Hydrogen is a component of spacecraft fuel that is explosive at atmospheric concentrations of four percent or higher. A study was undertaken to determine potential systems for use in tow types of hydrogen sensors that will be useful for real time hydrogen detection, both in ground storage and utilization facilities and in spacecraft. Quantitative detection demands a small, highly sensitive, and highly selective sensor. These detectors will be useful in areas such as the vicinity of joints, couplings, and stress points in the hydrogen storage and plumbing system of the space shuttle. Qualitative detection requires the other sensor to cover large areas, use no power, and be easily monitored visually or with a camera. Such a sensor will serve two purposes: it will allow general detection of hydrogen in a large space where poorly positioned point sensors would fail; it will also aid in locating and repairing any hydrogen leaks that might occur. A manganese (IV) oxide film was produced on the surface of a quartz crystal microbalance and this system was investigated for use as a small, quantitative hydrogen sensor. A reproducible response to hydrogen in the form of an increase in the frequency of vibration of the quartz crystal under an applied voltage was demonstrated. Other coatings were also investigated. A number of indicator compounds were screened for response to hydrogen to serve as large area sesnors. The metallochromic indicator, calmagite, produced a noticeable darkening upon exposure to hydrogen, demonstrating its potential for use as a qualitative, large area hydrogen sensor.

In this thesis, a new technique for using quartz crystal microbalance (QCM) in magnetic field was explored. This technique would take advantage of the sensitive nature of QCM to vibration changes. The idea is to perturb the QCM vibrations with magnetic materials on it by applying magnetic field. A new instrument called magnetic QCM (MQCM) was constructed to explore this technique. The thesis contains three bodies of work. The first body describes the development of the MQCM instrument and the demonstration of the technique. The resonance frequency of a QCM with conducting polymer (polyaniline) suspension in poly(ethylene glycol) was observed to increase with increasing applied DC magnetic field. The change in population of free spins through doping with HCl vapor is reflected in increased frequency-field curve magnitude. The second body of work describes the study of QCM proximity phenomenon discovered during the MQCM instrument development process. When an object approaches a vibrating QCM, the resonant frequency changes. This proximity effect is seen at the distance of 10 mm in air and becomes more pronounced as the distance decreases. This effect depends on the value of quality factor, conductivity of the object, and electrical connection of the object to the QCM electrodes. A simple modified Butterworth van-Dyke model is used to describe this effect. It must be recognized that this effect may lead to experimental artifacts in a variety of analytical QCM applications. The third body of work describes an improved version of MQCM. The complex geometry such as particle suspension were simplified to alternating stack of ferromagnetic and diamagnetic layers. When magnetic field was applied, changes in the QCM admittance magnitude and phase curves were observed. A mass-equivalent stack of continuous consecutive layers of nickel and gold was also exposed to magnetic field but no changes were observed. Butterworth-van-Dyke model attributed the effect to internal shear friction loss among other losses is modulated by the magnetic field. Quantum effect was considered. However, after examining SEM surface images, the source of acoustic response to magnetic field is more likely from interfacial stresses.

published_or_final_version / abstract / Chemistry / Doctoral / Doctor of Philosophy

Chow Ka-man. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2001. / Includes bibliographical references (leaves 52-55). / Abstracts in English and Chinese. / Chapter 1 --- Introduction / Chapter 1.1 --- Chemical sensors --- p.1 / Chapter 1.2 --- Quartz crystal microbalance --- p.4 / Chapter 1.3 --- Concept of affinity mass sensor --- p.8 / Chapter 1.4 --- Film immobilization technologies --- p.9 / Chapter 1.5 --- Research outlines --- p.13 / Chapter 2 --- Experimental / Chapter 2.1 --- Sensor fabrication --- p.14 / Chapter 2.2 --- Flow-through cell --- p.16 / Chapter 2.3 --- Analysis procedures --- p.19 / Chapter 2.4 --- Response curve --- p.19 / Chapter 2.5 --- Experimental setup --- p.21 / Chapter 3 --- Detection of ascorbic acid by affinity mass sensor based on 3-aminophenylboronic acid / Chapter 3.1 --- Conventional analytical methods --- p.23 / Chapter 3.2 --- Research method - affinity mass sensor based on APBA --- p.24 / Chapter 3.3 --- To locate the binding site in ascorbic acid --- p.25 / Chapter 3.3.1 --- Steric energy calculated by molecular modeling --- p.26 / Chapter 3.4 --- Optimization of experimental variables --- p.29 / Chapter 3.4.1 --- Effect of pH --- p.29 / Chapter 3.4.2 --- Effect of sample volume --- p.30 / Chapter 3.4.3 --- Effect of flow velocity --- p.30 / Chapter 3.5 --- Calibration and Reproducibility --- p.32 / Chapter 3.6 --- Kinetic analysis --- p.33 / Chapter 3.7 --- Stability of sensor --- p.37 / Chapter 3.8 --- Interference studies --- p.37 / Chapter 3.9 --- Determination of ascorbic acid in real samples --- p.39 / Chapter 3.9.1 --- Results and Discussion --- p.39 / Chapter 3.10 --- Comparison with conventional ascorbic acid sensors --- p.42 / Chapter 3.11 --- Summary --- p.42 / Chapter 4 --- Boronic acid derivatives for the detection of sugars / Chapter 4.1 --- Scope of this work --- p.43 / Chapter 4.2 --- Results and Discussion --- p.44 / Chapter 4.3 --- Summary --- p.49 / Conclusion --- p.50 / References --- p.52 / List for tables --- p.56 / List for figures --- p.57 / Appendix I --- p.59 / Appendix II --- p.61

Thesis (Ph. D.)--University of Hong Kong, 2007. / Title proper from title frame. Also available in printed format.

This thesis uses surface sensitive tools to characterize the effect of a solid surface on immobilized biomacromolecules. This includes understanding how the surface can change the affinity of these macromolecules to small molecules compared to bulk studies. Two classes of immobilized biomacromolecules, the supported lipid bilayer (SLB) and the Lac repressor protein (LacI), are characterized using microcantilever sensors and quartz crystal microbalance with dissipation (QCM-D). The first part of this thesis reports the use of microcantilever beams, an ultrasensitive sensor for measuring the surface free energy changes on a substrate induced by molecular adsorptions, to probe the interaction between a solid surface and a phospholipid bilayer. This sensing method integrates two well-developed techniques: solid-supported lipid bilayers (SLBs) and the microcantilever (MC) sensors. Studying the adsorption free energy of lipid bilayers on a solid surface allows better characterizing of the formation and stability of SLBs. Microcantilever converts the Gibbs free energy change taking place on its surface into a mechanical deformation. As molecules physisorb or chemisorb onto the surface of the microcantilevers, the microcantilevers bend, either due to induced compressive or tensile stresses, which result from the surface free energy change. By monitoring the deflection values of the microcantilevers, the real-time surface free energy change during the SLB formation can be detected. This thesis has led to the development of a novel biosensor--lipid membrane coated microcantilevers--to detect the adsorption, insertion, aggregation and solubilizing effect of membrane-active substances, such as surfactants and peptides, on the phospholipid membranes. To better characterize the surface free energy, SLBs doped with charged lipids or cholesterol are shown to alter the surface free energy. We can predict this change in surface free energy using a thermodynamic model. Application of this membrane-coated cantilever is put into use for detecting how amphiphilic molecules interact with SLBs, as well as for probing the abrupt conformational change of SLBs during a temperature induced phase-transition. This study systematically demonstrates various usage aspects of microcantilever to characterize the SLBs, and how this technique may advance the biophysical knowledge of the lipid membrane, one of the essential building blocks of life. The second part of this thesis reports the use of both microcantilever sensors and QCM-D to measure the adsorption free energy and mass of a model protein, the Lac repressor (LacI), and compare how a modified T334C mutant that includes a cysteine group to orient the protein on the gold surface through a covalent sulfur bonds retains its binding capabilities over that of wild type LacI. The main challenge of this work is to unravel how the adsorption of biomacromolecules at the solid/liquid interface leads to surface free energy changes and ultimately changes the stress of the underlying solid surface (the cantilever). The uses of microcantilever sensors and QCM to probe the interactions that take place on SLBs and surface-bound proteins have the advantage of being a sensitive, real-time, and label-free technique.

The primary objective of this study was to develop a sensitive and cost-effective sorption system to analyze adsorption and diffusion of different gases on micro porous materials and nanotubes. A high pressure Quartz Crystal Microbalance (QCM) based adsorption apparatus for single-component gas was developed. A QCM is an acoustic-wave resonator in which the acoustic wave propagates through the crystal. Therefore, it is highly responsive to addition or removal of small amounts of mass adsorbed or deposited on the surface of the crystal. This mass sensitivity makes the QCM an ideal tool for the study of gas adsorption. The QCM-based adsorption apparatus is advantageous over the commercialized none-gravimetric and gravimetric equipment in a way that it is low-cost, highly sensitive and accurate for mass sorption applications, satisfactorily stable in a controlled environment, and can be used for thin films. The high pressure apparatus was calibrated using Matrimid 5218, whose thermodynamic properties and adsorption parameters are known. The Matrimid was spin-coated onto a 14 mm-diameter QCM, and sorption equilibrium data for were obtained for CO₂ gas at 25, 30, 48, and 52 ºC and partial pressure range between 0 to 4 bar. In order to compare the experimental data with available literature data, the experimental data was fitted into a dual-mode adsorption model. The model results from Henry's law and a Langmuir mechanism. Comparison of the experimental adsorption isotherm of Matrimide for CO₂ gas with literature data showed reasonable agreement between the experimental and literature data. In this study, the adsorption parameters of aluminosilicate nanotubes are observed. Aluminosilicate nanotubes are ideal materials for chemical sensing, molecule separation, and gas storage; hence, there is a need for adsorption and diffusion data on this material. The adsorption of CO₂, N₂, and CH₄ gases on aluminosilicate nanotubes samples has been studied in the temperature range of 20° to 120° Celsius and pressure range of 0 to 8 bar. The experimental results yield the CO₂ and N₂ heat of adsorptions of -32.9 and -28.1 kJ/mol respectively.

The contamination of drinking water by microbial pathogens is recognized as one of the most pressing water supply problems of our day. To minimize the impact of pathogens and parasites on the environment and public health, accurate methods are needed to evaluate their presence and concentration. Although various techniques exist to detect certain pathogens in water (e.g., immunofluorescence or PCR techniques), these are time- and labor-intensive. A direct, real-time method for detection and quantification of target organisms would thus be very useful for rapid diagnosis of water safety. A quartz crystal microbalance with dissipation monitoring (QCM-D) based biosensor for detection of waterborne pathogens (i.e., Escherichia coli O157:H7) was developed. The detection platform is based on the immobilization of affinity purified antibodies onto gold coated QCM-D quartz crystals via a cysteamine self-assembled monolayer. The results show that the optimal sensor response is the initial slope of the dissipation shift. A highly log-log linear response is obtained for detection of E. coli O157:H7 over a broad range of cell concentration from 3 x 105 to 1 x 109 cells/mL. The prepared biosensor also exhibits a log-log linear working range from 107 to 109 cells/mL for E. coli K12 D21, a non-pathogenic model organism. The biosensor also shows satisfactory selectivity using Bacillus subtilis . To our knowledge, this is the first study demonstrating the use of the slope of the dissipation shift as a sensor response when using QCM-D technology. / Keywords: Biosensor, QCM-D, E. coli O157:H7, polyc1onal antibodies, dissipation slope, cysteamine, self-assembled monolayer

Thesis (M.S.)--University of Texas at El Paso, 2008. / Title from title screen. Vita. CD-ROM. Includes bibliographical references. Also available online.

Thesis (M.For.Sc.)--University of Western Australia, 2007.