Functionalized carbon nanotube nanoelectrodes for biomolecular recognition

The objective of this research is to develop nanoscale ultrasensitive transducers for detection of biological species at molecular level using carbon nanotubes as nanoelectrodes. Rapid detection of ultra low concentration or even single DNA molecules are essential for medical diagnosis and treatment, pharmaceutical applications, gene sequencing as well as forensic analysis. Here the use of functionalized single walled carbon nanotubes (SWNT) as nanoscale detection platform for rapid detection of single DNA molecules is demonstrated. The detection principle is based on obtaining electrical signal from a single amine terminated DNA molecule which is covalently bridged between two ends of an SWNT separated by a nanoscale gap. The synthesis, fabrication, chemical functionalization of nanoelectrodes and DNA attachment were optimized to perform reliable electrical characterization these molecules. Using this detection system fundamental study on charge transport in DNA molecule of both genomic and non genomic sequences is performed. We measured an electrical signal of about 30 pA through a hybridized DNA molecule of 80 base pair in length which encodes a portion of sequence of H5N1 gene of avian Influenza A virus. Due the dynamic nature of the DNA molecules the local environment such as ion concentration, pH and temperature significantly influence its physical properties. We observed a decrease in DNA conductance of about 33% in high vacuum conditions. The counterion variation was analyzed by changing the buffer from sodium acetate to tris(hydroxymethyl) aminomethane, which resulted in a two orders of magnitude increase in the conductivity of the DNA. The fabrication of large array of identical SWNT nanoelectrodes was achieved by using ultralong SWNTs. Using these nanoelectrode array we have investigated the sequence dependent charge transport in DNA. A systematic study performed on PolyG - PolyC sequence with varying number of intervening PolyA - PolyT pairs showed a decrease in electrical signal from 180 pA (PolyG - PolyC) to 30 pA with increasing number of the PolyA - PolyT pairs. This work also led to the development of ultrasensitive nanoelectrodes based on enzyme functionalized vertically aligned high density multiwalled CNTs for electrochemical detection of cholesterol. The nanoelectrodes exhibited selectively detection of cholesterol in the presence of common interferents found in human blood.

Socio-ecological vulnerability to climate change in South Florida

Awareness of extreme high tide flooding in coastal communities has been increasing in recent years, reflecting growing concern over accelerated sea level rise. As a low-lying, urban coastal community with high value real estate, Miami often tops the rankings of cities worldwide in terms of vulnerability to sea level rise. Understanding perceptions of these changes and how communities are dealing with the impacts reveals much about vulnerability to climate change and the challenges of adaptation. ^ This empirical study uses an innovative mixed-methods approach that combines ethnographic observations of high tide flooding, qualitative interviews and analysis of tidal data to reveal coping strategies used by residents and businesses as well as perceptions of sea level rise and climate change, and to assess the relationship between measurable sea levels and perceptions of flooding. I conduct a case study of Miami Beach's storm water master planning process which included sea level rise projections, one of the first in the nation to do so, that reveals the different and sometimes competing logics of planners, public officials, activists, residents and business interests with regards to climate change adaptation. By taking a deeply contextual account of hazards and adaptation efforts in a local area I demonstrate how this approach can be effective at shedding light on some of the challenges posed by anthropogenic climate change and accelerated rates of sea level rise. ^ The findings highlight challenges for infrastructure planning in low-lying, urban coastal areas, and for individual risk assessment in the context of rapidly evolving discourse about the threat of sea level rise. Recognition of the trade-offs and limits of incremental adaptation strategies point to transformative approaches, at the same time highlighting equity concerns in adaptation governance and planning. This new impact assessment method contributes to the integration of social and physical science approaches to climate change, resulting in improved understanding of socio-ecological vulnerability to environmental change.^

Synthesis of M2AC (M = Ti, V, Cr, Nb, Zr, A = Al, Sn, S) (MAX) carbide phases and study of their physical behavior under extreme conditions

Materials known as Mn+1AXn phases, where n is 1, 2, or 3, and M represents an early transition metal, A an A-group element, and X is either Carbon and/or Nitrogen [1], are fast becoming technologically important materials due to the interesting combination of unique properties. However, a lot of important information about the high temperature and high pressure behavior of many of these compounds is still missing, which needs to be determined systematically. ^ In this dissertation the synthesis of M2AC (M = Ti, V, Cr, Nb, Zr) and A = (Al, Sn, S) compounds by arc melting, vacuum sintering and piston cylinder synthesis is presented along with the synthesis of Zr 2SC, which has been synthesized for first time in bulk form, by piston cylinder technique. The microstructural analysis by electron microscopy and phase analysis by x-ray diffraction is presented next. Finally, a critical analysis of the behavior of these compounds under the application of extreme pressure (as high as 50 GPa) and temperature (≈ 1000°C) is presented. ^ The high pressure studies, up to 50 GPa, showed that these compounds were structurally intact and their bulk moduli ranged from 140 to 190 GPa. The high temperature studies in the inert atmosphere showed that the M 2SnC compounds were unstable above 650°C and the expansion along the a-axis was higher than that along the c-axis, unlike the other phases. M2SC compounds on the other hand showed negligible difference in the thermal expansion along the two axes. The oxidation study revealed that Ti2AC (Al, S) compounds had highest resistance to oxidation while the M2SnC compounds had the least. Furthermore, from the oxidation study of these compounds, which were short time oxidation experiments, it was found that all of these compounds oxidized to their respective binary oxides. ^

Exploring thermal and mechanical properties of selected transition elements under extreme conditions: Experiments at high pressures and high temperatures

Transition metals (Ti, Zr, Hf, Mo, W, V, Nb, Ta, Pd, Pt, Cu, Ag, and Au) are essential building units of many materials and have important industrial applications. Therefore, it is important to understand their thermal and physical behavior when they are subjected to extreme conditions of pressure and temperature. This dissertation presents: • An improved experimental technique to use lasers for the measurement of thermal conductivity of materials under conditions of very high pressure (P, up to 50 GPa) and temperature (T up to 2500 K). • An experimental study of the phase relationship and physical properties of selected transition metals, which revealed new and unexpected physical effects of thermal conductivity in Zr, and Hf under high P-T. • New phase diagrams created for Hf, Ti and Zr from experimental data. • P-T dependence of the lattice parameters in α-hafnium. Contrary to prior reports, the α-ω phase transition in hafnium has a negative dT/dP slope. • New data on thermodynamic and physical properties of several transition metals and their respective high P-T phase diagrams. • First complete thermodynamic database for solid phases of 13 common transition metals was created. This database has: All the thermochemical data on these elements in their standard state (mostly available and compiled); All the equations of state (EoS) formulated from pressure-volume-temperature data (measured as a part of this study and from literature); Complete thermodynamic data for selected elements from standard to extreme conditions. The thermodynamic database provided by this study can be used with available thermodynamic software to calculate all thermophysical properties and phase diagrams at high P-T conditions. For readers who do not have access to this software, tabulated values of all thermodynamic and volume data for the 13 metals at high P-T are included in the APPENDIX. In the APPENDIX, a description of several other high-pressure studies of selected oxide systems is also included. Thermophysical properties (Cp, H, S, G) of the high P-T ω-phase of Ti, Zr and Hf were determined during the optimization of the EoS parameters and are presented in this study for the first time. These results should have important implications in understanding hexagonal-close-packed to simple-hexagonal phase transitions in transition metals and other materials.

An analytical investigation into shear wall and slab interconnections between reinforced concrete modules for high -rise buildings utilising modular construction under extreme seismic and wind loading

This research investigates a new structural system utilising modular construction. Five-sided boxes are cast on-site and stacked together to form a building. An analytical model was created of a typical building in each of two different analysis programs utilising the finite element method (Robot Millennium and ETABS). The pros and cons of both Robot Millennium and ETABS are listed at several key stages in the development of an analytical model utilising this structural system. Robot Millennium was initially utilised but created an analytical model too large to be successfully run. The computation requirements were too large for conventional computers. Therefore Robot Millennium was abandoned in favour of ETABS, whose more simplistic algorithms and assumptions permitted running this large computation model. Tips are provided as well as pitfalls signalled throughout the process of modelling such complex buildings of this type. ^ The building under high seismic loading required a new horizontal shear mechanism. This dissertation has proposed to create a secondary floor that ties to the modular box through the use of gunwales, and roughened surfaces with epoxy coatings. In addition, vertical connections necessitated a new type of shear wall. These shear walls consisted of waffled external walls tied through both reinforcement and a secondary concrete pour. ^ This structural system has generated a new building which was found to be very rigid compared to a conventional structure. The proposed modular building exhibited a period of 1.27 seconds, which is about one-fifth of a conventional building. The maximum lateral drift occurs under seismic loading with a magnitude of 6.14 inches which is one-quarter of a conventional building's drift. The deflected shape and pattern of the interstorey drifts are consistent with those of a coupled shear wall building. In conclusion, the computer analysis indicate that this new structure exceeds current code requirements for both hurricane winds and high seismic loads, and concomitantly provides a shortened construction time with reduced funding. ^

Study of the physical properties of metals and oxides at extreme pressure and temperature conditions

The high-pressure and temperature investigations on transition metals, metal doped-oxide system, nanocrystalline materials are presented in this dissertation. The metal-doped oxide systems are technologically important because of their applications, e.g. LSC, opto electronic applications, luminescence from lasers, etc., and from the earth sciences point of view, e.g. the study of trace elements in the MgO-SiO2 system, which accounts for 50% of the Earth's chondritic model. We have carried out thorough investigations on Cr2O3 and on chromium bearing oxides at high PT-conditions using in situ X-ray diffractometry and florescence spectroscopy techniques. Having obtained exciting results, an attempt to focus on the mechanism of the coordination of transition metals in oxides has been made. Additionally, the florescence from the metals in host oxides was found to be helpful to obtain information on structural variations like changes in the coordination of the doped element, formation of new phases, the diffusion processes. The possible reactions taking place at extreme conditions in the MgO-SiO2 system has been observed using florescence as markers. A new heating assemblage has been designed and fabricated for a precise determination of temperature at high pressures. An equation combining pressure shifts of ruby wavelength and temperature has been proposed. We observed that the compressibility of nanocrystalline material (MgO and Ni) is independent of crystallite size. A reduction in the transition pressure of nanocrystalline ceria at high-pressure has been observed as compare to the corresponding bulk material. ^

Controlled growth of carbon nanotubes for high performance nanoelectronics

Unique electrical and mechanical properties of single-walled carbon nanotubes (SWNTs) have made them one of the most promising candidates for next-generation nanoelectronics. Efficient utilization of the exceptional properties of SWNTs requires controlling their growth direction (e.g., vertical, horizontal) and morphologies (e.g., straight, junction, coiled). ^ In this dissertation, the catalytic effect on the branching of SWNTs, Y-shaped SWNTs (Y-SWNTs), was investigated. The formation of Y-shaped branches was found to be dependent on the composition of the catalysts. Easier carbide formers have a strong tendency to attach to the sidewall of SWNTs and thus enhance the degree of branching. Y-SWNTs based field-effect transistors (FETs) were fabricated and modulated by the metallic branch of the Y-SWNTs, exhibiting ambipolar characteristics at room temperature. A subthreshold swing of 700 mV/decade and an on/off ratio of 105 with a low off-state current of 10-13 A were obtained. The transport phenomena associated with Y- and cross-junction configurations reveals that the conduction mechanism in the SWNT junctions is governed by thermionic emission at T > 100 K and by tunneling at T < 100 K. ^ Furthermore, horizontally aligned SWNTs were synthesized by the controlled modification of external fields and forces. High performance carbon nanotube FETs and logic circuit were demonstrated utilizing the aligned SWNTs. It is found that the hysteresis in CNTFETs can be eliminated by removing absorbed water molecules on the CNT/SiO2 interface by vacuum annealing, hydrophobic surface treatment, and surface passivation. SWNT “serpentines” were synthesized by utilization of the interaction between drag force from gas flow and Van der Waals force with substrates. The curvature of bent SWNTs could be tailored by adjusting the gas flow rate, and changing the gas flow direction with respect to the step-edges on a single-crystal quartz substrate. Resistivity of bent SWNTs was observed to increase with curvature, which can be attributed to local deformations and possible chirality shift at curved part. ^ Our results show the successful synthesis of SWNTs having controllable morphologies and directionality. The capability of tailoring the electrical properties of SWNTs makes it possible to build an all-nanotube device by integrating SWNTs, having different functionalities, into complex circuits. ^

Robust and high current cold electron source based on carbon nanotube field emitters and electron multiplier microchannel plate

The aim of this research was to demonstrate a high current and stable field emission (FE) source based on carbon nanotubes (CNTs) and electron multiplier microchannel plate (MCP) and design efficient field emitters. In recent years various CNT based FE devices have been demonstrated including field emission displays, x-ray source and many more. However to use CNTs as source in high powered microwave (HPM) devices higher and stable current in the range of few milli-amperes to amperes is required. To achieve such high current we developed a novel technique of introducing a MCP between CNT cathode and anode. MCP is an array of electron multipliers; it operates by avalanche multiplication of secondary electrons, which are generated when electrons strike channel walls of MCP. FE current from CNTs is enhanced due to avalanche multiplication of secondary electrons and in addition MCP also protects CNTs from irreversible damage during vacuum arcing. Conventional MCP is not suitable for this purpose due to the lower secondary emission properties of their materials. To achieve higher and stable currents we have designed and fabricated a unique ceramic MCP consisting of high SEY materials. The MCP was fabricated utilizing optimum design parameters, which include channel dimensions and material properties obtained from charged particle optics (CPO) simulation. Child Langmuir law, which gives the optimum current density from an electron source, was taken into account during the system design and experiments. Each MCP channel consisted of MgO coated CNTs which was chosen from various material systems due to its very high SEY. With MCP inserted between CNT cathode and anode stable and higher emission current was achieved. It was ∼25 times higher than without MCP. A brighter emission image was also evidenced due to enhanced emission current. The obtained results are a significant technological advance and this research holds promise for electron source in new generation lightweight, efficient and compact microwave devices for telecommunications in satellites or space applications. As part of this work novel emitters consisting of multistage geometry with improved FE properties were was also developed.

High pressure studies on group VI metal hexacarbonyl molecular solids

Group VI metal hexacarbonyls, M(CO)6 (M = Cr, Mo and W), are of extreme importance as catalysts in industry and also of fundamental interest due to the established charge transfer mechanism between the carbon monoxide and the metal. They condense to molecular solids at ambient conditions retaining the octahedral (Oh) symmetry of gas phase and have been extensively investigated by previous workers to understand their fundamental chemical bonding and possible industrial applications. However little is known about their behavior at high pressures which is the focus of this dissertation. Metal hexacarbonyls were subjected to high pressures in Diamond-Anvil cells to understand the pressure effect on chemical bonding using Raman scattering in situ. The high-pressure results on each of the three metal hexacarbonyls are presented and are followed by a critical analysis of the entire family. The Raman study was conducted at pressures up to 45 GPa and X-ray up to 58 GPa. This is followed by a discussion on infra red spectra in conjunction with Raman and X-ray analysis to provide a rationale for polymerization. Finally the probable synthesis of extremely reactive species under high-pressures and as identified via Raman is discussed. The high-pressure Raman scattering, up to 30 GPa, demonstrated the absence of Π-backbonding. The disappearance of parental Raman spectra for (M = Cr, Mo and W) at 29.6, 23.3 and 22.2 GPa respectively was attributed to the total collapse of the Oh symmetry. This collapse under high-pressure lead to metal-mediated polymeric phase characterized by Raman active δ(OCO) feature, originating from intermolecular vibrational coupling in the parent sample. Further increase in pressures up to 45 GPa, did not affect this feature. The pressure quenched Raman spectra, revealed various chemical groups non-characteristic of the parent sample and adsorption of CO in addition to the characteristic δ(OCO) feature. The thus recorded Raman, complemented with the far and mid-infrared pressure quenched spectra, reveal the formation of novel metal-mediated polymers. The X-ray diffraction on W(CO)6 up to 58 GPa revealed the generation of amorphous polymeric pattern which was retained back to ambient conditions.

Vacuum brazing of alumina ceramic to titanium for biomedical implants using pure gold as the filler metal

One of the many promising applications of metal/ceramic joining is in biomedical implantable devices. This work is focused on vacuum brazing of C.P titanium to 96% alumina ceramic using pure gold as the filler metal. A novel method of brazing is developed where resistance heating of C.P titanium is done inside a thermal evaporator using a Ta heating electrode. The design of electrode is optimized using Ansys resistive heating simulations. The materials chosen in this study are biocompatible and have prior history in implantable devices approved by FDA. This research is part of Boston Retinal implant project to make a biocompatible implantable device (www.bostonretina.org). ^ Pure gold braze has been used in the construction of single terminal feedthrough in low density hermetic packages utilizing a single platinum pin brazed to an alumina or sapphire ceramic donut (brazed to a titanium case or ferrule for many years in implantable pacemakers. Pure gold (99.99%) brazing of 96% alumina ceramic with CP titanium has been performed and evaluated in this dissertation. Brazing has been done by using electrical resistance heating. The 96% alumina ceramic disk was manufactured by high temperature cofired ceramic (HTCC) processing while the Ti ferrule and gold performs were purchased from outside. Hermetic joints having leak rate of the order of 1.6 × 10-8 atm-cc/ sec on a helium leak detector were measured. ^ Alumina ceramics made by HTCC processing were centreless grounded utilizing 800 grit diamond wheel to provide a smooth surface for sputtering of a thin film of Nb. Since pure alumina demonstrates no adhesion or wetting to gold, an adhesion layer must be used on the alumina surface. Niobium (Nb), Tantalum (Ta) and Tungsten (W) were chosen for evaluation since all are refractory (less dissolution into molten gold), all form stable oxides (necessary for adhesion to alumina) and all are readily thin film deposited as metals. Wetting studies are also performed to determine the wetting angle of pure gold to Ti, Ta, Nb and W substrates. Nano tribological scratch testing of thin film of Nb (which demonstrated the best wetting properties towards gold) on polished 96% alumina ceramic is performed to determine the adhesion strength of thin film to the substrate. The wetting studies also determined the thickness of the intermetallic compounds layers formed between Ti and gold, reaction microstructure and the dissolution of the metal into the molten gold.^

Developing a high density platinum/alumina hermetic feedthrough

Typically, hermetic feedthroughs for implantable devices, such as pacemakers, use a alumina ceramic insulator brazed to a platinum wire pin. This combination of material has a long history in implantable devices and has been approved by the FDA for implantable hermetic feedthroughs. The growing demand for increased input/output (I/O) hermetic feedthroughs for implantable neural stimulator applications could be addressed by developing a new, cofired platinum/alumina multilayer ceramic technology in a configuration that supports 300 plus I/Os, which is not commercially available. Seven platinum powders with different particle sizes were used to develop different conductive cofire inks to control the densification mismatch between platinum and alumina. Firing profile (ramp rate, burn- out and holding times) and firing atmosphere and concentrations (hydrogen (wet/dry), air, neutral, vacuum) were also optimized. Platinum and alumina exhibit the alloy formation reaction in a reduced atmosphere. Formation of any compound can increase the bonding of the metal/ceramic interface, resulting in enhanced hermeticity. The feedthrough fabricated in a reduced atmosphere demonstrated significantly superior performance than that of other atmospheres. A composite structure of tungsten/platinum ratios graded thru the via structure (pure W, 50/50 W/Pt, 80/20 Pt/W and pure Pt) exhibited the best performance in comparison to the performance of other materials used for ink metallization. Studies on the high temperature reaction of platinum and alumina, previously unreported, showed that, at low temperatures in reduced atmosphere, Pt 3Al or Pt8Al21 with a tetragonal structure would be formed. Cubic Pt3Al is formed upon heating the sample to temperatures above 1350 °C. This cubic structure is the equilibrium state of Pt-Al alloy at high temperatures. The alumina dissolves into the platinum ink and is redeposited as a surface coating. This was observed on both cofired samples and pure platinum thin films coated on a 99.6 Wt% alumina and fired at 1550 °C. Different mechanisms are proposed to describe this behavior based on the size of the platinum particle