The adsorption of cytochrome c onto mesoporous silica (MCM-41) was investigated in this study. MCM-41 was synthesized and characterized by different methods. The pore size of MCM-41 was calculated from each method and all were in agreement with each other. Result from SAXS method showed a well ordered 2D hexagonal structure of MCM- 41. To investigate the effect of pH on adsorption process, different buffers were used with various pH in the range from 3.8 to 10.7. It was observed that the maximum adsorption occurs at pH near the isoelectric point of cytochrome c. The surface charges of cytochrome c and MCM-41 play an essential role for the process of adsorption. Desorption of cytochrome c from MCM-41 was investigated as well. Pure water and buffers with pH 7.1 and 10.7 were used to study the desorption. The result shows that desorption of cytochrome c from MCM-41 takes place at a pH above its isoelectric point.

The resonance frequency of a silicon nitride (SiN) nano-electromechanical systems (MEMS/NEMS) can be measured precisely due to their large quality factor that is associated to low thermomechanical fluctuations. While these properties enable the fabrication of high performance sensors, their use will eventually raise questions regarding their long-term stability, notably for calibration purposes. The long-term frequency stability and aging of SiN are less studied than the short-term fluctuations such as thermomechanical noise. Long-term aging studies exist for quartz clocks as well as MEMS silicon clocks and accelerometers, but not for SiN resonators with high quality factors. Thus, in this work we conduct the aging study of SiN membranes fabricated by our lab, by constantly tracking changes of the resonance frequency of the device over a long period. The evolution of the frequency drift is tracked, by optical interrogation, continuously for 135 days with a digital phase locked loop (PLL). Our device is placed in a cell under high vacuum to suppress air damping on our resonating membrane. Furthermore, due to its high sensitivity to temperature changes, our silicon nitride resonator and vacuum chamber are placed in an air bath providing a stable temperature (within 0.5 K over 135 days in the present case). To compensate further the frequency drifts induced by temperature changes, a multimeter measures the resistance of a calibrated thermistor placed inside the vacuum environment. The measured frequency drift for the aging periods of 135 days was of 300 parts per million (ppm) and was consistent with previously reported double logarithmic models for quartz oscillators. The initial stage of negative frequency drift, in our aging data, is consistent with the behaviour expected from the desorption of water due to the transition from ambient air environment to high vacuum. We review models explaining how water adsorption/desorption impacts our membrane's frequency by (1) inducing chemical reaction stresses (most important effect), (2) through the contribution of the water surface tension stress (non-negligible effect), and (3) through mass loading from water molecules (weakest effect). After this initial negative trend, the membrane frequency drift inverts and increases almost linearly, in a fashion consistent with loss of mass from desorption of other chemical species. To identify these chemical species, X-ray photoelectron spectroscopy measurements were conducted on a reference membrane stored in an ambient setting and on our membrane placed under vacuum during our aging studies. The aged membrane, compared to its reference counterpart, contained substantially less alkaline ion contaminants (i.e., sodium, calcium and potassium), most likely due to desorption of these species during the aging measurement, and to the increase in adsorption occurring on the reference membrane concurrently. We therefore hypothesize that trapped negative charges, which is a typical phenomenon within dielectric materials such as SiN, might progressively attract positive ion contaminants over time when the device is exposed to ambient air.

<p>  </p> <p>The development of a novel technique employing the use of a linear quadrupole ion trap mass spectrometer coupled to a Nd:YAG laser and a home-built fast reagent-mixing apparatus is detailed and used to detect the short-lived tetrahedral reaction intermediate of the reaction of acetyl chloride with ethanol in microdroplets. Additionally, tandem and high-resolution mass spectrometry is used to characterize potential precursors for solution-processed metal selenide semiconductors in order to determine a synthetic route to sulfur-free thin films. Lastly, Raman MCR (multivariate curve resolution) spectroscopy is used to study the binding-induced conformational change of 1-bromopropane upon binding to α-cyclodextrin as a model system to examine guest conformational changes upon binding to a host molecule.</p>

Traditional occupational hygiene assessment of occupational exposures to organic gases and vapours rely on low flow (<200 ml/min) NIOSH sorbent tubes. This work investigates 3M charcoal filter media (JK50 and JK40, 3M, Inc.) for collection and analysis of organic vapours across 0.1 ¿ 5 l/min. To enable this work, a custom exposure facility was constructed and validated within which organic analyte gas/vapour concentrations could be introduced at known concentrations while controlling environmental variables such as temperature and humidity and other variables. This facility enabled experiments designed to investigate collection and desorption efficiencies across a range of sample flow rates, temperature and humidity conditions for both NIOSH sorbent tubes (e.g. SKC tube) and 3M charcoal filter media. As a result of the investigations described in this thesis, the following conclusions are drawn. Performance of the 3M charcoal filter media for collection and desorption efficiencies for loading, storage time, humidity and breakthrough at low flow rates (<0.5 l/min) were found comparable to the SKC sorbent tube. It is concluded that 3M charcoal media (JK50 and JK40) are suitable for sampling and analyses of hydrocarbons at flow rates <0.5 l/min. The collection efficiencies of the 3M charcoal filter media were investigated at high flow rates (>0.5l/min) for the same parameters, i.e., loading, temperature and humidity. It is concluded that 3M charcoal filter media can be used with confidence in sampling and analysis of airborne hydrocarbons up to 5 l/min. The Wheeler-Jonas model was found to satisfactorily predict the adsorption kinetics of the 3M charcoal filter media at different loading values of hydrocarbons. It was therefore concluded that the model can be applied to determine the suitable amount of 3M charcoal filter media prior to sampling for a given loading.

<p>  </p> <p>Mass spectrometry (MS) is a powerful tool for the molecular-level characterization of complex mixtures. It is susceptible, selective, versatile, and fast. MS provides molecular weight information for the ionized analytes based on their mass-to-charge (<em>m/z</em>) ratios. Elemental compositions of the ionized analytes can be provided by MS operated at high resolution. In addition, MS provides invaluable information through tandem mass spectrometric approaches. Tandem mass spectrometry (MSn, n ≥ 2, where n is the number of ion-separation steps) utilizing collision-activated dissociation (CAD) has proven especially effective for elucidating the structures of individual compounds in complex mixtures. MS can be coupled with various external desorption/ionization methods. Laser-induced acoustic desorption (LIAD) is a technique that enables the evaporation of nonvolatile and thermally labile compounds into a mass spectrometer from the surface of the metal foil. LIAD is a soft evaporation technique that is a great companion for MS because it causes minimal fragmentation to the desorbed neutral molecules. LIAD can also be coupled with instruments other than mass spectrometers, such as molecular rotational resonance (MRR) spectrophotometer as a versatile evaporation technique. </p> <p>This dissertation focuses on research using high-resolution tandem mass spectrometric methods for the structural characterization of isomeric cations of asphaltene model compounds. The fragmentation behaviors of seven isomeric n-pentylquinoline radical cations are studied. Mechanisms for the formation of several fragment ions are also discussed based on quantum chemical calculations. Additionally, a novel suspension spin coating method is reported to improve LIAD performance. Further discussed in the dissertation is the endeavor of expanding the field of LIAD applications to MRR spectroscopy.</p>

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