Method development for the analysis of smokeless powders and organic gunshot residue by ultra performance liquid chromatography with tandem mass spectrometry

The goal of this project was to develop a rapid separation and detection method for analyzing organic compounds in smokeless powders and then test its applicability on gunshot residue (GSR) samples. In this project, a total of 20 common smokeless powder additives and their decomposition products were separated by ultra performance liquid chromatography (UPLC) and confirmed by tandem mass spectrometry (MS/MS) using multiple reaction monitoring mode (MRM). Some of the targeted compounds included diphenylamines, centralites, nitrotoluenes, nitroglycerin, and various phthalates. The compounds were ionized in the MS source using simultaneous positive and negative electrospray ionization (ESI) with negative atmospheric pressure chemical ionization (APCI) in order to detect all compounds in a single analysis. The developed UPLC/MS/MS method was applied to commercially available smokeless powders and gunshot residue samples recovered from the hands of shooters, spent cartridges, and smokeless powder retrieved from unfired cartridges. Distinct compositions were identified for smokeless powders from different manufacturers and from separate manufacturing lots. The procedure also produced specific chemical profiles when tested on gunshot residues from different manufacturers. Overall, this thesis represents the development of a rapid and reproducible procedure capable of simultaneously detecting the widest possible range of components present in organic gunshot residue.^

Speciation, metabolism, toxicity, and protein-binding of different arsenic species in human cells

Despite of its known toxicity and potential to cause cancer, arsenic has been proven to be a very important tool for the treatment of various refractory neoplasms. One of the promising arsenic-containing chemotherapeutic agents in clinical trials is Darinaparsin (dimethylarsinous glutathione, DMA III(GS)). In order to understand its toxicity and therapeutic efficacy, the metabolism of Darinaparsin in human cancer cells was evaluated. With the aim of detecting all potential intermediates and final products of the biotransformation of Darinaparsin and other arsenicals, an analytical method employing high performance liquid chromatography inductively coupled mass spectrometry (HPLC-ICP-MS) was developed. This method was shown to be capable of separating and detecting fourteen human arsenic metabolites in one chromatographic run. The developed analytical technique was used to evaluate the metabolism of Darinaparsin in human cancer cells. The major metabolites of Darinaparsin were identified as dimethylarsinic acid (DMAV), DMA III(GS), and dimethylarsinothioyl glutathione (DMMTAV(GS)). Moreover, the method was employed to study the conditions and mechanisms of formation of thiol-containing arsenic metabolites from DMAIII(GS) and DMAV as the mechanisms of formation of these important As species were unknown. The arsenic sulfur compounds studied included but were not limited to the newly discovered human arsenic metabolite DMMTA V(GS) and the unusually highly toxic dimethylmonothioarsinic acid (DMMTAV). It was found that these species may form from hydrogen sulfide produced in enzymatic reactions or by utilizing the sulfur present in protein persulfides. Possible pathways of thiolated arsenical formation were proposed and supporting data for their existence provided. In addition to known mechanism of arsenic toxicity such as protein-binding and reactive oxygen formation, it was proposed that the utilization of thiols from protein persulfides during the formation of thiolated arsenicals may be an additional mechanism of toxicity. The toxicities of DMAV(GS), DMMTA V, and DMMTAV(GS) were evaluated in cancer cells, and the ability of these cells to take the compounds up were compared. When assessing the toxicity by exposing multiple myeloma cells to arsenicals externally, DMMTAV(GS) was much less toxic than DMAIII(GS) and DMMTAV, probably as a result of its very limited uptake (less than 10% and 16% of DMAIII(GS) and DMMTAV respectively).^

Design, development and control of a new generation high performance linear actuator for parallel robots and other applications

The main focus of this research is to design and develop a high performance linear actuator based on a four bar mechanism. The present work includes the detailed analysis (kinematics and dynamics), design, implementation and experimental validation of the newly designed actuator. High performance is characterized by the acceleration of the actuator end effector. The principle of the newly designed actuator is to network the four bar rhombus configuration (where some bars are extended to form an X shape) to attain high acceleration. Firstly, a detailed kinematic analysis of the actuator is presented and kinematic performance is evaluated through MATLAB simulations. A dynamic equation of the actuator is achieved by using the Lagrangian dynamic formulation. A SIMULINK control model of the actuator is developed using the dynamic equation. In addition, Bond Graph methodology is presented for the dynamic simulation. The Bond Graph model comprises individual component modeling of the actuator along with control. Required torque was simulated using the Bond Graph model. Results indicate that, high acceleration (around 20g) can be achieved with modest (3 N-m or less) torque input. A practical prototype of the actuator is designed using SOLIDWORKS and then produced to verify the proof of concept. The design goal was to achieve the peak acceleration of more than 10g at the middle point of the travel length, when the end effector travels the stroke length (around 1 m). The actuator is primarily designed to operate in standalone condition and later to use it in the 3RPR parallel robot. A DC motor is used to operate the actuator. A quadrature encoder is attached with the DC motor to control the end effector. The associated control scheme of the actuator is analyzed and integrated with the physical prototype. From standalone experimentation of the actuator, around 17g acceleration was achieved by the end effector (stroke length was 0.2m to 0.78m). Results indicate that the developed dynamic model results are in good agreement. Finally, a Design of Experiment (DOE) based statistical approach is also introduced to identify the parametric combination that yields the greatest performance. Data are collected by using the Bond Graph model. This approach is helpful in designing the actuator without much complexity.

High-resolution pore-water and solid-phase analyses of sediment cores GeoB6520-3 (Hydrate Hole) and GeoB6521-2 (Worm Hole) of the northern Congo Fan

The geochemical cycling of barium was investigated in sediments of pockmarks of the northern Congo Fan, characterized by surface and subsurface gas hydrates, chemosynthetic fauna, and authigenic carbonates. Two gravity cores retrieved from the so-called Hydrate Hole and Worm Hole pockmarks were examined using high-resolution pore-water and solid-phase analyses. The results indicate that, although gas hydrates in the study area are stable with respect to pressure and temperature, they are and have been subject to dissolution due to methane-undersaturated pore waters. The process significantly driving dissolution is the anaerobic oxidation of methane (AOM) above the shallowest hydrate-bearing sediment layer. It is suggested that episodic seep events temporarily increase the upward flux of methane, and induce hydrate formation close to the sediment surface. AOM establishes at a sediment depth where the upward flux of methane from the uppermost hydrate layer counterbalances the downward flux of seawater sulfate. After seepage ceases, AOM continues to consume methane at the sulfate/methane transition (SMT) above the hydrates, thereby driving the progressive dissolution of the hydrates "from above". As a result the SMT migrates downward, leaving behind enrichments of authigenic barite and carbonates that typically precipitate at this biogeochemical reaction front. Calculation of the time needed to produce the observed solid-phase barium enrichments above the present-day depths of the SMT served to track the net downward migration of the SMT and to estimate the total time of hydrate dissolution in the recovered sediments. Methane fluxes were higher, and the SMT was located closer to the sediment surface in the past at both sites. Active seepage and hydrate formation are inferred to have occurred only a few thousands of years ago at the Hydrate Hole site. By contrast, AOM-driven hydrate dissolution as a consequence of an overall net decrease in upward methane flux seems to have persisted for a considerably longer time at the Worm Hole site, amounting to a few tens of thousands of years.

Beyond Winning and Losing: Guidelines for Evaluating High Performance Coaches

This paper proposes a three-step method of evaluating high performance coaches involving feedback from the athletes. First, data are collected using an instrument such as the Coaching Behavior Scale for Sport (CBS-S: Côté, Yardley, Hay, Sedgwick, & Baker, 1999). Second, a summary report is prepared with descriptive information regarding the frequency of behaviors demonstrated by the coach that can be compared to previous results or to a criterion measure. The third step involves appropriate personnel reviewing the report and subsequently providing guidance for individual coach development. This three-step appraisal method provides useful evaluative feedback to coaches and has been used in several sport programs in Canada, the United States, and Australia.

Applied Research Sport Experiences, Milestones, and Educational Activities Associated With High-Performance Coaches' Development

What experiences are needed to become a high-performance coach? The present study addressed this question through structured retrospective quantitative interviews with 10 team- and 9 individual-sport coaches at the Canadian interuniversity-sport level. Minimum amounts of certain experiences were deemed necessary but not sufficient to become a high-performance coach (e.g., playing the sport they now coach and interaction with a mentor coach for all coaches, leadership opportunities as athletes for team-sport coaches only). Although coaches reported varying amounts of these necessary experiences, general stages of high-performance coach development were traced. Findings serve to identify and support potential high-performance coaches and increase the effectiveness of formal coaching-education programs.

The Organizational Tasks of High-Performance Gymnastic Coaches

The purpose of this study was to report the knowledge used by expert high performance gymnastic coaches in the organization of training and competition. In-depth interviews were conducted with 9 coaches who worked with male gymnasts and 8 coaches who worked with female gymnasts. Qualitative analyses showed that coaches of males and coaches of females planned training similarly, except that coaches of females appeared to emphasize esthetic and nutritional issues to a greater extent. Coaches of males revealed more concerns about the organization of gymnasts' physical conditioning. Analysis indicated that expert gymnastic coaches of males and females are constantly involved in dynamic social interactions with gymnasts, parents, and assistant coaches. Many areas of coaches' organizational work, such as dealing with the athletes' personal concerns and working with parents, are not part of the structure of coaches' training programs and emerged as crucial tasks of expert gymnastic coaches for developing elite gymnasts.

The Knowledge of High-Performance Gymnastic Coaches : Competition and Training Considerations

The purpose of this study is to report the knowledge used in training and competition by 17 expert high-performance gymnastic coaches. A qualitative research methodology was used to collect and inductively analyze the data. The knowledge elicited for the competition component was categorized as competition site, competition floor, and trial competitions. These categories indicated that the coaches are minimally involved with the gymnasts in competition. The knowledge of the coaches elicited within the training component were categorized as coach involvement in training, intervention style, technical skills, mental skills, and simulation. Properties of these categories that were extensively discussed by the expert coaches, such as teaching progressions, being supportive, and helping athletes to deal with stress,are consistent with the literature on coaching and on sport psychology. Other aspects considered important in the sport psychology literature, such as developing concentration skills, were not discussed as thoroughly by the expert coaches.

Underway spectrophotometry along the Atlantic Meridional Transect reveals high performance in satellite chlorophyll retrievals

To evaluate the performance of ocean-colour retrievals of total chlorophyll-a concentration requires direct comparison with concomitant and co-located in situ data. For global comparisons, these in situ match-ups should be ideally representative of the distribution of total chlorophyll-a concentration in the global ocean. The oligotrophic gyres constitute the majority of oceanic water, yet are under-sampled due to their inaccessibility and under-represented in global in situ databases. The Atlantic Meridional Transect (AMT) is one of only a few programmes that consistently sample oligotrophic waters. In this paper, we used a spectrophotometer on two AMT cruises (AMT19 and AMT22) to continuously measure absorption by particles in the water of the ship's flow-through system. From these optical data continuous total chlorophyll-a concentrations were estimated with high precision and accuracy along each cruise and used to evaluate the performance of ocean-colour algorithms. We conducted the evaluation using level 3 binned ocean-colour products, and used the high spatial and temporal resolution of the underway system to maximise the number of match-ups on each cruise. Statistical comparisons show a significant improvement in the performance of satellite chlorophyll algorithms over previous studies, with root mean square errors on average less than half (~ 0.16 in log10 space) that reported previously using global datasets (~ 0.34 in log10 space). This improved performance is likely due to the use of continuous absorption-based chlorophyll estimates, that are highly accurate, sample spatial scales more comparable with satellite pixels, and minimise human errors. Previous comparisons might have reported higher errors due to regional biases in datasets and methodological inconsistencies between investigators. Furthermore, our comparison showed an underestimate in satellite chlorophyll at low concentrations in 2012 (AMT22), likely due to a small bias in satellite remote-sensing reflectance data. Our results highlight the benefits of using underway spectrophotometric systems for evaluating satellite ocean-colour data and underline the importance of maintaining in situ observatories that sample the oligotrophic gyres.

Underway spectrophotometry along the Atlantic Meridional Transect reveals high performance in satellite chlorophyll retrievals

To evaluate the performance of ocean-colour retrievals of total chlorophyll-a concentration requires direct comparison with concomitant and co-located in situ data. For global comparisons, these in situ match-ups should be ideally representative of the distribution of total chlorophyll-a concentration in the global ocean. The oligotrophic gyres constitute the majority of oceanic water, yet are under-sampled due to their inaccessibility and under-represented in global in situ databases. The Atlantic Meridional Transect (AMT) is one of only a few programmes that consistently sample oligotrophic waters. In this paper, we used a spectrophotometer on two AMT cruises (AMT19 and AMT22) to continuously measure absorption by particles in the water of the ship's flow-through system. From these optical data continuous total chlorophyll-a concentrations were estimated with high precision and accuracy along each cruise and used to evaluate the performance of ocean-colour algorithms. We conducted the evaluation using level 3 binned ocean-colour products, and used the high spatial and temporal resolution of the underway system to maximise the number of match-ups on each cruise. Statistical comparisons show a significant improvement in the performance of satellite chlorophyll algorithms over previous studies, with root mean square errors on average less than half (~ 0.16 in log10 space) that reported previously using global datasets (~ 0.34 in log10 space). This improved performance is likely due to the use of continuous absorption-based chlorophyll estimates, that are highly accurate, sample spatial scales more comparable with satellite pixels, and minimise human errors. Previous comparisons might have reported higher errors due to regional biases in datasets and methodological inconsistencies between investigators. Furthermore, our comparison showed an underestimate in satellite chlorophyll at low concentrations in 2012 (AMT22), likely due to a small bias in satellite remote-sensing reflectance data. Our results highlight the benefits of using underway spectrophotometric systems for evaluating satellite ocean-colour data and underline the importance of maintaining in situ observatories that sample the oligotrophic gyres.

Molecular Characterization of Three Novel Phospholipase A2 Proteins from the Venom of Atheris chlorechis, Atheris nitschei and Atheris squamigera

Secretory phospholipase A2 (sPLA2) is known as a major component of snake venoms and displays higher-order catalytic hydrolysis functions as well as a wide range of pathological effects. Atheris is not a notoriously dangerous genus of snakes although there are some reports of fatal cases after envenomation due to the effects of coagulation disturbances and hemorrhaging. Molecular characterization of Atheris venom enzymes is incomplete and there are only a few reports in the literature. Here, we report, for the first time, the cloning and characterization of three novel cDNAs encoding phospholipase A2 precursors (one each) from the venoms of the Western bush viper (Atheris chlorechis), the Great Lakes bush viper (Atheris nitschei) and the Variable bush viper (Atheris squamigera), using a “shotgun cloning” strategy. Open-reading frames of respective cloned cDNAs contained putative 16 residue signal peptides and mature proteins composed of 121 to 123 amino acid residues. Alignment of mature protein sequences revealed high degrees of structural conservation and identity with Group II venom PLA2 proteins from other taxa within the Viperidae. Reverse-phase High Performance Liquid Chromatography (HPLC) profiles of these three snake venoms were obtained separately and chromatographic fractions were assessed for phospholipase activity using an egg yolk suspension assay. The molecular masses of mature proteins were all identified as approximately 14 kDa. Mass spectrometric analyses of the fractionated oligopeptides arising from tryptic digestion of intact venom proteins, was performed for further structural characterization.

Characterization of High-Performance Organic Dyes for Dye-Sensitized Solar Cell: A DFT/TDDFT Study

Dye-sensitized solar cell (DSSC) is currently a promising technology that makes solar energy efficient and cost-effective to harness. In DSSC, metal free dyes, such indoline-containing D149 and D205, are proved to be potential alternatives for traditional metal organic dyes. In this work, a DFT/TDDFT characterization for D149 and D205 were carried out using different functionals, including B3LYP, MPW1K, CAM-B3LYP and PBE0. Three different conformers for D149 and four different conformers for D205 were identified and calculated in vacuum. The performance of different functionals on calculating the maximum absorbance of the dyes in vacuum and five common solvents (acetonitrile, chloroform, ethanol, methanol, and THF) were examined and compared to determine the suitable computational setting for predicting properties of these two dyes. Furthermore, deprotonated D149 and D205 in solvents were also considered, and the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) were calculated, which elucidates the substitution effect on the rhodanine ring of D149 and D205 dyes on their efficiency. Finally, D149 and D205 molecules were confirmed to be firmly anchored on ZnO surface by periodic DFT calculations. These results would shed light on the design of new highly efficiency metal-free dyes.

A simply effective double-coating cathode with MnO2 nanosheets/graphene as functionalized interlayer for high performance lithium-sulfur batteries

Herein, we report a facile and effective adsorption strategy to improve the performance of Lithium-Sulfur (Li-S) batteries. MnO₂ nanosheets grown on the surface of highly conductive graphene resulted in a coupled composite bilayer electrode when coated onto a sulfur cathode. In this way, a high initial specific capacity of 1395 mA h g^-1 at a rate of 0.5C, a coulombic efficiency approaching 100% and steady cyclic efficiency with a fade rate of 0.3% per cycle from 10 to 100 cycles has been achieved. This hybrid electrode not only shows enhanced electrochemical performance but can also be easily controlled and scaled thereby aiding future commercialization of high-performance Li-S batteries.

High performance cobalt-free Cu1.4Mn1.6O4 spinel oxide as an intermediate temperature solid oxide fuel cell cathode

In this work Cu_1.4Mn_1.6O₄ (CMO) spinel oxide is prepared and evaluated as a novel cobalt-free cathode for intermediate temperature solid oxide fuel cells (IT-SOFCs). Single phase CMO powder with cubic structure is identified using XRD. XPS results confirm that mixed Cu⁺/Cu²⁺ and Mn³⁺/Mn⁴⁺ couples exist in the CMO sample, and a maximum conductivity of 78 S cm⁻¹ is achieved at 800 °C. Meanwhile, CMO oxide shows good thermal and chemical compatibility with a 10 mol% Sc₂O₃ stabilized ZrO₂ (ScSZ) electrolyte material. Impedance spectroscopy measurements reveals that CMO exhibits a low polarization resistance of 0.143 Ω cm² at 800 °C. Furthermore, a Ni-ScSZ/ScSZ/CMO single cell demonstrates a maximum power density of 1076 mW cm⁻² at 800 °C under H₂ (3% H₂O) as the fuel and ambient air as the oxidant. These results indicate that Cu_1.4Mn_1.6O₄ is a superior and promising cathode material for IT-SOFCs.

High-Performance WSe2 CMOS Technology and Integrated Circuits.

Because of their extraordinary structural and electrical properties, two dimensional materials are currently being pursued for applications such as thin-film transistors and integrated circuit. One of the main challenges that still needs to be overcome for these applications is the fabrication of air-stable transistors with industry-compatible complementary metal oxide semiconductor (CMOS) technology. In this work, we experimentally demonstrate a novel high performance air-stable WSe2 CMOS technology with almost ideal voltage transfer characteristic, full logic swing and high noise margin with different supply voltages. More importantly, the inverter shows large voltage gain (~38) and small static power (Pico-Watts), paving the way for low power electronic system in 2D materials.