As science and medicine advance, it becomes ever more important to be able to control and analyze smaller and smaller bioparticles all the way down to single molecules. In this dissertation several studies aimed at improving our ability to manipulate and monitor single biomolecules will be discussed. First, we will discuss a study on developing a way to map dielectrophoresis with nanoscale resolution using a novel atomic force microscopy technique. Dielectrophoresis can be applied on nanoparticles through micron-scale electrodes to separate and control said particles. Therefore, this new method of mapping this force will greatly improve our ability to manipulate single biomolecules through dielectrophoresis. The next two studies discussed will be aimed at using carbon nanotube nanocircuits to monitor single protein kinetics in real time. Drug development and delivery methods rely on the precise understanding of protein interactions, thus creating the need for information on single protein dynamics that our techniques provides. The proteins studied in these sections are MMP1 and HDAC8, both of which are known targets of anti-cancer drugs. Finally, we developed a new strategy for diagnosing pancreatic cancer. Our strategy involves using graphene nanotransistors to detect exosomes released from the pancreatic tumor. The ability to reliably diagnose pancreatic cancer before it reaches metastasis would greatly improve the life expectancy of patients who develop this condition. We were able to test our technique on samples from a number of patients and were successfully able to distinguish patients with pancreatic cancer from noncancerous patients.

Today, zeolites play a considerable role in many industrial fields, especially in heterogeneous catalysis. Well-defined microporous structure combined with acidity provides exceptional size and shape selectivity, making zeolites indispensable in petrochemistry. However, the micropores can cause diffusion limitations and, in turn, a drop in reaction rate and selectivity. Hence, the development of modification methodologies on zeolite textural properties is one of the attention-grabbing research topics nowadays. For example, to overcome transport limitations in zeolites, the particle size can be reduced, or a system of larger auxiliary pores can be introduced [1]. One of the most promising methods for introducing secondary pores on a large scale is desilication since it is low-cost, versatile, and easy [2]. Despite its simplicity, the desilication mechanism is still a matter of discussion. In detail, it is not well-understood: 1. The influence of different species on mesopore formation kinetics 2. How aluminum is assembled back into the zeolite 3. Which types of aluminum species form throughout the treatment. The present study tries to answer these questions by relating ex-situ and in-situ NMR. The proposed ex-situ 29Si MAS NMR approach allows monitoring the development of mesoporosity and silicon extraction by analyzing Q3 and Q4 changes. The combination of ex-situ with in-situ 29Si MAS NMR study showed that the limiting step of Si extraction is the transformation of Q3 into Q2. 27Al MAS NMR combined with MQMAS showed the formation of new aluminum species after desilication. It was shown that some of the Al framework T-sites might dissolve during alkaline treatment. In-situ 27Al NMR indicates redistribution of dissolved aluminum upon desilication.

The gas phase reactions of CH3O2 + CH3O2, HO2 + HO2, and CH3O2 + HO2 in the presence of water vapor have been studied at temperatures between 263 and 303 K using laser flash photolysis coupled with UV time-resolved absorption detection at 220 nm and 260 nm. Water vapor concentration was quantified using tunable diode laser spectroscopy operating in the mid-IR. The HO2 self-reaction rate constant is significantly enhanced by water vapor, consistent with what others have reported, whereas CH3O2 self-reaction and the cross-reaction (CH3O2 + HO2) rate constants are nearly unaffected. The enhancement in the HO2 self-reaction rate coefficient occurs because of the formation of a strongly bound (6.9 kcal mol-1) HO2-H2O complex during the reaction mechanism where the H2O acts as an energy chaperone. The nominal impact of water vapor on the CH3O2 self-reaction rate coefficient is consistent with recent high level ab initio calculations that predict a weakly bound CH3O2-H2O complex (3.2 kcal mol-1). The smaller binding energy of the CH3O2-H2O complex excludes its formation and consequent participation in the methyl peroxy self-reaction mechanism.

Sprinting on a curve is significantly slower than on a straightaway. Although the dimensions vary from track to track, indoor track curves are among the tightest curves that athletes will sprint at maximal speed. Previous studies have provided theories for how speed attenuation occurs when running on a curve. Yet, no previous research has determined how the variability of indoor track curve radii affects trained sprinters at maximal speeds. Purpose: To determine the differences in running speeds, ground time (GT), and medio-lateral (ML) impulse, with different indoor track radii. A secondary purpose was to understand the between-leg differences in GT and ML impulse during maximal sprinting on a curve. Methods: 10 male intercollegiate sprinters performed 45-m maximal sprints on a straightaway, 15-m track curve and 21-m track curve. A force platform embedded under an indoor track surface measured ground reaction forces while timing lights measured running speed. Analysis: A mixed models analysis of variance blocking on subjects was performed testing the main effects of the track curve on sprinting speed, GT and ML impulse (p<0.01). Results: Sprinting speed was significantly slower when running on a curve. GT increased for inside leg on both curved path conditions compared to straight. ML impulses increased as the radius of the track curve decreased. Discussion: If a 200m race were performed on both our track curves, the track with 21m curve would be 0.12s faster than the track with the 15m curve. GT and ML impulse results support leading explanations that the inside leg is the limiting factor during curve running. Tighter track curves require greater ML forces, but for a shorter period of time compared to larger track turns. Coaches and athletes should consider the radius of the track curve as they prepare for training and performance and consider injury risk. The speed differences observed due to the track curve radius may provide the first step to understanding how the radius of the indoor track curve affects sprinting speed and ultimately, performance.

With the emergence of new biorenewable transportation fuels, the role of heteroatoms in combustion has increased tremendously. While petroleum-based fuels are primarily hydrocarbons, many biorenewable fuels contain heteroatoms such as oxygen and nitrogen, introducing new challenges associated with toxic emissions. A fundamental understanding of the chemical kinetics of combustion of these heteroatomic fuels is necessary to elucidate the pathways by which these toxic emissions are formed and may be achieved through the development of combustion models. Reaction sets, the core of these combustion models, may be assembled for individual fuels through a balance of employing vetted rate constants from prior publications, quantum chemistry calculations, and rate constant estimations. For accuracy, reaction sets should be tested against experimental combustion studies such as low-pressure flame experiments using molecular-beam mass spectrometry (MBMS) or chemiluminescence and high-pressure shock-tube experiments. This dissertation presents the development of a new reaction set to describe gas-phase combustion chemistry of fuels containing only hydrogen, carbon, oxygen, and nitrogen. The foundation of this model was a reaction set to describe combustion of ammonia flames. This reaction set contains only H/N/O chemistry for simplicity. The new reaction set was tested against a pyrolysis shock-tube study, as well as 12 MBMS flame experiments under a variety of conditions, including different mixtures of fuels and oxidizers (NH3, N2O, H2, NO, O2), fuel equivalence ratios (lean to rich), pressures, and concentrations of diluent gas. Additionally, the base H/N/O mechanism was expanded to include carbon chemistry and was tested against flames of dimethylamine, ethylamine, and a methane/ammonia mixture. This reaction set was employed to study heterocyclic biofuels including a fuel-rich flame of tetrahydropyran, the monoether analogue to cyclohexane and the basic ring in cellulose. Additionally, the model was used in a study of morpholine, a 6-membered ring with both ether and amine functionalities, testing the model against fuel-rich flame studies using both MBMS and chemiluminescence techniques and high-pressure shock-tube studies for both oxidation and pyrolysis at elevated temperatures and pressures. Lastly, the model was used to study the combustion of hypergolic rocket fuels, specifically monomethyl hydrazine and tetramethylethyldiamine with red fuming nitric acid.

<p> The pulse response of a full scale aeration tank is mathematically modelled with an arbitrary network of idealized perfectly mixed and plug flow component vessels. The model is fitted in the frequency domain, then inverse transformed to the time domain. The soluble carbon concentration curve of batch biokinetic run is modelled by a modified logistics equation and a piecewise linear expression. The mixing and kinetic models are combined to predict the degree of conversion assuming the degree of segregation, J, to be one. The pulse responses of a lab scale tank for varying water flow rates are also modelled by the same methods. An attempt is made to correlate the mathematical model parameters to the water flow rate. </p> / Thesis / Master of Engineering (MEngr)

<p> The main objective of this study was to gain an understanding of the oxidation properties of iron at low oxygen pressures and at high temperature. </p> <p> A thermogravimetric technique was employed to investigate the oxidation of iron in oxygen over the pressure range 2.5×10⁻³ - 3.0×10⁻¹ torr at temperatures ranging between 750ºC and 1000ºC. The oxidation curves exhibited distinct intervals of linear kinetics followed by transition to intervals of parabolic kinetics during exposures extending to 125 min. Linear kinetics governing the growth of uniformly thick wustite scales; the linear rate constants showed a proportional dependence on oxygen pressure due to reaction control by a phase boundary reaction involving non-dissociation adsorption of oxygen. Parabolic kinetics governed growth of wustite-magnetite scales containing magnetite as outermost layers. The value of the parabolic rate constants were independent of oxygen pressure since scale growth was directly dependent on the iron vacancy gradient in wustite established by the oxygen activities at the Fe/FeO and FeO/Fe₃O₄ interfaces. </p> <p> Scanning electron microscopy techniques were used to gain information on the growth of magnetite and hematite layers in the multilayer scale consisting largely of wustite formed at high temperature in the pressure range 2.5×10⁻³ to 760 torr. </p> / Thesis / Master of Science (MSc)

Magnesium aluminate spinel inclusions are a concern in the steelmaking industry since these particles affect the processing and the properties of steel. During the refining of low carbon aluminum killed steel in the ladle furnace; the initial alumina inclusions shift their composition towards higher contents of MgO and eventually they become magnesium aluminate spinel inclusions. This research developed a kinetic model for the transformation of alumina inclusions to spinel in liquid steel. The aspects of simultaneous deoxidation and of solid state cation counterdiffusion were addressed in the model. Coupling the model for spinel inclusions to a kinetic model for the slag-steel reactions in the ladle furnace allowed verifying the modeled concentrations in the inclusions with the plant data measurements of ArcelorMittal Dofasco operations. Good agreement between the experimental and calculated Mg contents in the inclusions was obtained for most of the industrial heats analyzed. Finally, a sensitivity analysis of the coupled kinetic model was performed to compare the effect of the different processing conditions and mass transfer rates on the amount of Mg and spinel in the inclusions. Several results from this work indicate that the rate limiting step on the formation of magnesium aluminate spinel inclusions is the supply rate of dissolved [Mg] from the slag-steel reaction; the supply of [Mg] is in turn controlled by the changes at the slag-steel interface. / Thesis / Master of Applied Science (MASc)

<p> Polymerization of bulk styrene initiated thermally as well as with di-tertiary-butyl peroxide was studied in isothermal batch reactors. Thermal polymerization was carried out at 100, 140, 170 and 200°C while polymerization with di-tertiary butyl peroxide was at 100 and 140°C. A kinetic model was derived therefrom accounting for initiation reactions from a first order decomposition of catalyst and a second order reaction between two monomer molecules to form two monoradicals, propagation, chain transfer to monomer and termination by combination only. Gel effect was allowed by the variation of rate constants with conversion. Both the thermal initiation rate constant and the first order decomposition rate constant of di-tertiary butyl peroxide were found to agree with literature values with the present values slightly higher. The initial rate constants for propagation, chain transfer to monomer, and termination were extrapolated to the range, 100-200°C using literature data. This kinetic model was used in the simulation of polymer reactor systems studying the effect of recycle and operating conditions on the molecular weight distribution and rate of production of polymer products.</p> <p> The main body of this thesis reports the polymerization study and the development of the kinetic model. The details of the kinetic equations and methods of solution, experimental techniques involved, and the simulation of polymer reactor systems are reported in the Appendices.</p> / Thesis / Doctor of Philosophy (PhD)

<p> An investigation is reported on the kinetics of Ca0-β quartz solid state reaction on basal and prism planes of β-quartz at temperatures in the range between 1000 degrees Celsius and 1200 degrees Celsius. Excess lime present in all the samples ensured ensured the formation of c2s (dicalcium silicate) only. The thickness of the c2s product layer was measured on a Zeiss camera microscope Ultraphot II. The line scans for the distribution of Ca and Si across the reaction layer were obtained on the electron microprobe analyser. The kinetics of the reaction on basal and prism planes of a-quartz in wet and dry nitrogen atmospheres in the temperature range considered was studied by measuring the thickness of c2s as a function of time of reaction. </p> <p> The CaO-β quartz reaction was found to be anisotropic, the basal plane reaction being faster than the .Prism plane reaction. The reaction on both basal and prism planes in the temperature range between l000°C and 1200°C was found to be enhanced in the presence of moisture. The enhancement due to the presence of moisture was found to be more on the basal plane reaction than on the prism plane reaction. This appears to be due to the fact that different polymorphs of c2s with different sensitivities to the presence of moisture are produced on different crystallographic planes of a-quartz considered. The activation energies for the reaction on basal plane and prism plane were found to be about 53 kcal/mole and 63 kcal/mole respectively. They have good agreement with the activation energies of 55 kcal/mole and 65 kcal/mole for Ca diffusion in a-c2s and a-c2s respectively as reported by Lindner. </p> / Thesis / Master of Engineering (MEngr)