Non-Target Analysis Using High-Resolution Mass Spectrometry to Characterize and Remediate Urban Waters

The first part of this dissertation will focus on the development of a simple, robust online solid phase extraction liquid chromatography high resolution mass spectrometry (SPE LC-HRMS) method followed by the use of computational software workflows for non-target analysis (NTA) of environmental samples (development). The benchmarks to assess reproducibility are not well defined for non-target analysis. Parameters to evaluate analytical performance, such as accuracy, precision and selectivity, are well defined for target analysis, but remain elusive for non-target screening analysis. In this study, quality control (QC) guidelines are proposed to assure reliable data in NTA methodologies using a simple set of standards. We have specifically evaluated method specificity, precision, accuracy and reproducibility in terms of peak area and retention time variability, true positive identification rate, intraday and interday variations and the use of QC samples to reduce false positives. The second part of this dissertation will focus on the evaluation of different bodies of water in order to characterize different sources (application). Here we have compared electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI) for the detection and identification of organic contaminants in tap and surface waters from South Florida using a combination of Kendrick mass defect (KMD) plots and Van Krevelen diagrams (VKD). This work will lead to the creation of a unique “fingerprint” for each water body that can be used to track water quality and its point of impact. The chemical space coverage of both ESI and APCI for the purpose of non-targeted analysis was explored and documented with respect to the Environmental Protection Agency’s (EPA) ToxCast chemical library. In addition, the performance of the developed NTA workflow was evaluated by analyzing 10 complex mixtures from an inter-laboratory study as part of the EPA’s Non-Targeted Analysis Collaborative Trial (ENTACT). The final part of this dissertation will focus on the development of a simple and inexpensive polydimethylsiloxane (PDMS) sponge composite for the adsorption and removal of pollutants from high flow systems. The work also explores if the polymer can be functionalized with activated charcoal to enhance its adsorption capabilities and copper to deactivate bacteria (remediation). The PDMS sponge composites worked as expected, showing adsorption potential dominated by equilibrium partitioning according to the compounds Log Kow. Adding activated charcoal to the polymer improved its adsorption capabilities. Copper is a biocide and functionalizing the polymer with it deactivated E. coli

Leg Sympathetic Response to Noxious Skin Stimuli is Similar in High and Low Level Human Spinal Cord Injury

Objective To determine if sympathetically mediated vasoconstriction in the lower extremities is injury level dependent. Although sympathetic responses have been measured in the limbs of people with high and low level SCI using blood flow measurements, including Doppler ultrasound and venous plethysmography, a direct comparison between injury levels has not been made. Methods Volunteers with chronic SCI were grouped according to injury level. Above T6: high level (HL, n = 7), and T6 and below: low level (LL, n = 6). All subjects had complete motor and sensory loss. Leg arterial flows were recorded by venous occlusion plethysmography, and continuous heart rate and mean arterial pressure (MAP) were measured. The conditioning stimulus consisted of transcutaneous stimulation to the arch of the contralateral foot. Results HL and LL subjects demonstrated a significant decrease in arterial conductance during stimulation with no significant difference found between groups. As expected, only group HL demonstrated a significant increase in MAP. Conclusions These results support our hypothesis that local (leg) sympathetic responses are similar for both high and low level SCI. Significance While low level SCI does not typically present with autonomic dysreflexia, bouts of increased reflex sympathetic activity could have ramifications for metabolism as well as renal and motor system functio

Leg Sympathetic Response to Noxious Skin Stimuli is Similar in High and Low Level Human Spinal Cord Injury

Objective To determine if sympathetically mediated vasoconstriction in the lower extremities is injury level dependent. Although sympathetic responses have been measured in the limbs of people with high and low level SCI using blood flow measurements, including Doppler ultrasound and venous plethysmography, a direct comparison between injury levels has not been made. Methods Volunteers with chronic SCI were grouped according to injury level. Above T6: high level (HL, n = 7), and T6 and below: low level (LL, n = 6). All subjects had complete motor and sensory loss. Leg arterial flows were recorded by venous occlusion plethysmography, and continuous heart rate and mean arterial pressure (MAP) were measured. The conditioning stimulus consisted of transcutaneous stimulation to the arch of the contralateral foot. Results HL and LL subjects demonstrated a significant decrease in arterial conductance during stimulation with no significant difference found between groups. As expected, only group HL demonstrated a significant increase in MAP. Conclusions These results support our hypothesis that local (leg) sympathetic responses are similar for both high and low level SCI. Significance While low level SCI does not typically present with autonomic dysreflexia, bouts of increased reflex sympathetic activity could have ramifications for metabolism as well as renal and motor system functio

Sintered aluminium heat pipe (SAHP)

This work is the product of an ongoing PhD project in the School of the Built and Natural Environment of Northumbria University in collaboration with the University of Liverpool and Thermacore Europe Ltd. The achievements at the end of the first year are summarized. The main objective of the project is to develop an aluminum ammonia heat pipe with a sintered wick structure. Currently available ammonia heat pipes mainly use extruded axially grooved aluminum tubes as a capillary wick. There have been a few attempts of employing porous steel or nickel wicks in steel tubes with ammonia as the working fluid (Bai, Lin et al. 2009)although it is a common practice in loop heat pipes but there is no report of aluminum-ammonia heat pipes porous aluminium wick structures. The main barrier is the difficulty of sintering aluminum powders to manufacture porous wicks. So far during this project promising sintered aluminum heat pipe samples have been manufactured using the Selective Laser Melting (SLM) technique with various wick characteristics. This SLM method has proven to be capable of manufacturing very complicated wick structures with different thickness, porosity, permeability and pore sizes in different regions of a heat pipe. In addition the entire heat pipe including the end cap, outer tube wall, wick and the fill tube can be generated in a single process

Structural balance emerges and explains performance in risky decision-making.

Polarization affects many forms of social organization. A key issue focuses on which affective relationships are prone to change and how their change relates to performance. In this study, we analyze a financial institutional over a two-year period that employed 66 day traders, focusing on links between changes in affective relations and trading performance. Traders' affective relations were inferred from their IMs (>2 million messages) and trading performance was measured from profit and loss statements (>1 million trades). Here, we find that triads of relationships, the building blocks of larger social structures, have a propensity towards affective balance, but one unbalanced configuration resists change. Further, balance is positively related to performance. Traders with balanced networks have the "hot hand", showing streaks of high performance. Research implications focus on how changes in polarization relate to performance and polarized states can depolarize

Critical Density for Connectivity in 2D and 3D Wireless Multi-Hop Networks

In this paper we investigate the critical node density required to ensure that an arbitrary node in a large-scale wireless multi-hop network is connected (via multi-hop path) to infinitely many other nodes with a positive probability. Specifically we con

FPGA implementation of a predictive vector quantization image compression algorithm for image sensor applications

This paper presents a hybrid image compression scheme based on a block based compression algorithm referred to as Vector Quantization (VQ) combined with the Differential Pulse Code Modulation (DPCM) technique. The proposed image compression technique called the PVQ scheme results in enhanced image quality as compared to the standalone VQ. The generated codebooks for the PVQ scheme are more robust for image coding than that of the VQ. This made our system a suitable candidate for developing on chip image sensor with integrated data compression processor. The proposed system was validated through FPGA implementation. The resulting implementation achieved good compression and image quality with moderate system complexity

Low Levels of p53 Protein and Chromatin Silencing of p53 Target Genes Repress Apoptosis in Drosophila Endocycling Cells

Apoptotic cell death is an important response to genotoxic stress that prevents oncogenesis. It is known that tissues can differ in their apoptotic response, but molecular mechanisms are little understood. Here, we show that Drosophila polyploid endocycling cells (G/S cycle) repress the apoptotic response to DNA damage through at least two mechanisms. First, the expression of all the Drosophila p53 protein isoforms is strongly repressed at a post-transcriptional step. Second, p53-regulated pro-apoptotic genes are epigenetically silenced in endocycling cells, preventing activation of a paused RNA Pol II by p53-dependent or p53-independent pathways. Over-expression of the p53A isoform did not activate this paused RNA Pol II complex in endocycling cells, but over-expression of the p53B isoform with a longer transactivation domain did, suggesting that dampened p53B protein levels are crucial for apoptotic repression. We also find that the p53A protein isoform is ubiquitinated and degraded by the proteasome in endocycling cells. In mitotic cycling cells, p53A was the only isoform expressed to detectable levels, and its mRNA and protein levels increased after irradiation, but there was no evidence for an increase in protein stability. However, our data suggest that p53A protein stability is regulated in unirradiated cells, which likely ensures that apoptosis does not occur in the absence of stress. Without irradiation, both p53A protein and a paused RNA pol II were pre-bound to the promoters of pro-apoptotic genes, preparing mitotic cycling cells for a rapid apoptotic response to genotoxic stress. Together, our results define molecular mechanisms by which different cells in development modulate their apoptotic response, with broader significance for the survival of normal and cancer polyploid cells in mammals

A Bayesian Nonparametric model for textural pattern heterogeneity

Cancer radiomics is an emerging discipline promising to elucidate lesion phenotypes and tumor heterogeneity through patterns of enhancement, texture, morphology, and shape. The prevailing technique for image texture analysis relies on the construction and synthesis of Gray-Level Co-occurrence Matrices (GLCM). Practice currently reduces the structured count data of a GLCM to reductive and redundant summary statistics for which analysis requires variable selection and multiple comparisons for each application, thus limiting reproducibility. In this article, we develop a Bayesian multivariate probabilistic framework for the analysis and unsupervised clustering of a sample of GLCM objects. By appropriately accounting for skewness and zero-inflation of the observed counts and simultaneously adjusting for existing spatial autocorrelation at nearby cells, the methodology facilitates estimation of texture pattern distributions within the GLCM lattice itself. The techniques are applied to cluster images of adrenal lesions obtained from CT scans with and without administration of contrast. We further assess whether the resultant subtypes are clinically oriented by investigating their correspondence with pathological diagnoses. Additionally, we compare performance to a class of machine-learning approaches currently used in cancer radiomics with simulation studies.Comment: 45 pages, 7 figures, 1 Tabl