Micellar electrokinetic chromatography (MEKC) and capillary electrochromatography (CEC) are two of the major capillary electrophoresis (CE) modes that have been interfaced to mass spectrometry (MS) for sensitive and selective analysis of chiral compounds. This research combines these two modes and expands their applications in chiral CE analysis. Chapter 1 is a review of amino acid based molecular micelles used in MEKC-MS for enantioselective analysis over the past five years. In this chapter, a typical MEKC-MS experiment setup as well as detailed standard operating procedure in synthesis of molecular micelles and running a typical MEKC-MS experiment using the molecular micelles is discussed. Chapter 2 described a multivariate MEKC-MS optimization for the simultaneous analysis of two negatively charged model chiral compounds in negative ion mode with molecular micelles. In this chapter, a central composite design (CCD) is used to first construct a series of experiments to optimize all the important MEKC-MS parameters. Next, response surface methodology (RSM) was used to analyze the interactions between the factors, picking up the best separation and detection conditions, predicting the result of the chiral separation/MS detection, and finally running the actual experiment and comparing the chromatographic results with the predicted parameters. Chapter 3 demonstrates a similar multivariate MEKC-MS optimization for analysis of a positively charged model chiral compound in a positive ion mode. The same CCD and RSM methods were used to optimize the separations and MS sensitivity. Chapter 4 describes a chiral analysis of four neutral benzoin derivatives (hydrobenzoin, benzoin, benzoin methyl ether, and benzoin ethyl ether) using MEKC coupled to atmospheric pressure photo-ionization mass spectrometry (APPI-MS). The same multivariate experimental design strategy was used to optimize the MEKC as well as APPI-MS parameters. Simultaneous chiral separation of all four benzoin derivatives was achieved with high detection sensitivity compared to UV-detection. Chapter 5 introduces a novel one-pot synthesis scheme for an acryloyl-terminated, carbamate-linked surfactant-bound monolith with leucine head group and different chain lengths. The method promises to open up the discovery of new amino acid based polymeric monoliths for chiral separations and enhanced chemoselectivity for simultaneous chiral separations and enhanced detection in CEC and CEC-MS. In Chapter 6, five amide-linked surfactant-bound monoliths with different chain lengths and head groups (leucine, valine, and phenylalanine) were synthesized and characterized. Enantioseparation of several test compounds was achieved by CEC using the monolithic columns. One of the chiral surfactant, sodium 11-acrylamidoundecanoyl-L-leucinate (SAAUL), was polymerized in aqueous solution under 60Co radiation to form molecular micelle poly-SAAUL. MEKC experiments were carried out with the poly-SAAUL molecular micelle to separate ten cationic chiral compounds. The result was compared with the CEC separation using the AAUL monolithic column. This study is the first comparison of chiral CEC and MEKC with the same surfactant monomer, which has the capability of forming both chiral stationary phase for CEC and chiral pseudophase for MEKC.

This thesis researchs the design of quadrature modulator consists of 120MHz quadrature modulator that is fabricated using hybrid elements and print circuit board (PCB) technology for digital signal generator and quadrature modulator monolithic-microwave integrated-circuit (MMIC) that is fabricated using GaAs heterojunction bipolar transistor (HBT) technology for Personal Communication Service (PCS) applications. The 120MHz quadrature modulator incorporates power divider/combiner, phase shifter and doubly balanced mixer; the design architecture, principle and measurement results of division are presented in this thesis. A quadrature modulator is implemented by combining every division and measures specifications accurately, comparing with that of Agilent ESG-D series digital signal generator with the same carrier frequency and digital modulation. The quadrature modulator MMIC for PCS applications incorporates phase shifter, Gilbert cell mixer, differential to single-ended converter and RF amplifier at output; the design architecture, principle and simulation results of division are presented in this thesis. A quadrature modulator is integrated by combining every division and simulates parameters strictly.For troublesome specification measurement of quadrature modulator, this thesis also presents measurement method and instrument setup detailedly.

Drift time ion mobility spectrometry (DTIMS) is a rapid post ionization gas-phase separation technique that distinguishes between compounds based on their differences in reduced mass, charge and collisional cross-section while under a weak, time-invariant electric field. Standalone DTIMS is currently employed throughout the world for the detection of explosives, drugs and chemical-warfare agents. The coupling of IMS to MS (IM-MS) has enabled the performance of time-nested multidimensional separations with high sample throughput and enhanced peak capacity, allowing for the separation of ions not only based on their mass/charge (m/z) ratios, but also their shape. This allows for the elucidation of valuable structural information that can be utilized for determining gas phase ion conformation and differentiation between closely related ionic species. Over the past decade, these advances have transformed IM-MS applications and instrumental designs into one of the most rapidly growing areas of mass spectrometry. The work presented in this thesis is aimed at the development and subsequent characterization of a novel high-resolution resistive-glass atmospheric pressure DTIMS, and the application of this prototype DTIMS to the detection of environmentally relevant compounds. A review of the different types of ion mobility spectrometers, their principles of operation, and the advantages and disadvantages of each type are presented in Chapter 1. Chapter 2 describes the design and development of our prototype resistive glass DTIMS. A detailed description of the IMS hardware, including the ion sources, custom-built control computer, pulsing electronics, data acquisition system, and the timing schemes developed to operate the instrument in standalone DTIMS, multiplexed DTIMS, and IM-MS mode, are presented. Chapter 3 presents an initial characterization of the performance of a prototype resistive glass DTIMS under a wide range of instrumental parameters and also characterizes the radial ion distribution of the ions in the drift region of the spectrometer. Chapter 4 addresses the lack of sensitivity in DTIMS and explores ion trapping and multiplexing methods, introduces the principles of multiplexing and describes an extended multiplexing approach that encompasses arbitrary binary ion injection waveforms with variable duty cycles. Chapter 5 presents a detailed theoretical and experimental study of the separation power of our DTIMS and presents an evaluation of the field homogeneity and the performance of the ion gate.

A monolithic approach to aero-structural analysis and optimization has been developed and implemented. In contrast to a partitioned approach which uses individual fluid and structural solvers to solve their respective systems separately, the monolithic approach solves a fully-coupled system simultaneously, enforcing solution compatibility across the sub-system interfaces at each iteration. In this work, a three-field formulation is used, consisting of fluid, structural, and fluid mesh-movement sub-systems. The performance of the monolithic approach is characterized using 1-D unsteady and 2-D steady analysis problems, and compared with a partitioned approach. Four steady model aero-structural optimization problems are also investigated. Gradients of the objective function are computed using the discrete-adjoint and flow-sensitivity (direct) methods. In each case, the monolithic approach is shown to be a promising option for efficient aero-structural analysis and optimization, though the implementation requires additional development of coupling sub-matrices when compared to a partitioned approach.

This thesis explores the design and applications of subharmonic mixers in CMOS microwave integrated circuits. First, a 2x down-converting subharmonic mixer is demonstrated with a measured conversion gain of 8 dB using a 2.1 GHz RF signal. Extending the concept of the 2x subharmonic mixer, a 4x subharmonic mixer is proposed that operates in the 12 GHz Ku-band. This circuit is the first 4x subharmonic mixer in CMOS, and achieves a 6 dB conversion gain, which is the highest for any 4x subharmonic mixer regardless of circuit topology or fabrication technology. Furthermore, it achieves very high measured isolation between its ports (e.g. 4LO-RF: 59 dB). Since both the 2x and the 4x subharmonic mixers require a quadrature oscillator, a new oscillator circuit is presented that could be used with either of the aforementioned mixers. This quadrature oscillator uses active superharmonic coupling to establish the quadrature fundamental relationship. The oscillation frequency is 3.0 GHz and the measured output power is -6 dBm. A dual-band mixer/oscillator is also demonstrated that can operate as either a fundamental mixer or a subharmonic mixer depending on a control voltage. This circuit operates from 5.0 GHz to 6.0 GHz or from 9.8 GHz to 11.8 GHz by using either the fundamental output or the second harmonic output of the quadrature oscillator circuit described above and achieves conversion gain over both frequency bands. A novel frequency tripler circuit is presented based on a subharmonic mixer. This circuit uses the 2x subharmonic mixer discussed above, along with a feedforward fundamental cancellation circuit. The measured fundamental suppression is up to 30 dB and the conversion gain is up to 3 dB. Finally, a frequency divider circuit based on a subharmonic mixer is presented that divides the input signal frequency by a factor of three. This circuit uses a single-balanced version of the 2x subharmonic mixer described above in a regenerative divider topology. The measured input signal bandwidth is 300 MHz (5.2 GHz to 5.5 GHz) with an input power of -7 dBm and the maximum conversion gain is 0 dB. / Thesis (Ph.D, Electrical & Computer Engineering) -- Queen's University, 2009-03-24 16:08:31.805

In this thesis, three low-noise active mixing circuits are presented in CMOS technology. Mixers can be found at the front-end of almost every communication systems. However, despite many advantages the active mixers have, one drawback is their poor noise performance. One mixer that has been widely used in integrated circuit is the Gilbert cell. This thesis demonstrated that by merging the low-noise amplifier (LNA) with the Gilbert cell, a low-noise active mixer can be realized. This kind of mixer relaxes the front-end design, allows higher circuit integration, and reduces power consumption. The first circuit is a narrowband low-noise mixer that operates at 5.4 GHz in 0.18 um CMOS. An inductive degenerated LNA is used as the transconductor. Together with a current bleeding circuit, a gain of 13.1 dB and a low 7.8 dB single-sideband noise figure are achieved. The circuit was fabricated and measured. Simulation and measurement results are compared and discussed. The second circuit is a broadband low-noise mixer that operates between 1 and 5.5 GHz in 0.13 um CMOS. The noise-cancelling technique is used to design the transconductors. This technique does not require the use of inductors while able to achieve a sub 3 dB noise figure and input matching over a large bandwidth. To further extend the mixer bandwidth, the series inductive peaking was used. Measured and simulated results showed great agreement. It has a high gain of 17.5 dB, a bandwidth of 4.5 GHz, and a low average double-sideband noise figure of 3.9 dB. This mixer has the best broadband noise performance ever reported in CMOS. Finally, a double-balanced low-noise self-oscillating mixer (SOM) in 0.13 um CMOS is presented. This is a current-reuse, highly integrated circuit that combines an LNA, mixer, and oscillator seamlessly into a single component. The oscillator generates the required LO while serving as the mixer load simultaneously. Measured and simulated results showed excellent agreement. A low double-sideband noise figure of 4.4 dB and a gain of 11.6 dB were measured. This type of SOM and loading structure are the first ever reported. / Thesis (Master, Electrical & Computer Engineering) -- Queen's University, 2009-08-23 12:41:20.445

This thesis explores the design of fast-settling pulse generators and pulsed low noise amplifiers (LNAs) for Ultra-Wideband (UWB) applications. These components are critical in pulsed UWB transceivers, and a high energy efficiency is sought without adversely affecting RF performance and functionality. To this end, new pulse generators with a subnanosecond settling time and a low energy consumption of only a few picojoules per pulse are targeted. Moreover, a novel pulsed LNA is investigated for a low power consumption that can be scaled with the duty cycle. First, an energy-efficient tunable pulse generator is proposed for high-data-rate 3.1-10.6 GHz UWB applications. A current-starved ring oscillator is quickly switched on and off, and the amplitude envelope is shaped using a passive attenuator. The energy consumption per pulse is below 4.2 pJ while the pulse amplitude is 150 mV, yielding a high energy efficiency. A quadrature pulse generator is then presented for 22-29 GHz UWB applications with a settling time below 0.5 ns. An inductor-capacitor (LC) oscillator is quickly switched on and off with a new technique, and the amplitude envelope is shaped using a variable passive attenuator. The energy consumption per pulse is only 6.2 pJ, and the pulse amplitude is more than 240 mV, yielding the highest energy efficiency reported to date in CMOS. Next, a 3-10 GHz pulsed ring oscillator that offers direct quadrature phase modulation is demonstrated. Current impulses are injected into the oscillator to enable fast startup and implement quadrature phase modulation. The energy consumption and voltage swing varies from 13 pJ and 300 mV at 3 GHz to 18 pJ and 200 mV at 10 GHz respectively, yielding a high energy efficiency. Lastly, a fast switching noise cancelling LNA is proposed for 3.1-10.6 GHz UWB applications that settles within 1.3 ns for switching speeds as high as 200 MHz. Inductive peaking is introduced in the noise cancelling topology to achieve a sub-4dB flat noise figure and a high gain of 16.6 dB for frequencies up to 10 GHz. The average power consumption is also below 10 mW with a 50% duty cycle clock. / Thesis (Ph.D, Electrical & Computer Engineering) -- Queen's University, 2011-08-23 15:29:58.93

An improved steady-state method combining experiment and mathematical modelling has been developed to characterize the scalable convective heat transfer coefficient, hvol [W*m^(-3)*K^(-1)], of uncoated and catalyst-support coated aluminium foam monoliths. The values of hvol were recovered by parameter fitting its model values to experimental temperature data for steady-state air-cooled monoliths under a known heating flux. The model was built with experimentally recovered values of the monolith’s thermal conductivity and fluid permeability along with known values for other physical parameters. The volumetric heat transfer coefficients of 10, 20 and 40 pore-per-inch uncoated aluminium foams were determined to range between 2,700 and 20,000 W*m^(-3)*K^(-1) at channel Reynolds numbers between 85 and 1,700. The presence of a 76 micron thick anodized layer of catalyst support on monolith foams effected a small but significant reduction in the value of hvol. Coating with an anodized layer also reduced the permeabilities of the monoliths to air flow by 4-20%. Knowledge of the scalable parameter, hvol, was used to model a steady-state non-isothermal, non-isobaric heat-coupled methanol reformer. The model shows that changes to the convective transfer coefficient due to coating the monolith with catalyst support may have significant consequences for the thermal profile of the model reactor and for the product yield. / Thesis (Master, Chemical Engineering) -- Queen's University, 2011-12-12 20:11:18.046

For the last four decades, the semiconductor industry has experienced an exponential growth. According to the ITRS, as we advance into the era of nanotechnology, the traditional CMOS electronics is reaching its physical and economical limits. The main objective of this thesis is to explore novel design opportunities for reconfigurable architectures given by the emerging technologies. On the one hand, the thesis will focus on the traditional FPGA architecture scheme, and survey some structural improvements brought by disruptive technologies. While the memories and routing structures occupy the major part of the FPGAs total area and mainly limit the performances, 3-D integration appears as a good candidate to embed all this circuitry into the metal layers. Configuration and routing circuits based on back-end compatible resistive memories, a monolithic 3-D process flow and a prospective vertical FETs process flow are introduced and assessed within a complete architectural context. On the other hand, the thesis will present some novel architectural schemes for ultra-fine grain computing. The size of the logic elements can be reduced thanks to inherent properties of the technologies, such as the crossbar organization or the controllable polarity of carbon electronics. Considering the granularity of the logic elements, specific fixed and incomplete interconnection topologies are required to prevent the large overhead of a configurable interconnection pattern. To evaluate the potentiality of this new architectural scheme, a specific benchmarking flow will be presented in order to explore the ultra-fine grain architectural design space.

Sample preparation has a critical role as a first step in analytical processes, especially in bioanalysis and environmental analysis. A good sample preparation technique should be robust and stable, regardless of the sample matrix. The aim of this thesis is to design and synthesize molecularly imprinted polymers that can be used in various sample preparation techniques, such as on-line MEPS, on-line SPE and on-line monolithic pre-columns used for the extraction of drugs, hormones, and cancer biomarkers from human plasma and urine samples. Additional aim was to provide full automation, on-line coupling, short sample preparation time and high-throughput. In this thesis MIP in MEPS was used on-line with liquid chromatography-tandem mass spectrometry (LC/MS/MS) for the determination of sarcosine in human urine and plasma samples. The method was fully automated and the packed sorbent could be used for about hundred extractions. In additional work a coated needle with MIP-Sol-Gel as thin layer was prepared and used for the microextraction of bilirubin from human plasma and urine. Small sample volumes could be handled and the validation of the method showed that the method was robust and selective. In a further work MIP-SPE on-line with HPLC was used for the extraction and determination of dextromethorphan in human plasma samples. MIP-SPE showed a good selectivity and high recovery (87% - 92%). On-line MIP monolithic pre-column was prepared and used in a coupled system for the extraction of tramadol in human plasma and urine samples. The MIP monolithic pre-column showed good selectivity and high extraction recovery was obtained (91-96%). The extraction and analysis of human insulin in plasma and pharmaceutical formulation solutions were carried out using MIP-SPE on-line with HPLC. The validation of the method showed that the method was accurate and robust. / <p>At the time of the doctoral defense, the following paper was unpublished and had a status as follows: Paper 5: Submitted.</p>