Improved dynamic headspace sampling and detection using capillary microextraction of volatiles coupled to gas chromatography mass spectrometry

Sampling and preconcentration techniques play a critical role in headspace analysis in analytical chemistry. My dissertation presents a novel sampling design, capillary microextraction of volatiles (CMV), that improves the preconcentration of volatiles and semivolatiles in a headspace with high throughput, near quantitative analysis, high recovery and unambiguous identification of compounds when coupled to mass spectrometry. The CMV devices use sol-gel polydimethylsiloxane (PDMS) coated microglass fibers as the sampling/preconcentration sorbent when these fibers are stacked into open-ended capillary tubes. The design allows for dynamic headspace sampling by connecting the device to a hand-held vacuum pump. The inexpensive device can be fitted into a thermal desorption probe for thermal desorption of the extracted volatile compounds into a gas chromatography-mass spectrometer (GC-MS). The performance of the CMV devices was compared with two other existing preconcentration techniques, solid phase microextraction (SPME) and planar solid phase microextraction (PSPME). Compared to SPME fibers, the CMV devices have an improved surface area and phase volume of 5000 times and 80 times, respectively. One (1) minute dynamic CMV air sampling resulted in similar performance as a 30 min static extraction using a SPME fiber. The PSPME devices have been fashioned to easily interface with ion mobility spectrometers (IMS) for explosives or drugs detection. The CMV devices are shown to offer dynamic sampling and can now be coupled to COTS GC-MS instruments. Several compound classes representing explosives have been analyzed with minimum breakthrough even after a 60 min. sampling time. The extracted volatile compounds were retained in the CMV devices when preserved in aluminum foils after sampling. Finally, the CMV sampling device were used for several different headspace profiling applications which involved sampling a shipping facility, six illicit drugs, seven military explosives and eighteen different bacteria strains. Successful detection of the target analytes at ng levels of the target signature volatile compounds in these applications suggests that the CMV devices can provide high throughput qualitative and quantitative analysis with high recovery and unambiguous identification of analytes.

Boundary : an exploration of architecture's power to mark a boundary

Cities are no longer recognizing their boundaries beyond their legal or political implications. This thesis explored the architecture of a boundary in the design of a structure that visually and symbolically marked the current Miami-Dade County development limit along Krome Avenue. This limit ultimately separates the city from the endangered Everglades ecosystem. Through the examination of ancient boundaries such as Medieval and Renaissance Military fortifications, as well as contemporary interventions such as Steven Holl's "Edge of the City Projects", an architectural vocabulary was developed considering the Double Wall, Bastion, Rampart, and Gate principles. However, rather than considering these principles to defend the city from outside forces, the focus of this exploration is their inversion in order to contain the city by strengthening its periphery visually and symbolically. From this exploration, it was concluded that a successful boundary or limit should be visible and significant. Furthermore, it should serve as an informative and reflective landmark.

Improved Dynamic Headspace Sampling and Detection using Capillary Microextraction of Volatiles Coupled to Gas Chromatography Mass Spectrometry

Sampling and preconcentration techniques play a critical role in headspace analysis in analytical chemistry. My dissertation presents a novel sampling design, capillary microextraction of volatiles (CMV), that improves the preconcentration of volatiles and semivolatiles in a headspace with high throughput, near quantitative analysis, high recovery and unambiguous identification of compounds when coupled to mass spectrometry. The CMV devices use sol-gel polydimethylsiloxane (PDMS) coated microglass fibers as the sampling/preconcentration sorbent when these fibers are stacked into open-ended capillary tubes. The design allows for dynamic headspace sampling by connecting the device to a hand-held vacuum pump. The inexpensive device can be fitted into a thermal desorption probe for thermal desorption of the extracted volatile compounds into a gas chromatography-mass spectrometer (GC-MS). The performance of the CMV devices was compared with two other existing preconcentration techniques, solid phase microextraction (SPME) and planar solid phase microextraction (PSPME). Compared to SPME fibers, the CMV devices have an improved surface area and phase volume of 5000 times and 80 times, respectively. One (1) minute dynamic CMV air sampling resulted in similar performance as a 30 min static extraction using a SPME fiber. The PSPME devices have been fashioned to easily interface with ion mobility spectrometers (IMS) for explosives or drugs detection. The CMV devices are shown to offer dynamic sampling and can now be coupled to COTS GC-MS instruments. Several compound classes representing explosives have been analyzed with minimum breakthrough even after a 60 min. sampling time. The extracted volatile compounds were retained in the CMV devices when preserved in aluminum foils after sampling. Finally, the CMV sampling device were used for several different headspace profiling applications which involved sampling a shipping facility, six illicit drugs, seven military explosives and eighteen different bacteria strains. Successful detection of the target analytes at ng levels of the target signature volatile compounds in these applications suggests that the CMV devices can provide high throughput qualitative and quantitative analysis with high recovery and unambiguous identification of analytes.

Soft power as the new norm: How the Chinese-Russian strategic partnership (soft) balances American hegemony in an era of unipolarity

This study explores how great powers not allied with the United States formulate their grand strategies in a unipolar international system. Specifically, it analyzes the strategies China and Russia have developed to deal with U.S. hegemony by examining how Moscow and Beijing have responded to American intervention in Central Asia. The study argues that China and Russia have adopted a soft balancing strategy of to indirectly balance the United States at the regional level. This strategy uses normative capabilities such as soft power, alternative institutions and regionalization to offset the overwhelming material hardware of the hegemon. The theoretical and methodological approach of this dissertation is neoclassical realism. Chinese and Russian balancing efforts against the United States are based on their domestic dynamics as well as systemic constraints. Neoclassical realism provides a bridge between the internal characteristics of states and the environment which those states are situated. Because China and Russia do not have the hardware (military or economic power) to directly challenge the United States, they must resort to their software (soft power and norms) to indirectly counter American preferences and set the agenda to obtain their own interests. Neoclassical realism maintains that soft power is an extension of hard power and a reflection of the internal makeup of states. The dissertation uses the heuristic case study method to demonstrate the efficacy of soft balancing. Such case studies help to facilitate theory construction and are not necessarily the demonstrable final say on how states behave under given contexts. Nevertheless, it finds that China and Russia have increased their soft power to counterbalance the United States in certain regions of the world, Central Asia in particular. The conclusion explains how soft balancing can be integrated into the overall balance-of-power framework to explain Chinese and Russian responses to U.S. hegemony. It also suggests that an analysis of norms and soft power should be integrated into the study of grand strategy, including both foreign policy and military doctrine.

A hermeneutic phenomenology of graduate education students' understandings of instructor power in a higher education classroom

Higher education is a distribution center of knowledge and economic, social, and cultural power (Cervero & Wilson, 2001). A critical approach to understanding a higher education classroom begins with recognizing the instructor's position of power and authority (Tisdell, Hanley, & Taylor, 2000). The power instructors wield exists mostly unquestioned, allowing for teaching practices that reproduce the existing societal patterns of inequity in the classroom (Brookfield, 2000). ^ The purpose of this hermeneutic phenomenological study was to explore students' experiences with the power of their instructors in a higher education classroom. A hermeneutic phenomenological study intertwines the interpretations of both the participants and the researcher about a lived experience to uncover layers of meaning because the meanings of lived experiences are usually not readily apparent (van Manen, 1990). Fifteen participants were selected using criterion, convenience, and snowball sampling. The primary data gathering method were semi-structured interviews guided by an interview protocol (Creswell, 2003). Data were interpreted using thematic reflection (van Manen, 1990). ^ Three themes emerged from data interpretation: (a) structuring of instructor-student relationships, (b) connecting power to instructor personality, and (c) learning to navigate the terrains of higher education. How interpersonal relationships were structured in a higher education classroom shaped how students perceived power in that higher education classroom. Positive relationships were described using the metaphor of family and a perceived ethic of caring and nurturing by the instructor. As participants were consistently exposed to exercises of instructor power in a higher education classroom, they attributed those exercises of power to particular instructor traits rather than systemic exercises of power. As participants progressed from undergraduate to graduate studies, they perceived the benefits of expertise in content or knowledge development as secondary to expertise in successfully navigating the social, cultural, political, and interpersonal terrains of higher education. Ultimately, participants expressed that higher education is not about what you know; it is about learning how to play the game. Implications for teaching in higher education and considerations for future research conclude the study.^

Optimization of wireless power transfer via magnetic resonance in different media

A wide range of non-destructive testing (NDT) methods for the monitoring the health of concrete structure has been studied for several years. The recent rapid evolution of wireless sensor network (WSN) technologies has resulted in the development of sensing elements that can be embedded in concrete, to monitor the health of infrastructure, collect and report valuable related data. The monitoring system can potentially decrease the high installation time and reduce maintenance cost associated with wired monitoring systems. The monitoring sensors need to operate for a long period of time, but sensors batteries have a finite life span. Hence, novel wireless powering methods must be devised. The optimization of wireless power transfer via Strongly Coupled Magnetic Resonance (SCMR) to sensors embedded in concrete is studied here. First, we analytically derive the optimal geometric parameters for transmission of power in the air. This specifically leads to the identification of the local and global optimization parameters and conditions, it was validated through electromagnetic simulations. Second, the optimum conditions were employed in the model for propagation of energy through plain and reinforced concrete at different humidity conditions, and frequencies with extended Debye's model. This analysis leads to the conclusion that SCMR can be used to efficiently power sensors in plain and reinforced concrete at different humidity levels and depth, also validated through electromagnetic simulations. The optimization of wireless power transmission via SMCR to Wearable and Implantable Medical Device (WIMD) are also explored. The optimum conditions from the analytics were used in the model for propagation of energy through different human tissues. This analysis shows that SCMR can be used to efficiently transfer power to sensors in human tissue without overheating through electromagnetic simulations, as excessive power might result in overheating of the tissue. Standard SCMR is sensitive to misalignment; both 2-loops and 3-loops SCMR with misalignment-insensitive performances are presented. The power transfer efficiencies above 50% was achieved over the complete misalignment range of 0°-90° and dramatically better than typical SCMR with efficiencies less than 10% in extreme misalignment topologies.

Optimization of Wireless Power Transfer via Magnetic Resonance in Different Media

A wide range of non-destructive testing (NDT) methods for the monitoring the health of concrete structure has been studied for several years. The recent rapid evolution of wireless sensor network (WSN) technologies has resulted in the development of sensing elements that can be embedded in concrete, to monitor the health of infrastructure, collect and report valuable related data. The monitoring system can potentially decrease the high installation time and reduce maintenance cost associated with wired monitoring systems. The monitoring sensors need to operate for a long period of time, but sensors batteries have a finite life span. Hence, novel wireless powering methods must be devised. The optimization of wireless power transfer via Strongly Coupled Magnetic Resonance (SCMR) to sensors embedded in concrete is studied here. First, we analytically derive the optimal geometric parameters for transmission of power in the air. This specifically leads to the identification of the local and global optimization parameters and conditions, it was validated through electromagnetic simulations. Second, the optimum conditions were employed in the model for propagation of energy through plain and reinforced concrete at different humidity conditions, and frequencies with extended Debye's model. This analysis leads to the conclusion that SCMR can be used to efficiently power sensors in plain and reinforced concrete at different humidity levels and depth, also validated through electromagnetic simulations. The optimization of wireless power transmission via SMCR to Wearable and Implantable Medical Device (WIMD) are also explored. The optimum conditions from the analytics were used in the model for propagation of energy through different human tissues. This analysis shows that SCMR can be used to efficiently transfer power to sensors in human tissue without overheating through electromagnetic simulations, as excessive power might result in overheating of the tissue. Standard SCMR is sensitive to misalignment; both 2-loops and 3-loops SCMR with misalignment-insensitive performances are presented. The power transfer efficiencies above 50% was achieved over the complete misalignment range of 0°-90° and dramatically better than typical SCMR with efficiencies less than 10% in extreme misalignment topologies.

Improved sampling and detection of ignitable liquid residues and explosives by mass spectrometry and ion mobility spectrometry

Fire debris evidence is submitted to crime laboratories to determine if an ignitable liquid (IL) accelerant was used to commit arson. An ignitable liquid residue (ILR) may be difficult to analyze due to interferences, complex matrices, degradation, and low concentrations of analytes. Debris from an explosion and pre-detonated explosive compounds are not trivial to detect and identify due to sampling difficulties, complex matrices, and extremely low amounts (nanogram) of material present. The focus of this research is improving the sampling and detection of ILR and explosives through enhanced sensitivity, selectivity, and field portable instrumentation. Solid Phase MicroExtraction (SPME) enhanced the extraction of ILR by two orders of magnitude over conventional activated charcoal strip (ACS) extraction. Gas chromatography tandem mass spectrometry (GC/MS/MS) improved sensitivity of ILR by one order of magnitude and explosives by two orders of magnitude compared to gas chromatography mass spectrometry (GC/MS). Improvements in sensitivity were attributed to enhanced selectivity. An interface joining SPME to ion mobility spectrometry (IMS) has been constructed and evaluated to improve field detection of hidden explosives. The SPME-IMS interface improved the detection of volatile and semi-volatile explosive compounds and successfully adapted the IMS from a particle sampler into a vapor sampler. ^

Seizure detection in subdural recordings using nonlinear decision functions

This dissertation proposed a new approach to seizure detection in intracranial EEG recordings using nonlinear decision functions. It implemented well-established features that were designed to deal with complex signals such as brain recordings, and proposed a 2-D domain of analysis. Since the features considered assume both the time and frequency domains, the analysis was carried out both temporally and as a function of different frequency ranges in order to ascertain those measures that were most suitable for seizure detection. In retrospect, this study established a generalized approach to seizure detection that works across several features and across patients. ^ Clinical experiments involved 8 patients with intractable seizures that were evaluated for potential surgical interventions. A total of 35 iEEG data files collected were used in a training phase to ascertain the reliability of the formulated features. The remaining 69 iEEG data files were then used in the testing phase. ^ The testing phase revealed that the correlation sum is the feature that performed best across all patients with a sensitivity of 92% and an accuracy of 99%. The second best feature was the gamma power with a sensitivity of 92% and an accuracy of 96%. In the frequency domain, all of the 5 other spectral bands considered, revealed mixed results in terms of low sensitivity in some frequency bands and low accuracy in other frequency bands, which is expected given that the dominant frequencies in iEEG are those of the gamma band. In the time domain, other features which included mobility, complexity, and activity, all performed very well with an average a sensitivity of 80.3% and an accuracy of 95%. ^ The computational requirement needed for these nonlinear decision functions to be generated in the training phase was extremely long. It was determined that when the duration dimension was rescaled, the results improved and the convergence rates of the nonlinear decision functions were reduced dramatically by more than a 100 fold. Through this rescaling, the sensitivity of the correlation sum improved to 100% and the sensitivity of the gamma power to 97%, which meant that there were even less false negatives and false positives detected. ^

Disparities in Teacher Certification

The United States Constitution did not give the federal government the power to regulate education. Consequently there is a lack of cohesion and standardization within the United States in teacher certification. The differences and quantity of teacher training and certification leads to inconsistency in teacher certification.

ALBA: A Political Tool for Venezuela’s Foreign Policy

Despite its founding by Hugo Chávez on the heels of the failed Free Trade Area for the Americas (FTAA) negotiations which took place November 2003, the Bolivarian Alliance for the Americas (ALBA, as it is known for its Spanish acronym) has evolved into a political tool that uses “social power” to facilitate Venezuela‟s positioning as the leader of the anti-U.S. agenda in the region. Fostering political favors and goodwill through the financing of social development projects, ALBA has created a political environment whereby countries on the take and their respective leaders seem deterred from taking public opposing viewpoints to Chávez. To that end, it has provided billions in economic aid to several nations in Latin American and the Caribbean, winning their favor and support for its policies. To date, ALBA counts on eight member nations. Besides Venezuela, it includes Antigua and Barbuda, Bolivia, Cuba, Dominica, Ecuador, Nicaragua, and Saint Vincent and the Grenadines. It also has several observer nations, among them, Grenada, Haiti, Paraguay, Uruguay, and a non-Latin American country, Syria. Throughout its recent history Venezuela has used its oil wealth to pursue political capital. Under the Chávez government it is doing so as part of a strategic effort countering the U.S. Following Cuba‟s demise in the region as the anti-American socialist camp leader, Chávez is attempting to step into Cuba‟s shoes, picking up where Cuba left off over a decade ago and has used the ALBA as a mechanism to help promote his foreign policy. Relying on its own resources, not those of the Soviet Union as Cuba once did, Venezuela has already shown its influence in the international arena, challenging U.S. positions at the Organization of American States (OAS), the United Nations, and even in matters having little if nothing to do with the region, such as Iran‟s nuclear proliferation. Taking advantage of Venezuela‟s oil prices bonanza, Chávez has been spreading economic aid throughout the region, funding several development projects. From stepping in to buy Bolivia‟s soy beans when the U.S. ceased doing so, to helping finance and construct an airport in Dominica, Venezuela‟s ALBA has provided assistance to many states in the region. As in the past, Venezuela has invested significantly both in time and money in the Caribbean, providing development assistance and oil at a discount to Haiti, St. Kitts and Nevis, and the Dominican Republic, although the latter two are neither member nor observer states of ALBA. The aid Chávez has been spreading around may be coming at a cost. It seems it has begun to cause cracks within the CARICOM community, where ALBA already counts on six of its 15 members, leading experts and leaders in the region to question traditional alliances to each other and the U.S. Yet, ALBA‟s ability to influence through aid is dependent on the Venezuelan economy. Its success hinges on continued Venezuelan oil sales at stable prices and the ability of Chávez to remain in power.

Emergence and Fate of Siloxanes in Waste Streams: Release Mechanisms, Partitioning and Persistence in Three Environmental Compartments

Siloxanes are widely used in personal care and industrial products due to their low surface tension, thermal stability, antimicrobial and hydrophobic properties, among other characteristics. Volatile methyl siloxanes (VMS) have been detected both in landfill gas and biogas from anaerobic digesters at wastewater treatment plants. As a result, they are released to gas phase during waste decomposition and wastewater treatment. During transformation processes of digester or landfill gas to energy, siloxanes are converted to silicon oxides, leaving abrasive deposits on engine components. These deposits cause increased maintenance costs and in some cases complete engine overhauls become necessary. The objectives of this study were to compare the VMS types and levels present in biogas generated in the anaerobic digesters and landfills and evaluate the energetics of siloxane transformations under anaerobic conditions. Siloxane emissions, resulting from disposal of silicone-based materials, are expected to increase by 29% within the next 10 years. Estimated concentrations and the risk factors of exposure to siloxanes were evaluated based on the initial concentrations, partitioning characteristics and persistence. It was determined that D4 has the highest risk factor associated to bioaccumulation in liquid and solid phase, whereas D5 was highest in gas phase. Additionally, as siloxanes are combusted, the particle size range causes them to be potentially hazardous to human health. When inhaled, they may affix onto the alveoli of the lungs and may lead to development of silicosis. Siloxane-based COD-loading was evaluated and determined to be an insignificant factor concerning COD limits in wastewater. Removal of siloxane compounds is recommended prior to land application of biosolids or combustion of biogas. A comparison of estimated costs was made between maintenance practices for removal of siloxane deposits and installation/operation of fixed-bed carbon absorption systems. In the majority of cases, the installation of fixed-bed adsorption systems would not be a feasible option for the sole purpose of siloxane removal. However they may be utilized to remove additional compounds simultaneously.

Docking and simulation study of the enantiospecificity of chiral epoxidation reactions catalyzed by chloroperoxidase

Chloroperoxidase (CPO), a 298-residue glycosylated protein from the fungus Caldariomyces fumago, is probably the most versatile heme enzyme yet discovered. Interest in CPO as a catalyst is based on its power to produce enantiomerically enriched products. Recent research has focused its attention on the ability of CPO to epoxidize alkenes in high regioselectivity and enantioselectivity as an efficient and environmentally benign alternative to traditional synthetic routes. There has been little work on the nature of ligand binding, which probably controls the regio- and enantiospecifity of CPO. Consequently it is here that we focus our work. We report docking calculations and computer simulations aimed at predicting the enantiospecificity of CPO-catalyzed epoxidation of three model substrates. On the basis of this work candidate mutations to improve the efficiency of CPO are predicted. In order to accomplish these aims, a simulated annealing and molecular dynamics protocol is developed to sample potentially reactive substrate/CPO complexes.

Emergence and fate of siloxanes in waste streams: Release mechanisms, partitioning and persistence in three environmental compartments

Siloxanes are widely used in personal care and industrial products due to their low surface tension, thermal stability, antimicrobial and hydrophobic properties, among other characteristics. Volatile methyl siloxanes (VMS) have been detected both in landfill gas and biogas from anaerobic digesters at wastewater treatment plants. As a result, they are released to gas phase during waste decomposition and wastewater treatment. During transformation processes of digester or landfill gas to energy, siloxanes are converted to silicon oxides, leaving abrasive deposits on engine components. These deposits cause increased maintenance costs and in some cases complete engine overhauls become necessary. ^ The objectives of this study were to compare the VMS types and levels present in biogas generated in the anaerobic digesters and landfills and evaluate the energetics of siloxane transformations under anaerobic conditions. Siloxane emissions, resulting from disposal of silicone-based materials, are expected to increase by 29% within the next 10 years. Estimated concentrations and the risk factors of exposure to siloxanes were evaluated based on the initial concentrations, partitioning characteristics and persistence. It was determined that D4 has the highest risk factor associated to bioaccumulation in liquid and solid phase, whereas D5 was highest in gas phase. Additionally, as siloxanes are combusted, the particle size range causes them to be potentially hazardous to human health. When inhaled, they may affix onto the alveoli of the lungs and may lead to development of silicosis. Siloxane-based COD-loading was evaluated and determined to be an insignificant factor concerning COD limits in wastewater. ^ Removal of siloxane compounds is recommended prior to land application of biosolids or combustion of biogas. A comparison of estimated costs was made between maintenance practices for removal of siloxane deposits and installation/operation of fixed-bed carbon absorption systems. In the majority of cases, the installation of fixed-bed adsorption systems would not be a feasible option for the sole purpose of siloxane removal. However they may be utilized to remove additional compounds simultaneously.^