Background: Pulsed amperometric detection is a relatively new method for detection of ions and especially non-electrolytes such as carbohydrates in aqueous solutions. Pulsed amperometric detection relies on a redox reaction while electrochemical impedance simply measures the real and capacitive resistant of the solution. There is a correlation between the real impedance of a solution and the ionic strength of the solution. Method: This work explores measuring real impedance of pure water as a function of temperature from 25.0 to 60.0 °C to determine the relationship between impedance and temperature. Maintaining temperature at 25.0 °C, solutions of sodium chloride, potassium carbonate, sodium sulfate acetate and bicarbonate have been measured using impedance spectroscopy. Results: Regression analysis shows that measuring anions using impedance spectroscopy and simple stainless steel cylinders that detection limits at the parts per trillion (ppt) level are possible. There was no statistical difference when comparing impedance values of the same concentration of acetate and chloride in solution, showing real impedance is not dependent on ion size. However, ions with higher charge do result in lower impedance measurements. Conclusions: This work establishes the use of simple, small, robust stainless steel cylinders and impedance measurements following separation for the identification and quantification of ions in solution.

Biosensors monitor physiological activities for diagnosis and treatment of disease. Molecularly imprinted polymers (MIPs) are a viable synthetic approach for molecular recognition in biosensing. For biosensing purposes, the most important properties in MIP optimization are sensitivity and selectivity towards a desired analyte. This study aims to optimize MIP sensitivity and selectivity by varying the amount and type of cross-linker used in the synthesis of cortisol and melatonin. The four cross-linkers tested were trimethylpropane trimethacrylate (TRIM), ethyleneglycodimethacrylate (EGDMA), divinylbenzene (DVB), and pentaerythritol triacrylate (PETRA). Based on literature, the following ratios were used for the template molecule to functional monomer to cross-linker in MIP synthesis: for EGDMA cross-linked polymers, 1:6:30; for TRIM and PETRA cross-linked polymers, 1:8:8, 1:6:3, and 1:8:35; for DVB cross-linked polymers, 1:6:30, 1:4:16, and 4:1:60. The polymers were ground and washed, then suspended in a polyvinyl matrix which was spin-coated onto an organic electrochemical transducer (OECT). The device performance was evaluated using electrochemical impedance spectroscopy. For each device, the impedance was measured in electrolyte solutions containing target molecules in concentrations ranging from 1 pM to 100 uM. The impedance was plotted against the analyte concentration to give the sensing slope, which is a measurement for the binding affinity of the polymer. For a device to be considered sensitive, its sensing slope should be greater than its non-imprinted counterpart by a factor above the error margin (+/- 1.79). Of the devices tested, CM1835T (highly cross-linked with TRIM) showed sensitivity towards cortisol, but lacks selectivity towards cortisol over its structural analog, estradiol. Of the melatonin selective polymers, MM163T (low cross-linking with TRIM), MM1630D, and MM4160D (both highly cross-linked with DVB) all showed promising results in sensitivity to melatonin. Overall, the results indicate that high degrees of cross-linking in MIPs improve sensitivity for large, rigid, non-aromatic molecules such as cortisol; however there is no correlation between selectivity and the degree of cross-linking. Meanwhile, divinylbenzene as a cross-linker improves sensitivity and selectivity towards aromatic analytes such as melatonin and estradiol. This study could be improved upon by further characterization of imprinted and non-imprinted polymers, investigation of molecular dynamics, and optimization of devices.

No description available.

This work measured relative permittivity from 15.0 to 55.0 °C of aqueous solutions containing acetone or tetrahydrofuran using a BI 870 dielectric meter. A cubic polynomial fit resulted in coefficients for calculating permittivity as a function of temperature and mole fraction. Literature values for other co-solvent system resulted in similar polynomial coefficients. Using BI 870, permittivity measurements of ionic solutions were not possible because of high conductivity. A simple method using impedance spectroscopy measured these solutions. Impedance decreases with increasing temperature and decreases with increasing ionic strength. Due to the temperature dependence of impedance, all measurements were at 25.0 °C. Anions including bicarbonate, sulfate, acetate, and carbonate were determined using this method. Detection limits were at parts per trillion (ppt) levels. A simple sensor based on smaller stainless steel cylinders and a circuit to determine impedance is currently being developed in combination with an anion exchange column.

Thermal barrier coatings (TBCs) are widely used for thermal protection of hot section components in turbines for propulsion and power generation. Applications of TBCs based on a clearer understanding of failure mechanisms can help increase the performance and life-cycle cost of advanced gas turbine engines. Development and refinement of robust nondestructive evaluation techniques can also enhance the reliability, availability and maintainability of hot section components in gas turbines engines. In this work, degradation of TBCs was non-destructively examined by photostimulated luminescence spectroscopy (PSLS) and electrochemical impedance spectroscopy (EIS) as a function of furnace thermal cycling carried out in air with 10-minute heat-up, 0.67, 9.6 and 49.6 - hour dwell duration at 1121°C (2050°F), and 10-minute forced-air quench. TBCs examined in this study consisted of either electron beam physical vapor deposited and air plasma sprayed yttria-stabilized zirconia (YSZ) on a variety of bond coat / superalloy substrates including bond coats of NiCoCrAlY and (Ni,Pt)Al, and superalloys of CMSX-4, Rene‟N5, Haynes 230 and MAR-M-509. Detailed microstructural characterization by scanning electron microscopy and energy dispersive spectroscopy was carried out to document the degradation and failure characteristics of TBC failure, and correlate results of PSLS and EIS. Mechanisms of microstructural damage initiation and progression varied as a function of TBC architecture and thermal cycling dwell time, and included undulation of the interface between the thermally grown oxide (TGO) and bond coats, internal oxidation of the bond coats, and formation of Ni/Co-rich TGO. These microstructural observations were correlated to the evolution in compressive residual stress in the TGO scale determined by PSLS shift. Correlations iv include stress-relief and corresponding luminescence shift towards stress-free luminescence (i.e. = 14402 cm-1 and  = 14432 cm-1 ) associated with subcritical cracking of the TGO scale and stress-relaxation associated with gradual shift in the luminescence towards stress-free luminescence (i.e.  = 14402 cm-1 and  =14432 cm-1 ) is related to the undulation of TGO/bondcoat interface (e.g., rumpling and ratcheting). Microstructural changes in TBCs such as YSZ sintering, TGO growth, and subcritical damages within the YSZ and TGO scale were also correlated to the changes in electrochemical resistance and capacitance of the YSZ and TGO, respectively. With thermal exposure the YSZ/TGO resistance and capacitance increased and decreased as result of sintering and TGO growth. With progressive thermal cycling damages in the TGO was related to the TGO capacitance showing a continuous increase and at failure TGO capacitance abruptly increased with the exposure of bondcoat. Further correlations among the microstructural development, PSLS and EIS are documented and discussed, particularly as a function of dwell time used during furnace thermal cycling test, with due respect for changes in failure characteristics and mechanisms for various types of TBCs

No description available.

State-of-Health (SoH), a specified measure of stability, is a critical parameter for determining the safe operating area of a battery cell and battery packs to avoid abuse and prevent failure and accidents. A series of experiments were performed to evaluate the performance of a 4P1S battery array using electrochemical impedance spectroscopy to identify key frequencies that may describe battery state of health at any state of charge. Using a large sample number of cells, the state of health frequency, fSoH, for these LiFePO4 26650 cells is found to be 158 Hz. Four experiments were performed to evaluate the lifetime in different configurations: single-cell at 1C (2.6A), single-cell at 10C (26A), four cells in parallel at 10C (ideal match), and four cells in parallel (manufacturer match). The lifetime for each experiment set degraded substantially, with the final parallel series reaching end of life at 400 cycles, a 75.32% reduction in life compared to operating solo. Analysis of the fSoH data for these cells revealed a change in imaginary impedance at the critical frequency that corresponded to changes in the capacity and current data, supporting the development of a single-frequency diagnostic tool. An electrochemical model of the battery was generated, and it indicated the anode material was aging faster than the SEI layer, the opposite of normal cell degradation. A post-mortem analysis of cells from three configurations (baseline, single-cell, and parallel-cell) supported the modeling, as physical damage to the copper current collector in the anode was visible in the parallel-connected cell. / Ph. D. / Lithium-ion batteries are used in a large number of applications, from cellular phones to laptops and electric vehicles. In low power devices, such as a laptop, these batteries can be relatively stable if the associated circuitry is designed properly. However, as the amount of power required from the battery increases, the possibility of an internal battery fault will also increase. The ability to determine the stability of the battery for military applications such as laser weapon systems, electromagnetic railguns or commercial systems such as electric vehicles or industrial-scale micro-grids becomes critical to prevent catastrophic events such as fires. Additionally, the ability to determine the battery State-of-Health (SoH), a specified measure of stability, will enable advance warning of a failing battery to optimize the logistics chain in an operational system. A battery marked as “bad” can be scheduled for replacement before a failure actually occurs. This dissertation has designed a series of experiments that establishes the technology to detect these internals faults, and applies them to a scaled battery system that represents a much larger system. When batteries are placed in parallel and discharged at very high currents, typical of the military applications, the lifetime for the cells was reduced by 75% when compared to batteries discharged under the same conditions by themselves. A post-mortem analysis of cells from three different conditions (uncycled, single-cell, parallel-cell) reveals physical damage to the internal electrodes that indicates a high level of internal destruction occurs at high currents when in parallel arrays.

Cancer is a major health issue that has been associated with over 80 million deaths worldwide in the last decade. Recently, significant improvements have been made in terms of treatment and diagnosis. However, despite these advancements there is still a demand for low-cost, high-accuracy, and easy-to-use technologies capable of classifying cells. Analysis of cell behavior in microfluidic deformability assays provides a label-free method of observing cell response to physical and chemical stimuli. This body of work shows advancements made toward reaching our goal of a robust and cost-effective biosensing device that allows for the identification of normal and cancer cells. These devices can also monitor cell responses to physical and chemical stimuli in the form of mechanical deformation and chemotherapeutic drugs, respectively. Our initial design was a microfluidic device that consisted of three channels with varying deformation and relaxation regions. Cell velocities from the deformations regions allowed us to distinguish between normal and cancer cells at the single-cell level. The next design used a singular deformation channel that was embedded with an array of electrodes in order to measure entry time, transit time and velocities as a single cell passes through the channel. These factors were found to reveal information about the biomechanical properties of single cells. Embedded electrodes were implemented in order to reduce post processing times of the data analysis and provide more insight into the bioelectrical information of cells. Finally, we report a microfluidic device with parallel deformation channels and a single electrode pair to improve throughput and automate data collection of deformability assays. This thesis demonstrates how microfluidic deformability assays, with and without embedded electrodes, show promising capabilities to classify different cells based on their biophysical traits which can be utilized as a valuable tool for testing responses to physical and chemical stimuli. / MS / Cancer is a worldwide health issue with approximately 1.7 million new cases each year in the United State alone. Although a great amount of research has been conducted in this field, the numerous uncertainties and heterogeneity among tumors, which is amplified by the large diversity between patients, has limit progress in both diagnostics and therapy. Traditionally, cancer studies have primarily focused on biological and chemical techniques. However, more recently, researchers have begun to leverage engineering techniques to acquire a new perspective on cancer to better understand the underlying biophysical attributes. Thus far, various engineering methodologies have produced meaningful results, but these techniques are costly and tend to be laborious. As a result, there is a need for low-cost, high-accuracy, and easy-to-use technologies to aid with cancer research, diagnostics, and treatment. An emerging field to alleviate these concerns is microfluidics, which is a science involving the flow of fluids in micro-scale channels. The field of microfluidics shows a great deal of promise for the development of clinically ready devices for analyzing cancer cells at both the population and single cell levels. Investigating the behavior of cancer cells at a single cell level can provide valuable information to help better understand the responsiveness of tumors to physical or chemical stimuli, such as chemotherapeutic drugs. This thesis reports multiple robust and cost-effective biomedical micro-devices that are used to analyze normal and cancerous cells. These devices consist of a microfluidic channel with sensors and are created using micro-fabrication techniques. The unique designs have enabled the evaluation of cells based on their mechanical and electrical properties. Specifically, the mechanical properties can be measured by forcing a cell into a microfluidic channel that is smaller than the diameter of the cell and recording its response to this physical stimulus. Electrical properties are measured simultaneously as the cells are probed for their mechanical properties. In general, the mechanical and electrical properties of cells can be altered when they undergo internal change (i.e. diseased cells) or experience external stimuli. Thus, these properties can be utilized as indicators of cancer progression and can be used to distinguish tumorigenic from non-tumorigenic cells. Data collection from these devices is automated, allowing for the rapid acquisition of mechanical and electrical properties of cells with minimal post-processing. Results from these devices have been promising in their ability to indicate significant differences among various normal and cancer populations based on their mechanical and electrical attributes.

Recent attempts to investigate living systems from a biophysical point of view has opened new windows for development of new diagnostic methods and therapies. Pulsed electric fields (PEFs) are a new class of therapies that take advantage of biophysical properties and have proven to be effective in drug delivery and treating several disorders including tumors. While animal models are commonly being used for development of new therapies, the high cost and complexity of these models along with the difficulties to control the electric field in the animal tissue are some of the obstacles toward the development of PEFs-based therapies. Microengineered models of organs or Organs-on-Chip have been recently introduced to overcome the hurdles of animal models and provide a flexible and cost-effective platform for early investigation of a variety of new therapies. In this study microfluidic platforms with integrated micro-sensors were designed, fabricated and employed to study the consequences of PEFs at the cellular level. These platforms were specifically used to study the effects of PEFs on the permeabilization of the blood-brain barrier for enhanced drug delivery to the brain. Different techniques such as fluorescent microscopy and electrical impedance spectroscopy were used to monitor the response of the cell monolayers under investigation. Irreversible electroporation is a new focal ablation therapy based on PEFs that has enabled ablation of tumors in a non-thermal, minimally invasive procedure. Despite promising achievements and treatment of more than 5500 human patients by this technique, real-time monitoring of the treatment progress in terms of the size of the ablated region is still needed. To address that necessity we have developed micro-sensor arrays that can be implemented on the ablation probe and give real-time feedback about the size of the ablated region by measuring the electrical impedance spectrum of the tissue. / Ph. D.

No description available.