells will react to rapid changes in frequency and will provide the user with curve that can be matched the theoretical dielectrophoretic response curves. As a whole this project shows that it is possible to distinguish human erythrocytes by their ABO-Rh blood type via three different dielectrophoretic methods. This work builds on the foundation of that it is possible to distinguish healthy from infected cells2-7, similar cell types1,7-14 and other work regarding the dielectrophoresis of human erythrocytes1,10,11. This work has implications in both medical diagnostics and future dielectrophoretic work because it has shown that ABO-Rh blood type is now a factor, which must be identified when working with a human blood sample. It also shows that the creation of a microfluidic device that subjects human erythrocytes to a dielectrophoretic impulse and then exports an ABO-Rh blood type is a near future possibility.

Fish contaminants through the tribal perspective : an ethnography of the Keweenaw Bay Indian Community's tribal fish harvest

It has been well documented that many tribal populations and minority groups across the nation have been identified as being at high risk of the adverse health effects created by consuming fish that have been contaminated with mercury, PCBs, DDT, dioxins, and other chemicals. Although fish consumption advisories are intended to inform fish consumers of risks associated with specific species and water bodies, advisories have been the subject of both environmental injustices and treaty rights’ injustices. This means that understanding fish contaminants, through community perspectives is essential to good environmental policy. This study examined the fish contaminant knowledge, impacts on fishing and fish consumption, and the factors that contribute to harvesting decisions and behaviors in one tribal nation in the Upper Peninsula of Michigan, the Keweenaw Bay Indian Community. Using ethnographic methods, participant observation and semi-structured interviewing, fieldnotes were kept and all interviews were fully transcribed for data analysis. Among seventeen fishermen and women, contaminants are poorly understood, have had a limited impact on subsistence fishing but have had a substantial impact on commercial fishing activity. But ultimately, all decisions and behaviors are based on their own criteria and within a larger context of knowledge and understanding: the historical and cultural context. The historical context revealed that advisories are viewed as another attack on tribal fishing. The cultural context revealed that it is the fundamental guidance and essential framework associated with all harvesting beliefs, values, and traditional lifeways. These results have implications for advisories. ‘Fish’ and ‘contaminants’ appear differently based on the perceptions and priorities of those who encounter them.