The utilization of chiral ion mobility spectrometry for the detection of enantiomeric mixtures and thermally labile compounds

This dissertation utilized electrospray ion mobility mass spectrometry (ESI-IMS-MS) to develop methods necessary for the separation of chiral compounds of forensic interest. The compounds separated included ephedrines and pseudoephedrines, that occur as impurities in confiscated amphetamine type substances (ATS) in an effort to determine the origin of these substances. The ESI-IMS-MS technique proved to be faster and more cost effective than traditional chromatographic methods currently used to conduct chiral separations such as gas and liquid chromatography. Both mass spectrometric and computational analysis revealed the separation mechanism of these chiral interactions allowing for further development to separate other chiral compounds by IMS. Successful separation of chiral compounds was achieved utilizing a variety of modifiers injected into the IMS drift tube. It was found that the modifiers themselves did not need to be chiral in nature and that achiral modifiers were sufficient in performing the required separations. The ESI-IMS-MS technique was also used to detect thermally labile compounds which are commonly found in explosive substances. The methods developed provided mass spectrometric identification of the type of ionic species being detected from explosive analytes as well as the appropriate solvent that enhances detection of these analytes in either the negative or positive ion mode. An application of the developed technique was applied to the analysis of a variety of low explosive smokeless powder samples. It was found that the developed ESI-IMS-MS technique not only detected the components of the smokeless powders, but also provided data that allowed the classification of the analyzed smokeless powders by manufacturer or make. ^

The Effects of the Use of Technology In Mathematics Instruction on Student Achievement

The purpose of this study was to examine the effects of the use of technology on students’ mathematics achievement, particularly the Florida Comprehensive Assessment Test (FCAT) mathematics results. Eleven schools within the Miami-Dade County Public School System participated in a pilot program on the use of Geometers Sketchpad (GSP). Three of these schools were randomly selected for this study. Each school sent a teacher to a summer in-service training program on how to use GSP to teach geometry. In each school, the GSP class and a traditional geometry class taught by the same teacher were the study participants. Students’ mathematics FCAT results were examined to determine if the GSP produced any effects. Students’ scores were compared based on assignment to the control or experimental group as well as gender and SES. SES measurements were based on whether students qualified for free lunch. The findings of the study revealed a significant difference in the FCAT mathematics scores of students who were taught geometry using GSP compared to those who used the traditional method. No significant differences existed between the FCAT mathematics scores of the students based on SES. Similarly, no significant differences existed between the FCAT scores based on gender. In conclusion, the use of technology (particularly GSP) is likely to boost students’ FCAT mathematics test scores. The findings also show that the use of GSP may be able to close known gender and SES related achievement gaps. The results of this study promote policy changes in the way geometry is taught to 10th grade students in Florida’s public schools.

A geometria do compasso (1797) de Mascheroni (1750 – 1800) em atividades com o GeoGebra

The present work aims to show a possible relationship between the use of the History of Mathematics and Information and Communication Technologies (TIC) in teaching Mathematics through activities that use geometric constructions of the “Geometry of the Compass” (1797) by Lorenzo Mascheroni (1750-1800). For this, it was performed a qualitative research characterized by an historical exploration of bibliographical character followed by an empirical intervention based on use of the History of Mathematics combined with TIC through Mathematical Investigation. Thus, studies were performed in papers dealing with the topic, as well as a survey to highlight problems and /or episodes of the history of mathematics that can be solved with the help of TIC, allowing the production of a notebook of activities addressing the resolution of historical problems in a computer environment. In this search, we came across the problems of geometry that are presented by Mascheroni stated previously in the work that we propose solutions and investigations using GeoGebra software. The research resulted in the elaboration of an educational product, a notebook of activities, which was structure to allow during its implementation, students can conduct historical and/or Mathematics research, therefore, we present the procedures for realization of each construction, followed at some moments by original solution of the work. At the same time, we encourage students to investigate/reflect its construction (GeoGebra), in addition to making comparisons with the solution Mascheroni. This notebook was applied to two classes of the course of Didactics of Mathematics I (MAT0367) Course in Mathematics UFRN in 2014. Knowing the existence of some unfavorable arguments regarding the use of history of mathematics, such as loss of time, it was found that this factor can be mitigated with the aid of computational resource, because we can make checks using only the dynamism of and software without repeating the construction. It is noteworthy that the minimized time does not mean loss of reflection or maturation of ideas, when we adopted the process of historical and/or Mathematics Investigation

Uso de metamaterial em antenas de microfita com supercondutor

Metamaterials have attracted great attention in recent decades, due to their electromagnetic properties which are not found in nature. Since metamaterials are now synthesized by the insertion of artificially manufactured inclusions in a specified homogeneous medium, it became possible for the researcher to work with a wide collection of independent parameters, for example, the electromagnetic properties of the material. An investigation of the properties of ring resonators was performed as well as those of metamaterials. A study of the major theories that clearly explain superconductivity was presented. The BCS theory, London Equations and the Two-Fluid Model are theories that support the application of superconducting microstrip antennas. Therefore, this thesis presents theoretical, numerical and experimental-computational analysis using full-wave formalism, through the application of the Transverse Transmission Line – LTT method applied in the Fourier Transform Domain (FTD). The LTT is a full wave method, which, as a rule, obtains the electromagnetic fields in terms of the transverse components of the structure. The inclusion of the superconducting patch is performed using the complex resistive boundary condition. Results of resonant frequency as a function of antenna parameters are obtained. To validate the analysis, computer programs were developed using Fortran, simulations were created using the commercial software, with curves being drawn using commercial software and MATLAB, in addition to comparing the conventional patch with the superconductor as well as comparing a metamaterial substrate with a conventional one, joining the substrate with the patch, observing what improves on both cas

Modelagem multiescala de fenômenos eletrocinéticos em meios porosos carregados eletricamente: aplicação a meios porosos argilosos

In this master thesis, we propose a multiscale mathematical and computational model for electrokinetic phenomena in porous media electrically charged. We consider a porous medium rigid and incompressible saturated by an electrolyte solution containing four monovalent ionic solutes completely diluted in the aqueous solvent. Initially we developed the modeling electrical double layer how objective to compute the electrical potential, surface density of electrical charges and considering two chemical reactions, we propose a 2-pK model for calculating the chemical adsorption occurring in the domain of electrical double layer. Having the nanoscopic model, we deduce a model in the microscale, where the electrochemical adsorption of ions, protonation/ deprotonation reactions and zeta potential obtained in the nanoscale, are incorporated through the conditions of interface uid/solid of the Stokes problem and transportation of ions, modeled by equations of Nernst-Planck. Using the homogenization technique of periodic structures, we develop a model in macroscopic scale with respective cells problems for the e ective macroscopic parameters of equations. Finally, we propose several numerical simulations of the multiscale model for uid ow and transport of reactive ionic solute in a saturated aqueous solution of kaolinite. Using nanoscopic model we propose some numerical simulations of electrochemical adsorption phenomena in the electrical double layer. Making use of the nite element method discretize the macroscopic model and propose some numerical simulations in basic and acid system aiming to quantify the transport of ionic solutes in porous media electrically charged.

Modelagem multiescala de fenômenos eletrocinéticos em meios porosos carregados eletricamente: aplicação a meios porosos argilosos

In this master thesis, we propose a multiscale mathematical and computational model for electrokinetic phenomena in porous media electrically charged. We consider a porous medium rigid and incompressible saturated by an electrolyte solution containing four monovalent ionic solutes completely diluted in the aqueous solvent. Initially we developed the modeling electrical double layer how objective to compute the electrical potential, surface density of electrical charges and considering two chemical reactions, we propose a 2-pK model for calculating the chemical adsorption occurring in the domain of electrical double layer. Having the nanoscopic model, we deduce a model in the microscale, where the electrochemical adsorption of ions, protonation/ deprotonation reactions and zeta potential obtained in the nanoscale, are incorporated through the conditions of interface uid/solid of the Stokes problem and transportation of ions, modeled by equations of Nernst-Planck. Using the homogenization technique of periodic structures, we develop a model in macroscopic scale with respective cells problems for the e ective macroscopic parameters of equations. Finally, we propose several numerical simulations of the multiscale model for uid ow and transport of reactive ionic solute in a saturated aqueous solution of kaolinite. Using nanoscopic model we propose some numerical simulations of electrochemical adsorption phenomena in the electrical double layer. Making use of the nite element method discretize the macroscopic model and propose some numerical simulations in basic and acid system aiming to quantify the transport of ionic solutes in porous media electrically charged.

Structure, energetics and reactions of metal cation complexes of dipeptides in the gas phase

Structure, energetics and reactions of ions in the gas phase can be revealed by mass spectrometry techniques coupled to ions activation methods. Ions can gain enough energy for dissociation by absorbing IR light photons introduced by an IR laser to the mass spectrometer. Also collisions with a neutral molecule can increase the internal energy of ions and provide the dissociation threshold energy. Infrared multiple photon dissociation (IRMPD) or sustained off-resonance irradiation collision-induced dissociation (SORI-CID) methods are combined with Fourier Transform Ion Cyclotron Resonance (FT-ICR) mass spectrometers where ions can be held at low pressures for a long time. The outcome of ion activation techniques especially when it is compared to the computational methods results is of great importance since it provides useful information about the structure, thermochemistry and reactivity of ions of interest. In this work structure, energetics and reactivity of metal cation complexes with dipeptides are investigated. Effect of metal cation size and charge as well as microsolvation on the structure of these complexes has been studied. Structures of bare and hydrated Na and Ca complexes with isomeric dipeptides AlaGly and GlyAla are characterized by means of IRMPD spectroscopy and computational methods. At the second step unimolecular dissociation reactions of singly charged and doubly charged multimetallic complexes of alkaline earth metal cations with GlyGly are examined by CID method. Also structural features of these complexes are revealed by comparing their IRMPD spectra with calculated IR spectra of possible structures. At last the unimolecular dissociation reactions of Mn complexes are studied. IRMPD spectroscopy along with computational methods is also employed for structural elucidation of Mn complexes. In addition the ion-molecule reactions of Mn complexes with CO and water are explored in the low pressures obtained in the ICR cell.

Perforated tunnel exit regions and micro-pressure waves : geometrical influence

ACKNOWLEDGEMENTS The authors are grateful to the following bodies that provided financial support for the project: (i) China Scholarship Council, (ii) National Natural Science Foundation of China (Grant No. U1334201 and (iii) UK Engineering and Physical Sciences Research Council (Grant No. EP/G069441/1).

Models and empirical data for the production of referring expressions

Article Accepted Date: 29 May 2014 Acknowledgements The authors gratefully acknowledge the support of the Cognitive Science Society for the organisation of the Workshop on Production of Referring Expressions: Bridging the Gap between Cognitive and Computational Approaches to Reference, from which this special issue originated. Funding Emiel Krahmer and Albert Gatt thank The Netherlands Organisation for Scientific Research (NWO) for VICI grant Bridging the Gap between Computational Linguistics and Psycholinguistics: The Case of Referring Expressions (grant number 277-70-007).

Memory-Based Attentional Guidance: A Window to the Relationship between Working Memory and Attention

Attention, the cognitive means by which we prioritize the processing of a subset of information, is necessary for operating efficiently and effectively in the world. Thus, a critical theoretical question is how information is selected. In the visual domain, working memory (WM)—which refers to the short-term maintenance and manipulation of information that is no longer accessible by the senses—has been highlighted as an important determinant of what is selected by visual attention. Furthermore, although WM and attention have traditionally been conceived as separate cognitive constructs, an abundance of behavioral and neural evidence indicates that these two domains are in fact intertwined and overlapping. The aim of this dissertation is to better understand the nature of WM and attention, primarily through the phenomenon of memory-based attentional guidance, whereby the active maintenance of items in visual WM reliably biases the deployment of attention to memory-matching items in the visual environment. The research presented here employs a combination of behavioral, functional imaging, and computational modeling techniques that address: (1) WM guidance effects with respect to the traditional dichotomy of top-down versus bottom-up attentional control; (2) under what circumstances the contents of WM impact visual attention; and (3) the broader hypothesis of a predictive and competitive interaction between WM and attention. Collectively, these empirical findings reveal the importance of WM as a distinct factor in attentional control and support current models of multiple-state WM, which may have broader implications for how we select and maintain information.

Identifying the Structure and Fate of Wastewater Derived Organic Micropollutants by High-resolution Mass Spectrometry

Human activities represent a significant burden on the global water cycle, with large and increasing demands placed on limited water resources by manufacturing, energy production and domestic water use. In addition to changing the quantity of available water resources, human activities lead to changes in water quality by introducing a large and often poorly-characterized array of chemical pollutants, which may negatively impact biodiversity in aquatic ecosystems, leading to impairment of valuable ecosystem functions and services. Domestic and industrial wastewaters represent a significant source of pollution to the aquatic environment due to inadequate or incomplete removal of chemicals introduced into waters by human activities. Currently, incomplete chemical characterization of treated wastewaters limits comprehensive risk assessment of this ubiquitous impact to water. In particular, a significant fraction of the organic chemical composition of treated industrial and domestic wastewaters remains uncharacterized at the molecular level. Efforts aimed at reducing the impacts of water pollution on aquatic ecosystems critically require knowledge of the composition of wastewaters to develop interventions capable of protecting our precious natural water resources.

The goal of this dissertation was to develop a robust, extensible and high-throughput framework for the comprehensive characterization of organic micropollutants in wastewaters by high-resolution accurate-mass mass spectrometry. High-resolution mass spectrometry provides the most powerful analytical technique available for assessing the occurrence and fate of organic pollutants in the water cycle. However, significant limitations in data processing, analysis and interpretation have limited this technique in achieving comprehensive characterization of organic pollutants occurring in natural and built environments. My work aimed to address these challenges by development of automated workflows for the structural characterization of organic pollutants in wastewater and wastewater impacted environments by high-resolution mass spectrometry, and to apply these methods in combination with novel data handling routines to conduct detailed fate studies of wastewater-derived organic micropollutants in the aquatic environment.

In Chapter 2, chemoinformatic tools were implemented along with novel non-targeted mass spectrometric analytical methods to characterize, map, and explore an environmentally-relevant “chemical space” in municipal wastewater. This was accomplished by characterizing the molecular composition of known wastewater-derived organic pollutants and substances that are prioritized as potential wastewater contaminants, using these databases to evaluate the pollutant-likeness of structures postulated for unknown organic compounds that I detected in wastewater extracts using high-resolution mass spectrometry approaches. Results showed that application of multiple computational mass spectrometric tools to structural elucidation of unknown organic pollutants arising in wastewaters improved the efficiency and veracity of screening approaches based on high-resolution mass spectrometry. Furthermore, structural similarity searching was essential for prioritizing substances sharing structural features with known organic pollutants or industrial and consumer chemicals that could enter the environment through use or disposal.

I then applied this comprehensive methodological and computational non-targeted analysis workflow to micropollutant fate analysis in domestic wastewaters (Chapter 3), surface waters impacted by water reuse activities (Chapter 4) and effluents of wastewater treatment facilities receiving wastewater from oil and gas extraction activities (Chapter 5). In Chapter 3, I showed that application of chemometric tools aided in the prioritization of non-targeted compounds arising at various stages of conventional wastewater treatment by partitioning high dimensional data into rational chemical categories based on knowledge of organic chemical fate processes, resulting in the classification of organic micropollutants based on their occurrence and/or removal during treatment. Similarly, in Chapter 4, high-resolution sampling and broad-spectrum targeted and non-targeted chemical analysis were applied to assess the occurrence and fate of organic micropollutants in a water reuse application, wherein reclaimed wastewater was applied for irrigation of turf grass. Results showed that organic micropollutant composition of surface waters receiving runoff from wastewater irrigated areas appeared to be minimally impacted by wastewater-derived organic micropollutants. Finally, Chapter 5 presents results of the comprehensive organic chemical composition of oil and gas wastewaters treated for surface water discharge. Concurrent analysis of effluent samples by complementary, broad-spectrum analytical techniques, revealed that low-levels of hydrophobic organic contaminants, but elevated concentrations of polymeric surfactants, which may effect the fate and analysis of contaminants of concern in oil and gas wastewaters.

Taken together, my work represents significant progress in the characterization of polar organic chemical pollutants associated with wastewater-impacted environments by high-resolution mass spectrometry. Application of these comprehensive methods to examine micropollutant fate processes in wastewater treatment systems, water reuse environments, and water applications in oil/gas exploration yielded new insights into the factors that influence transport, transformation, and persistence of organic micropollutants in these systems across an unprecedented breadth of chemical space.

Challenges and Opportunities in Edge Computing

Many cloud-based applications employ a data centre as a central server to process data that is generated by edge devices, such as smartphones, tablets and wearables. This model places ever increasing demands on communication and computational infrastructure with inevitable adverse effect on Quality-of-Service and Experience. The concept of Edge Computing is predicated on moving some of this computational load towards the edge of the network to harness computational capabilities that are currently untapped in edge nodes, such as base stations, routers and switches. This position paper considers the challenges and opportunities that arise out of this new direction in the computing landscape.

Detección y evitación de objetos flotantes en el contexto de un vehículo autónomo de superficie

[ES]El Instituto Universitario de Sistemas Inteligentes y Aplicaciones Numéricas en Ingeniería y en especial la División de Robótica y Oceanografía Computacional está desarrollando un velero autónomo de superficie que requiere de un sistema para la detección y evasión de obstáculos. Dicho sistema se ha desarrollado sobre una Raspberry Pi con un servicio para la captura de imágenes, así como un servidor web que permita la modificación de la configuración de la cámara. Una vez completada dicha infraestructura se tomaron las fotografías que conformarán el conjunto de entrenamiento para el sistema de visión por computador y se desarrollará este último. Los resultados se han integrado con el sistema del control modificando el rumbo cuando se detecte un obstáculo.

A finite volume approach to dynamic fluid structure interaction

Abstract not available

A generic strategy for dynamic load balancing of distributed memory parallel computational mechanics using unstructured meshes

A large class of computational problems are characterised by frequent synchronisation, and computational requirements which change as a function of time. When such a problem is solved on a message passing multiprocessor machine [5], the combination of these characteristics leads to system performance which deteriorate in time. As the communication performance of parallel hardware steadily improves so load balance becomes a dominant factor in obtaining high parallel efficiency. Performance can be improved with periodic redistribution of computational load; however, redistribution can sometimes be very costly. We study the issue of deciding when to invoke a global load re-balancing mechanism. Such a decision policy must actively weigh the costs of remapping against the performance benefits, and should be general enough to apply automatically to a wide range of computations. This paper discusses a generic strategy for Dynamic Load Balancing (DLB) in unstructured mesh computational mechanics applications. The strategy is intended to handle varying levels of load changes throughout the run. The major issues involved in a generic dynamic load balancing scheme will be investigated together with techniques to automate the implementation of a dynamic load balancing mechanism within the Computer Aided Parallelisation Tools (CAPTools) environment, which is a semi-automatic tool for parallelisation of mesh based FORTRAN codes.