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Rodríguez, Cuesta Mª José. "Limit of detection for second-order calibration methods." Doctoral thesis, Universitat Rovira i Virgili, 2006. http://hdl.handle.net/10803/9013.
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Analytical chemistry can be split into two main types, qualitative and quantitative. Most modern analytical chemistry is quantitative. Popular sensitivity to health issues is aroused by the mountains of government regulations that use science to, for instance, provide public health information to prevent disease caused by harmful exposure to toxic substances. The concept of the minimum amount of an analyte or compound that can be detected or analysed appears in many of these regulations (for example, to discard the presence of traces of toxic substances in foodstuffs) generally as a part of method validation aimed at reliably evaluating the validity of the measurements.The lowest quantity of a substance that can be distinguished from the absence of that substance (a blank value) is called the detection limit or limit of detection (LOD). Traditionally, in the context of simple measurements where the instrumental signal only depends on the amount of analyte, a multiple of the blank value is taken to calculate the LOD (traditionally, the blank value plus three times the standard deviation of the measurement). However, the increasing complexity of the data that analytical instruments can provide for incoming samples leads to situations in which the LOD cannot be calculated as reliably as before.
Measurements, instruments and mathematical models can be classified according to the type of data they use. Tensorial theory provides a unified language that is useful for describing the chemical measurements, analytical instruments and calibration methods. Instruments that generate two-dimensional arrays of data are second-order instruments. A typical example is a spectrofluorometer, which provides a set of emission spectra obtained at different excitation wavelengths.
The calibration methods used with each type of data have different features and complexity. In this thesis, the most commonly used calibration methods are reviewed, from zero-order (or univariate) to second-order (or multi-linears) calibration models. Second-order calibration models are treated in details since they have been applied in the thesis.
Concretely, the following methods are described:
- PARAFAC (Parallel Factor Analysis)
- ITTFA (Iterative Target Transformation Analysis)
- MCR-ALS (Multivariate Curve Resolution-Alternating Least Squares)
- N-PLS (Multi-linear Partial Least Squares)
Analytical methods should be validated. The validation process typically starts by defining the scope of the analytical procedure, which includes the matrix, target analyte(s), analytical technique and intended purpose. The next step is to identify the performance characteristics that must be validated, which may depend on the purpose of the procedure, and the experiments for determining them. Finally, validation results should be documented, reviewed and maintained (if not, the procedure should be revalidated) as long as the procedure is applied in routine work.
The figures of merit of a chemical analytical process are 'those quantifiable terms which may indicate the extent of quality of the process. They include those terms that are closely related to the method and to the analyte (sensitivity, selectivity, limit of detection, limit of quantification, ...) and those which are concerned with the final results (traceability, uncertainty and representativity) (Inczédy et al., 1998). The aim of this thesis is to develop theoretical and practical strategies for calculating the limit of detection for complex analytical situations. Specifically, I focus on second-order calibration methods, i.e. when a matrix of data is available for each sample.
The methods most often used for making detection decisions are based on statistical hypothesis testing and involve a choice between two hypotheses about the sample. The first hypothesis is the "null hypothesis": the sample is analyte-free. The second hypothesis is the "alternative hypothesis": the sample is not analyte-free. In the hypothesis test there are two possible types of decision errors. An error of the first type occurs when the signal for an analyte-free sample exceeds the critical value, leading one to conclude incorrectly that the sample contains a positive amount of the analyte. This type of error is sometimes called a "false positive". An error of the second type occurs if one concludes that a sample does not contain the analyte when it actually does and it is known as a "false negative". In zero-order calibration, this hypothesis test is applied to the confidence intervals of the calibration model to estimate the LOD as proposed by Hubaux and Vos (A. Hubaux, G. Vos, Anal. Chem. 42: 849-855, 1970).
One strategy for estimating multivariate limits of detection is to transform the multivariate model into a univariate one. This strategy has been applied in this thesis in three practical applications:
1. LOD for PARAFAC (Parallel Factor Analysis).
2. LOD for ITTFA (Iterative Target Transformation Factor Analysis).
3. LOD for MCR-ALS (Multivariate Curve Resolution - Alternating Least Squares)
In addition, the thesis includes a theoretical contribution with the proposal of a sample-dependent LOD in the context of multivariate (PLS) and multi-linear (N-PLS) Partial Least Squares.
La Química Analítica es pot dividir en dos tipus d'anàlisis, l'anàlisi quantitativa i l'anàlisi qualitativa. La gran part de la química analítica moderna és quantitativa i fins i tot els govern fan ús d'aquesta ciència per establir regulacions que controlen, per exemple, nivells d'exposició a substàncies tòxiques que poden afectar la salut pública. El concepte de mínima quantitat d'un analit o component que es pot detectar apareix en moltes d'aquestes regulacions, en general com una part de la validació dels mètodes per tal de garantir la qualitat i la validesa dels resultats.
La mínima quantitat d'una substància que pot ser diferenciada de l'absència d'aquesta substància (el que es coneix com un blanc) s'anomena límit de detecció (limit of detection, LOD). En procediments on es treballa amb mesures analítiques que són degudes només a la quantitat d'analit present a la mostra (situació d'ordre zero) el LOD es pot calcular com un múltiple de la mesura del blanc (tradicionalment, 3 vegades la desviació d'aquesta mesura). Tanmateix, l'evolució dels instruments analítics i la complexitat creixent de les dades que generen, porta a situacions en les que el LOD no es pot calcular fiablement d'una forma tan senzilla. Les mesures, els instruments i els models de calibratge es poden classificar en funció del tipus de dades que utilitzen. La Teoria Tensorial s'ha utilitzat en aquesta tesi per fer aquesta classificació amb un llenguatge útil i unificat. Els instruments que generen dades en dues dimensions s'anomenen instruments de segon ordre i un exemple típic és l'espectrofluorímetre d'excitació-emissió, que proporciona un conjunt d'espectres d'emissió obtinguts a diferents longituds d'ona d'excitació.
Els mètodes de calibratge emprats amb cada tipus de dades tenen diferents característiques i complexitat. En aquesta tesi, es fa una revisió dels models de calibratge més habituals d'ordre zero (univariants), de primer ordre (multivariants) i de segon ordre (multilinears). Els mètodes de segon ordre estan tractats amb més detall donat que són els que s'han emprat en les aplicacions pràctiques portades a terme.
Concretament es descriuen:
- PARAFAC (Parallel Factor Analysis)
- ITTFA (Iterative Target Transformation Analysis)
- MCR-ALS (Multivariate Curve Resolution-Alternating Least Squares)
- N-PLS (Multi-linear Partial Least Squares)
Com s'ha avançat al principi, els mètodes analítics s'han de validar. El procés de validació inclou la definició dels límits d'aplicació del procediment analític (des del tipus de mostres o matrius fins l'analit o components d'interès, la tècnica analítica i l'objectiu del procediment). La següent etapa consisteix en identificar i estimar els paràmetres de qualitat (figures of merit, FOM) que s'han de validar per, finalment, documentar els resultats de la validació i mantenir-los mentre sigui aplicable el procediment descrit.
Algunes FOM dels processos químics de mesura són: sensibilitat, selectivitat, límit de detecció, exactitud, precisió, etc. L'objectiu principal d'aquesta tesi és desenvolupar estratègies teòriques i pràctiques per calcular el límit de detecció per problemes analítics complexos. Concretament, està centrat en els mètodes de calibratge que treballen amb dades de segon ordre.
Els mètodes més emprats per definir criteris de detecció estan basats en proves d'hipòtesis i impliquen una elecció entre dues hipòtesis sobre la mostra. La primera hipòtesi és la hipòtesi nul·la: a la mostra no hi ha analit. La segona hipòtesis és la hipòtesis alternativa: a la mostra hi ha analit. En aquest context, hi ha dos tipus d'errors en la decisió. L'error de primer tipus té lloc quan es determina que la mostra conté analit quan no en té i la probabilitat de cometre l'error de primer tipus s'anomena fals positiu. L'error de segon tipus té lloc quan es determina que la mostra no conté analit quan en realitat si en conté i la probabilitat d'aquest error s'anomena fals negatiu. En calibratges d'ordre zero, aquesta prova d'hipòtesi s'aplica als intervals de confiança de la recta de calibratge per calcular el LOD mitjançant les fórmules d'Hubaux i Vos (A. Hubaux, G. Vos, Anal. Chem. 42: 849-855, 1970)
Una estratègia per a calcular límits de detecció quan es treballa amb dades de segon ordre es transformar el model multivariant en un model univariant. Aquesta estratègia s'ha fet servir en la tesi en tres aplicacions diferents::
1. LOD per PARAFAC (Parallel Factor Analysis).
2. LOD per ITTFA (Iterative Target Transformation Factor Analysis).
3. LOD per MCR-ALS (Multivariate Curve Resolution - Alternating Least Squares)
A més, la tesi inclou una contribució teòrica amb la proposta d'un LOD que és específic per cada mostra, en el context del mètode multivariant PLS i del multilinear N-PLS.
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Rens, Bram Antonius Philomena van. "Detection of magnetic monopoles below the Cherenkov limit." [S.l. : Amsterdam : s.n.] ; Universiteit van Amsterdam [Host], 2006. http://dare.uva.nl/document/23682.
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Yavrucuk, Ilkay. "Adaptive limit margin detection and limit avoidance." Diss., Georgia Institute of Technology, 2003. http://hdl.handle.net/1853/12354.
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Horn, Joe. "Flight envelope limit detection and avoidance." Diss., Georgia Institute of Technology, 1999. http://hdl.handle.net/1853/12435.
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Tallawi, Reham. "FPGA-based Speed Limit Sign Detection." Master's thesis, Universitätsbibliothek Chemnitz, 2017. http://nbn-resolving.de/urn:nbn:de:bsz:ch1-qucosa-229018.
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This thesis presents a new hardware accelerated approach using image processing and detection algorithms for implementing fast and robust traffic sign detection system with focus on speed limit sign detection. The proposed system targets reconfigurable integrated circuits particularly Field Programmable Gate Array (FPGA) devices. This work propose a fully parallelized and pipelined parallel system architecture to exploit the high performance and flexibility capabilities of FPGA devices. This thesis is divided into two phases, the first phase, is a software prototype implementation of the proposed system. The software system was designed and developed using C++ and OpenCV library on general purpose CPU. The prototype is used to explore and investigate potential segmentation and detection algorithms that might be feasible to design and implement in hardware accelerated environments. These algorithms includes RGB colour conversion, colour segmentation through thresholding, noise reduction through median filter, morphological operations through erosion and dilation, and sign detection through template matching. The second phase, a hardware-based design of the system was developed using the same algorithms used in the software design. The hardware design is composed of 20 image processing components each designed to xxx fully parallelized and pipelined xxx. The hardware implementation was developed using VHDL as the hardware description language targeting a Xilinix Virtex-6 FPGA XC6VLX240T device. The development environment is Xilinx ISE®Design Suite version 14.3. A set of 20 640x480 test images was used as the test data for the verification and testing of this work. The images was captured by a smart-phone camera in various weather and lightning conditions. The software implementation delivered speed limit detection results with a success rate of 75%. The hardware implementation was only simulated using Xilinx ISE Simulator (ISim) with a overall system latency of 12964 clock cycles. According to the Place and Route report the maximum operation frequency for the proposed hardware design is 71,2 MHz. The design only utilized 2% of the slice registers, 4% of the slice Look up Tables (LUT), and 11% of the block memory. This thesis project concludes the work based on the provided software and hardware implementation and performance analysis results. Also the conclusions chapter provides recommendations and future work for possible extension of the project.
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Kirwa, Abraham Tuwei. "Self-referenced evanescent wave sensor for low limit of detection applications." Thesis, University of Sheffield, 2018. http://etheses.whiterose.ac.uk/22475/.
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We have designed and implemented a low noise evanescent wave sensor (EWS) based on lock-in amplifier and sensitized glass optical fibre for detection of waterborne and airborne analytes. We stripped the buffer and cladding from a 2 cm section in the middle of a 20 cm long 400 μm core multimode glass optical fibre and coated it with a film of a sensitive molecule. We then ran the coated optical fibre through a sample vessel such that the film was in contact with a sample that may contain analyte, and probed with modulated light, coupled into the fibre from an LED. We matched the LED peak emission wavelength to the absorption peak of the sensitizer-analyte complex formed and used the reference voltage output of a digital lock-in amplifier for modulation. To account for possible LED drift, we propagated the modulated light through a 50:50 beam splitter, where one beam was coupled to the coated fibre (sample beam) and the other acts as a reference beam. We then projected the two beams onto two photodiodes connected to a 'light balance' circuit that delivers a differential current ∆i, which is proportional to the absorbance along the sample beam and converts it into a voltage. Finally, this voltage was fed into the digital lock-in amplifier for low- noise measurement. As a proof of concept, we spray-coated the stripped section of the optical fibre with 5,10,15,20-tetrakis[3,4-bis(2-ethylhexyloxy)phenyl]-21H,23H-porphine (EHO), which is sensitive to acetic acid and ran the fibre through a gas exposure chamber. Then we exposed acetic acid vapour, which is being detected, into the chamber and found a limit of detection (LoD), (defined as the lowest concentration that a sensor can detect) equal to 1.491 ppt (61.48 µM). To compare the performance of our EWS in air and in aqueous media, we coated the same sensitizer (EHO) to the stripped section of the fibre and run through deionised water in a sample vessel. Titrating acetic acid solution into the vessel, we obtained a LoD equal to 18.43 µM, which is 3.3 times better than in air. We further tested the performance of our EWS by spray-coating the stripped section of the fibre with 1-(2-pyridylazo)-2-naphthol (PAN) to detect aqueous Zn2+ and obtained 31.07 nM as a LoD. To improve the analytical performance of our EWS, we roughened the stripped section of the sensing fibre with a home-made roughening tool based on a Dremel tool. Then we spray-coated optical fibres with a macrocyclic sensitizer, zinc 5-(4-carboxyphenyl),10,15,20-triphenyl porphyrin (Zn(P-CO2H-TPP)) and used them to detect waterborne octylamine realizing a LoD equal to 2.17 μM. In conclusion, we find EWS sensors are particularly useful for sensing in the aqueous medium, as the higher refractive index (1.333) of water, (compared to air (1)) allows deeper evanescence of the light propagating inside the fibre, and hence better coupling to the sensitizer coating, than in gas sensing.
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Heaney, S. F. "Development of a low detection limit Cu(II) ISE for complexation studies." Thesis, Queen's University Belfast, 2005. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.419362.
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Dick, Nicole Marie. "Methods for handling missing data due to a limit of detection in longitudinal lognormal data." Manhattan, Kan. : Kansas State University, 2008. http://hdl.handle.net/2097/867.
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Jin, Yan. "Bayesian Solution to the Analysis of Data with Values below the Limit of Detection (LOD)." University of Cincinnati / OhioLINK, 2008. http://rave.ohiolink.edu/etdc/view?acc_num=ucin1227293204.
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Láznička, Jan. "Analýza spolehlivosti měření látek pomocí biosenzorů - návrh robustní metody stanovení limitu detekce." Master's thesis, Vysoké učení technické v Brně. Fakulta elektrotechniky a komunikačních technologií, 2008. http://www.nusl.cz/ntk/nusl-217622.
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Detection limit of any method is affected by device (electronics, noise), evaluation, software (timing inaccuracy, rounding mistakes, errors determination of parameters using measured values by numerical methods) and by a chemical reaction (diluting errors, the reaction mixture design, chemical interferents, temperature, the accuracy of pipetting). In this work was proposed a metod for determination of detection limit for measuring of inhibitors of acetylcholine esterase by biosensor analysator of toxicity (BTA). The analysator was developed by BVT Technologies a.s. in 2004. To determine the exact detection limit a calibration of output signal was done. Presently the analysator is able to detect only presence of toxins, not their concentration. Not least are mentioned all founded errors of software, which are continuously eliminated.
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Sharma, Siddhartha Mohan. "Optimizing the lower limit of detection of proteins for use in a novel diagnostic device for cancer." Thesis, Boston University, 2012. https://hdl.handle.net/2144/12620.
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Thesis (M.A.)--Boston University
PLEASE NOTE: Boston University Libraries did not receive an Authorization To Manage form for this thesis or dissertation. It is therefore not openly accessible, though it may be available by request. If you are the author or principal advisor of this work and would like to request open access for it, please contact us at open-help@bu.edu. Thank you.Cancer is a major health concern throughout the United States and around the world. It is the second most common cause of death in the United States. However, since the 1970's survivorship has increased for many types of cancer. Cancer diagnostics, in addition to better and more targeted treatment, have been critical to this success. Current gold standard methods have significant limitations which can lead to delays in treatment or require more invasive procedures that need a significant amount of tissue for accurate diagnosis. One approach to improve current diagnostic methods is to use proteomics and microfluidic devices to create an integrated diagnostic device. A microfluidic device, built as a porous polymer monolith, can be utilized for solid phase extraction for protein biomarkers that are indicative of cancer. Microfluidic devices have already been used to extract RNA from bacteria, viruses and, in a previous study, for extracting miRNA from human cancer cells in large enough quantities to be useful as a diagnostic assay and require a significant amount of tissue. The aim of this study is to validate the presence of select protein biomarkers, to determine the lower limit of detection of these biomarkers and to quantify them from two cancer cell lines. This study is being conducted in support of a larger project's goal to design a cheap, disposable, plastic microfluidic chip for the analysis of protein biomarkers that are indicative of cancer and intended for use in a bench top machine. Ultimately, the chip's utility will be validated by analyzing small volume human specimens. BCPAP, a thyroid cancer cell line, and MCF-7, a breast cancer cell line, will be used to demonstrate the chips ability to extract, from whole cell lysates, the following protein biomarkers: Estrogen Receptor-alpha, Estrogen Receptor-beta, Thyroid Transcription Factor-1, Thyroglobulin, Human Epidermal Growth Factor Receptor-2, and E-cadherin from whole celllysates.
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Muro, Claire K. "Further Development of Raman Spectroscopy for Body Fluid Investigation| Forensic Identification, Limit of Detection, and Donor Characterization." Thesis, State University of New York at Albany, 2017. http://pqdtopen.proquest.com/#viewpdf?dispub=10275358.
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The challenges to forensic body fluid analysis have placed limitations on the type of information that investigators can acquire and how that information can be collected. In recent years, Raman spectroscopy has proven itself useful for characterizing body fluids. In 2008, a large-scale investigation was undertaken to explore the use of Raman spectroscopy as a means of identifying body fluids. This work resulted in multidimensional Raman spectroscopic signatures for the five main body fluids: semen, peripheral blood, saliva, vaginal fluid, and sweat. These studies were incredibly successful and created the foundation for years of continued research. Accordingly, the studies included in this thesis have been specifically chosen to frame the previous research projects. They include a suite of projects aimed to advance and validate the developed method.
First, a statistical model was developed to automatically identify and differentiate body fluids based on their Raman spectra. The multidimensional spectroscopic signatures mentioned above are very effective at identification, but they are body fluid-specific. In other words, they individually evaluate whether or not an unknown spectrum is from a particular body fluid, such as blood. Additionally, each signature was built on spectra from a limited number of donors. To improve on this capability, a single classification model was built on the Raman spectra from 60 donors (12 for each body fluid). This model was externally validated with an additional 15 donors in order to objectively assess the model’s performance. All of the external validation donors were correctly identified, illustrating how accurate and robust the model is.
Second, the limit of detection (LOD) for the classification model was explored as a form of validation. It is vitally important that a method’s limits be established before deploying it into use. The LOD of peripheral blood was investigated. Peripheral blood is unique from other body fluids because its Raman spectrum has been attributed almost entirely to one molecule- hemoglobin. Because hemoglobin is only found in red blood cells (RBCs), the Raman spectrum of peripheral blood essentially results purely from RBCs. Given this, we chose to start with a single RBC, and then increase the volume until identification was successful. We found that we were able to conclusively and confidently identify peripheral blood using a single red blood cell. This limit is 5000X smaller than the amount of blood required for DNA analysis, demonstrating the sensitivity of the developed method.
Finally, the method was further advanced by incorporating donor characterization into the process. Besides identifying body fluids, the method can now extract “phenotypic” information about the donor. Raman spectroscopy and multivariate data analysis were used to determine the biological sex of saliva donors, and the race of semen donors. These studies will help forensic investigators extract incredibly useful information about a potential suspect or victim, and can be performed directly at a crime scene for instant results.
Altogether, these studies combine to strengthen the method previously developed by our research group. More importantly, they help to bridge the gap between research and application. Creating a universal method to differentiate and identify body fluids, investigating the method’s LOD, and developing additional techniques to characterize body fluids represents a significant contribution to the field of forensic chemistry. The universal method created within this thesis will be adapted to perform on-site analysis of physical evidence at crime scenes. The methods’ incredible sensitivity has been demonstrated by determining that it can identify peripheral blood based on a single RBC. Finally, by developing models to characterize body fluid donors, investigators will be able to extract useful information about individuals that may have been present at a crime scene. Additional studies are already being conducted to make further improvements, and our method is poised to make a significant contribution to the field of crime scene investigation.
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Sherman, Brook W. "The Examination and Evaluation of Dynamic Ship Quiescence Prediction and Detection Methods for Application in the Ship-Helicopter Dynamic Interface." Thesis, Virginia Tech, 2007. http://hdl.handle.net/10919/32436.
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Motion sensitive operations at sea are conducted in an unpredictable environment. While occasionally these operations can be planned around suitable weather forecast or delayed until smoother motions are apparent, naval ships conducting flight operations may have little liberty in their mission planning and execution. Tools exist to translate the oceanâ s harsh conditions into discretely defined low motion operational periods. Particularly of interest, the identification of discrete lull periods or quiescence for shipboard helicopter operations can be better defined using a landing period indicator than with the current method of utilizing static deck angle measurements. While few of these systems exist, assessing their operational benefits is difficult due to a lack of well-defined performance metrics.
This thesis defines and examines the use of two methodical approaches to evaluating Landing Period Indicators (LPIs) and their subject ship-helicopter dynamic interface system. First a methodology utilizing the comparison of a basic transparent algorithm is detailed and a case study employing this methodology is examined. Second, a system dynamics approach is taken to pilot workload analysis, utilizing a dynamic systems model characterizing a subset of the Dynamic Interface. This approach illustrates the realistic gains in understanding and development that can be accomplished by utilizing system dynamics in the analysis of the Dynamic Interface and LPI insertion.
Master of Science
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Urbano, Simone. "Detection and diagnostic of freeplay induced limit cycle oscillation in the flight control system of a civil aircraf." Thesis, Toulouse, INPT, 2019. http://www.theses.fr/2019INPT0023/document.
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Cette étude est le résultat d’une thèse CIFRE de trois ans entre le bureau d’étude d’Airbus (domaine du contrôle de l’avion) et le laboratoire TéSA à Toulouse. L’objectif principal est de proposer, développer et valider une solution logicielle pour la détection et le diagnostic d’un type spécifique de vibrations des gouvernes de profondeur et direction, appelée oscillation en cycle limite (limit cycle oscillation ou LCO en anglais), basée sur les signaux existants dans les avions civils. LCO est un terme mathématique générique définissant un mode périodique indépendant de conditions initiales et se produisant dans des systèmes non linéaires non conservatifs. Dans cette étude, nous nous intéressons au phénomène de LCO induit par les jeux mécaniques dans les gouvernes d’un avion civil. Les conséquences du LCO sont l’augmentation locale de la charge structurelle, la dégradation des qualités de vol, la réduction de la durée de vie de l’actionneur, la dégradation du confort du poste de pilotage et de la cabine, ainsi que l’augmentation des coûts de maintenance. L’état de l’art en matière de détection et de diagnostic du LCO induit par le jeu mécanique est basé sur la sensibilité du pilote aux vibrations et sur le contrôle périodique du jeu sur les gouvernes. Cette étude propose une solution basée sur les données (issues de la boucle d’asservissement des actionneurs qui agissent sur les gouvernes) pour aider au diagnostic du LCO et à l’isolement du jeu mécanique. L’objectif est d’améliorer encore plus la disponibilité des avions et de réduire les coûts de maintenance en fournissant aux compagnies aériennes un signal de contrôle pour le LCO et les jeux mécaniques. Pour cette raison, deux solutions algorithmiques pour le diagnostic des vibrations et des jeux ont été proposées. Un détecteur en temps réel pour la détection du LCO est tout d’abord proposé basé sur la théorie du rapport de vraisemblance généralisé (generalized likelihood ratio test ou GLRT en anglais). Certaines variantes et simplifications sont également proposées pour satisfaire les contraintes industrielles. Un détecteur de jeu mécanique est introduit basé sur l’identification d’un modèle de Wiener. Des approches paramétrique (estimateur de maximum de vraisemblance) et non paramétrique (régression par noyau) sont explorées, ainsi que certaines variantes des méthodes non paramétriques. En particulier, le problème de l’estimation d’un cycle d’hystérésis (choisi comme la non-linéarité de sortie d’un modèle de Wiener) est abordé. Ainsi, les problèmes avec et sans contraintes sont étudiés. Une analyse théorique, numérique (sur simulateur) et expérimentale (données de vol et laboratoire) est réalisée pour étudier les performances des détecteurs proposés et pour identifier les limitations et la faisabilité industrielle. Les résultats numériques et expérimentaux obtenus confirment que le GLRT proposé (et ses variantes / simplifications) est une méthode très efficace pour le diagnostic du LCO en termes de performance, robustesse et coût calculatoire. D’autre part, l’algorithme de diagnostic des jeux mécaniques est capable de détecter des niveaux de jeu relativement importants, mais il ne fournit pas de résultats cohérents pour des niveaux de jeu relativement faibles. En outre, des types d’entrée spécifiques sont nécessaires pour garantir des résultats répétitifs et cohérents. Des études complémentaires pourraient être menées afin de comparer les résultats de GLRT avec une approche Bayésienne et pour approfondir les possibilités et les limites de la méthode paramétrique proposée pour l’identification du modèle de WienerThis research study is the result of a 3 years CIFRE PhD thesis between the Airbus design office(Aircraft Control domain) and TéSA laboratory in Toulouse. The main goal is to propose, developand validate a software solution for the detection and diagnosis of a specific type of elevator andrudder vibration, called limit cycle oscillation (LCO), based on existing signals available in flightcontrol computers on board in-series aircraft. LCO is a generic mathematical term defining aninitial condition-independent periodic mode occurring in nonconservative nonlinear systems. Thisstudy focuses on the LCO phenomenon induced by mechanical freeplays in the control surface ofa civil aircraft. The LCO consequences are local structural load augmentation, flight handlingqualities deterioration, actuator operational life reduction, cockpit and cabin comfort deteriorationand maintenance cost augmentation. The state-of-the-art for freeplay induced LCO detection anddiagnosis is based on the pilot sensitivity to vibration and to periodic freeplay check on the controlsurfaces. This study is thought to propose a data-driven solution to help LCO and freeplaydiagnosis. The goal is to improve even more aircraft availability and reduce the maintenance costsby providing to the airlines a condition monitoring signal for LCO and freeplays. For this reason,two algorithmic solutions for vibration and freeplay diagnosis are investigated in this PhD thesis. Areal time detector for LCO diagnosis is first proposed based on the theory of the generalized likeli hood ratio test (GLRT). Some variants and simplifications are also proposed to be compliantwith the industrial constraints. In a second part of this work, a mechanical freeplay detector isintroduced based on the theory of Wiener model identification. Parametric (maximum likelihoodestimator) and non parametric (kernel regression) approaches are investigated, as well as somevariants to well-known nonparametric methods. In particular, the problem of hysteresis cycleestimation (as the output nonlinearity of a Wiener model) is tackled. Moreover, the constrainedand unconstrained problems are studied. A theoretical, numerical (simulator) and experimental(flight data and laboratory) analysis is carried out to investigate the performance of the proposeddetectors and to identify limitations and industrial feasibility. The obtained numerical andexperimental results confirm that the proposed GLR test (and its variants/simplifications) is a very appealing method for LCO diagnostic in terms of performance, robustness and computationalcost. On the other hand, the proposed freeplay diagnostic algorithm is able to detect relativelylarge freeplay levels, but it does not provide consistent results for relatively small freeplay levels. Moreover, specific input types are needed to guarantee repetitive and consistent results. Further studies should be carried out in order to compare the GLRT results with a Bayesian approach and to investigate more deeply the possibilities and limitations of the proposed parametric method for Wiener model identification
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Zosiwe, Mlandeli Siphelele Ernest. "Cytochrome P450 2E1/Nickel-Poly(propylene imine) dendrimeric nanobiosensor for pyrazinamide - A first line TB Drug." University of the Western Cape, 2015. http://hdl.handle.net/11394/4703.
Full textAbstract:
>Magister Scientiae - MScThe tuberculosis (TB) disease to this day remains one of the world’s prominent killerdiseases. Pyrazinamide (PZA) is one of the most commonly prescribed anti- tuberculosis (anti-TB) drugs due to its ability to significantly shorten the TB treatment period from the former nine months to the current six months duration. However, excess PZA in the body causes hepatotoxicity and damages the liver. This hepatotoxicity, together with the resistance of the bacteria to treatment drugs, poor medication and inappropriate dosing, greatly contribute to the high incidents of TB deaths and diseases that are due to side effects (such as liver damage). This brings about the calls for alternative methods for ensuring reliable dosing of the drug, which will be specific from person to person due to inter-individual differences in drug metabolism. A novel biosensor system for monitoring the metabolism of PZA was prepared with a Ni-PPI-PPy star copolymer and cytochrome P450 2E1 (CYP2E1) deposited onto a platinum electrode. The nanobiosensor system exhibited enhanced electro-activity that is attributed to the catalytic effect of the incorporated star copolymer. The biosensor had a sensitivity of 0.142 µA.nM-1, and a dynamic linear range (DLR) of 0.01 nM-0.12 nM (1.231 – 7.386 ng/L PZA). The limit of detection of the biosensor was found to be 0.00114 nM (0.14 ng/L) PZA. From the HPLC peakconcentration (Cmax) of PZA determined 2 h after drug intake is 2.79 – 3.22 ng.L-1,which is very detectable with the nanobiosensor as it falls within the dynamic linear range.
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Schreiber, Emil [Verfasser]. "Gravitational-wave detection beyond the quantum shot-noise limit : the integration of squeezed light in GEO 600 / Emil Schreiber." Hannover : Gottfried Wilhelm Leibniz Universität Hannover, 2018. http://d-nb.info/1172414548/34.
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Martin-Rémy, Aurélie. "Analyse de données de biométrologie : aspects méthodologiques et applications." Thesis, Université de Lorraine, 2018. http://www.theses.fr/2018LORR0223/document.
Full textAbstract:
De nombreuses études de biométrologie sont menées à l’INRS, pour évaluer l’exposition professionnelle à des substances chimiques, en France, et pour compléter les connaissances en proposant des valeurs de références destinées à protéger des salariés exposés à ces substances. Ces études consistent à mesurer simultanément l’imprégnation biologique et l’exposition atmosphérique à une substance, chez des salariés exposés à celle-ci. La relation entre ces mesures biologiques et atmosphériques est ensuite estimée à travers un modèle de régression linéaire. Lorsque que cette relation existe et que la voie d’absorption du toxique est essentiellement inhalatoire, il est ensuite possible de dériver une Valeur Limite Biologique (VLB) à partir de la Valeur Limite d’Exposition Professionnelle (VLEP-8h) du toxique. Deux aspects de ces données ont été identifiés, qui ne sont pas ou seulement partiellement prises en compte dans les modélisations statistiques courantes : la censure due aux limites de détection (LD)/quantification (LQ) des mesures biologiques et atmosphériques et la variabilité inter-individuelle. Ignorer ces deux particularités lors de la modélisation mène à une perte de puissance statistique et à de potentielles conclusions biaisées. Les travaux menés dans le cadre de cette thèse ont permis d’adapter le modèle de régression à ces deux caractéristiques, dans un cadre bayésien. L’approche proposée repose sur la modélisation des mesures atmosphériques à l’aide de modèles à effets aléatoires prenant en compte les valeurs inférieures à la LD/LQ, et sur la modélisation simultanée des mesures biologiques, supposée être linéairement dépendantes sur une échelle logarithmique, de l'exposition atmosphérique, tout en tenant compte de la variabilité inter-individuelle. Ce travail a donné lieu à une publication scientifique dans une revue à comité de lecture. L’application de cette méthodologie a été réalisée sur des jeux d’exposition professionnelle au béryllium et au chrome, après avoir été cependant adaptée aux caractéristiques toxicocinétiques de ces deux substances. Il a ainsi été possible de proposer une VLB pour le béryllium (0,06 µg/g créatinine). L’exploitation de mesures de chrome dans deux secteurs d’activités différents (exposition professionnelle aux peintures de chromates, et exposition professionnelle dans le secteur du chromage électrolytique) a permis de mettre en évidence que le chrome urinaire dépend essentiellement de l’exposition au chrome VI, le chrome non VI ayant moins d’impact. Nous n’avons pas pu montrer de relation entre la solubilité du CrVI et le chrome urinaire. Une VLB de 0,41 µg/g créatinine, de l’ordre de la Valeur Biologique de Référence (VBR) proposée par l’ANSES (0,54 µg/g créatinine), a été estimée pour l’exposition professionnelle aux peintures de chromates, et une VLB de 1,85 µg/g créatinine a été estimée pour l’exposition professionnelle dans le secteur du chromage électrolytique, qui est en cohérence avec la VLB proposée par l’ANSES dans ce secteur, à savoir 1,8 µg/g créatinineMany biomonitoring studies are conducted at INRS, in order to assess occupational exposure to chemicals in France, and to propose reference values to protect workers exposed to these substances. These studies consist in measuring simultaneously biological and airborne exposure of workers exposed to a toxic substance. The relationship between these biological and airborne measurements is then estimated through a linear regression model. When this relationship exists and the route of absorption of the toxic is essentially inhalatory, it is possible to derive a Biological Limit Value (BLV) from the Occupational Exposure Limit Value (OEL) of the toxic substance. However, two characteristics of these data have been identified, which are not or only partially taken into account in the current statistical modelling: the left-censoring due to limits of detection (LoD)/quantification (LoQ) of biological and airborne measurements, and the between-individual variability. Ignoring both of these features in modelling leads to a loss of statistical power and potentially biased conclusions. The work carried out in this thesis allowed us to adapt the regression model to these two characteristics, in a Bayesian framework. The proposed approach is based on the modelling of airborne measurements using random effects models adapted for values below the LoD / LoQ, and on the simultaneous modelling of biological measurements, assumed to depend linearly on a logarithmic scale, on the airborne exposure, while taking into account between-subject variability. This work resulted in a scientific publication in a peer-reviewed journal. This methodology has been applied on beryllium and chromium occupational exposure datasets, after adaptation to the toxicokinetic characteristics of these two substances. It has thus been possible to propose a BLV for beryllium (0.06 μg / g creatinine). The analysis of chromium measurements in two different sectors of activity (occupational exposure to chromate paints, and occupational exposure in the electroplating sector) made it possible to show that urinary chromium depends mainly on airborne exposure to VI chromium, non-VI chromium having less impact. We were not able to show a relationship between the solubility of airborne VI chromium and urinary chromium. A BLV of 0.41 μg / g creatinine, close to the Biological Guidance Value (BGV) proposed by ANSES (0.54 μg / g creatinine), was estimated for occupational exposure to chromate paints, and a BLV of 1.85 μg/g creatinine was obtained for occupational exposure in the electrolytic chromium plating sector, which is consistent with the ANSES proposed BLV in this sector, i-e 1.8 μg / g creatinine
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Nqakala, Noniko Civilized. "Construction of an enzyme-free electrochemical sensor based on Ag-Fe2O3/POM/RGO novel nanocomposite for hydrogen peroxide detection." University of the Western Cape, 2018. http://hdl.handle.net/11394/6762.
Full textAbstract:
>Magister Scientiae - MScThe motivation to determine H2O2 lies in the fact that this chemical species plays a crucial role in diverse fields of practise such as cosmetic, food, diagnostic, pharmaceutical, clinical and environmental protection industries. Several methods such as chromatography, colorimetry, titrimetry and spectrophotometry have been developed for its detection. However, these methods are known to manifest underlying disadvantages such as high cost, time consuming, instability and complicated immobilization procedures. In this present study an enzyme-less electrochemical sensor based on Ag-Fe2O3/POM/RGO nanocomposite (POM stands for polyoxometalate and RGO stands for reduced graphene oxide) was successfully synthesised via a hydrothermal method and a photochemical reduction method for the detection of hydrogen peroxide (H2O2).
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Panahi, Tayyebeh. "Glutamic Acid Resorcinarene-based Molecules and Their Application in Developing New Stationary Phases in Ion Chromatography." BYU ScholarsArchive, 2016. https://scholarsarchive.byu.edu/etd/6436.
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Resorcinarenes can be functionalized at their upper and lower rims. In this work, the upper rim of a resorcinarene was functionalized with glutamic acids and the lower rim was functionalized with either methyl or undecyl alkyl groups. The cavitands were characterized by nuclear magnetic resonance (NMR), mass spectrometry (MS), UV-vis spectroscopy, dynamic light scattering (DLS) and electron microscopy. The binding of resorcinarene with amine guests was studied in DMSO by UV-vis titration. The obtained binding constants (K values) were in the range of 12,000-136000 M-1. The resorcinarenes were shown to form aggregates in a variety of solvents. The aggregates were spherical as confirmed by DLS, SEM and TEM experiments. Dynamic light scattering (DLS) experiments revealed the size of the aggregates could be controlled by cavitand concentration, pH, and temperature. The resorcinarene with undecyl alkyl group were adsorbed onto 55% cross-linked styrene-divinylbenzene resin to prepare a new stationary phases for ion chromatography (IC) columns. The new column packing material was applied in determination of uremic toxins and water contaminants. The new IC column afforded separation of the five uremic toxins : guanidinoacetic acid, guanidine, methylguanidine, creatinine, and guanidinobenzoic acid in 30 minutes. Detection and quantification of uremic toxins helps diagnose kidney problems and start patient care. Gradient elutions at ambient temperature with methanesulfonic acid (MSA) as eluent resulted in detection levels in water from 10 to 47 ppb and in synthetic urine from 28 to 180 ppb. Trace levels of creatinine (1 ppt) were detected in the urine of a healthy individual using the columns. The new IC stationary phase separated cationic pharmaceuticals including a group of guanidine compounds in surface water. Detection limits in the range of 5 - 32 µg L-1 were achieved using integrated pulsed amperometric detection (IPAD) for guanidine (G), methylguanidine (MG), 1,1-dimethylbiguanidine (DMG), agmatine (AGM), guanidinobenzoic acid (GBA) and cimetidine (CIM). Suppressed conductivity (CD) and UV-vis detection resulted in limits of detection similar to IPAD, in the range of 1.7 - 66 µg L-1, but were not able to detect all of the analytes. Three water sources, river, lake, and marsh, were analyzed and despite matrix effects, sensitivity for guanidine compounds was in the 100 µg L-1 range and apparent recoveries were 80-96 %. The peak area precision was 0.01 - 2.89% for IPAD, CD and UV-vis detection.
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Gutiérrez, Arenas Omar. "Sensitivity, Noise and Detection of Enzyme Inhibition in Progress Curves." Doctoral thesis, Uppsala University, Department of Biochemistry, 2006. http://urn.kb.se/resolve?urn=urn:nbn:se:uu:diva-6886.
Full textAbstract:
Starting with the development of an enzymatic assay, where an enzyme in solution hydrolysed a solid-phase bound peptide, a model for the kinetics of enzyme action was introduced. This model allowed the estimation of kinetic parameters and enzyme activity for a system that has the peculiarity of not being saturable with the substrate, but with the enzyme. In a derivation of the model, it was found that the sensitivity of the signal to variations in the enzyme concentration had a transient increase along the reaction progress with a maximum at high substrate conversion levels.
The same behaviour was derived for the sensitivity in classical homogeneous enzymatic assays and experimental evidence of this was obtained. The impact of the transient increase of the sensitivity on the error structure, and on the ability of homogeneous end-point enzymatic assays to detect competitive inhibition, came into focus. First, a non-monotonous shape in the standard deviation of progress curve data was found and it was attributed to the random dispersion in the enzyme concentration operating through the transient increase in the sensitivity. Second, a model for the detection limit of the quantity Ki/[I] (the IDL-factor) as a function of the substrate conversion level was developed for homogeneous end-point enzymatic assays.
It was found that the substrate conversion level where the IDL-factor reached an optimum was beyond the initial velocity range. Moreover, at this optimal point not only the ability to detect inhibitors but also the robustness of the assays was maximized. These results may prove to be relevant in drug discovery for optimising end point homogeneous enzymatic assays that are used to find inhibitors against a target enzyme in compound libraries, which are usually big (>10000) and crowded with irrelevant compounds.
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Liu, Jun. "Biomarker Detection at Risk Forecasting Level Using Metal-Enhanced Fluorescence Combined with Surface Acoustic Wave." Scholar Commons, 2016. http://scholarcommons.usf.edu/etd/6534.
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In this paper, metal-enhanced fluorescence (MEF) technique is used to lower the detection limit of carcinoembryonic antigen (CEA) which is able to be utilized in forecasting the risk of having certain kinds of cancers, especially colon and rectal cancer. By incubating silver nanocubes (Ag NCs) on the surface of the chips, the detection limit goes down to below 1ng/mL of CEA. Also, when combining MEF with surface acoustic wave (SAW) devices, the incubation time between antigen and antibody will decrease significantly with the fluorescence signal keeping similar or higher level.
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Keathley, Phillip Donald. "DESIGN AND ANALYSIS OF NANO-GAP ENHANCED SURFACE PLASMON RESONANCE SENSORS." UKnowledge, 2009. http://uknowledge.uky.edu/gradschool_theses/643.
Full textAbstract:
Surface plasmon resonance (SPR) sensors are advantageous to other techniques of sensing chemical binding, offering quantitative, real-time, label-free results. Previous work has demonstrated the effectiveness of using dual-mode SPR sensors to differentiate between surface and background effects, making the sensors more robust to dynamic environments. This work demonstrates a technique that improves upon a previously optimized planar film dual-mode SPR sensor’s LOD by introducing a periodic array of subwavelength nano-gaps throughout the plasmon supporting material. First, general figures of merit for a sensor having an arbitrary number of modes are studied. Next, the mode effective index dispersion and magnetic field profiles of the two strongly bound modes found using a gap width of 20nm are analyzed. Qualitative analysis of the results demonstrates how such a design can enable better LODs in terms of each figure of merit. By optimizing a nano-gap enhanced sensor containing 20nm gaps, it is quantitatively demonstrated that the resulting modes improve upon almost every figure of merit, especially with respect to the orthogonality and magnitude of the sensitivity vectors, resulting in LODs approximately a factor of five less than the optimal planar design.
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Willemse, Chandre Monique. "Nanocomposite-graphene based platform for heavy metal detection." Thesis, University of the Western Cape, 2010. http://etd.uwc.ac.za/index.php?module=etd&action=viewtitle&id=gen8Srv25Nme4_8123_1323852117.
Full textAbstract:
This study reports the synthesis of graphene by oxidizing graphite to graphite oxide using H2SO4 and KMnO4 and reducing graphene oxide to graphene by using NaBH4. Graphene was then characterized using FT-IR, TEM, AFM, XRD, Raman spectroscopy and solid state NMR. Nafion-Graphene in combination with a mercury film electrode, bismuth film electrode and antimony film electrode was used as a sensing platform for trace metal analysis in 0.1 M acetate buffer (pH 4.6) at 120 s deposition time, using square-wave anodic stripping voltammetry (SWASV). Detection limits were calculated using 3Ïblank/slope. For practical applications recovery studies was done by spiking test samples with known concentrations of metal ions and comparing the results to inductively coupled plasma mass spectrometry (ICPMS). This was then followed by real sample analyses.
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Dhingra, Manuj. "Compressor stability management." Diss., Available online, Georgia Institute of Technology, 2006, 2006. http://etd.gatech.edu/theses/available/etd-01102006-174943/.
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Thesis (Ph. D.)--Aerospace Engineering, Georgia Institute of Technology, 2006.Prasad, J.V.R., Committee Chair ; Neumeier, Yedidia, Committee Member ; Seitzman, Jerry, Committee Member ; Sankar, Lakshmi, Committee Member ; Wadia, Aspi, Committee Member.
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Skočovská, Katarína. "Detekce těžkých kovů v kapalinách metodou spektrometrie laserem buzeného plazmatu." Master's thesis, Vysoké učení technické v Brně. Fakulta strojního inženýrství, 2015. http://www.nusl.cz/ntk/nusl-231994.
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The diploma thesis deals with the use of laser induced breakdown spectroscopy (LIBS) for detection of heavy metals traces, copper and lead, in aqueous solution of copper(II) sulphate pentahydrate and lead(II) ethanoate trihydrate. Results obtained by using single and double-pulse LIBS are compared. The theoretical section focuses on the issue of heavy metals and detection possibilities, describes the fundamental principle of LIBS technique and its modification for liquid analysis. The experimental section describes analyzed samples, the experimental apparatus, double-pulse technique, and method of spectral analysis. The moving breakdown model, which theoretically predicts optimal values of some experimental parameters, is explained briefly in section Optimalizácia. This model has been tested, however the results of experiments did not prove the theory. Furthermore, the experimental section reports the process and results of the optimization of all key measurement parameters and obtaining limits of detection from calibration curves.
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Oranzie, Marlon. "Electrochemical Aptasensing of B-Type Natriuretic Peptide-A Biomarker for Myocardial Infarction." University of the Western Cape, 2019. http://hdl.handle.net/11394/7707.
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>Magister Scientiae - MScinfarction (MI) affects many parts of the western world and in South Africa alone it is estimated that MI is responsible for 1 in 6 deaths (17.3%). Traditional diagnostic methods for MI include an electrocardiograms and blood tests. The problem with these diagnostic methods are that they are time consuming, require large sample volumes, expensive equipment and complicated machinery. To achieve early detection of MI the discovery of specific, sensitive and reliable biomarkers are required. Brain natriuretic peptide (BNP) has been identified as a reliable biomarker for MI due to the fact that it has a defined cutoff of 100 pg/ml and it is not susceptible to patient‘s age which could make early detection of BNP complicated. Early detection methods for BNP has been based on immunoradiometric assays but problems associated with immunoradiometric assays are that there is a restricted availability of antigens and incubation of the labeled antibody could take up to two weeks which affects the patients waiting time on results. Electrochemical biosensors are emerging as early detection method for MI because they can be designed to be sensitive, specific to BNP at a low cost. This research study reported for the first the successful fabrication and implementation of highly sensitive mercaptosuccinic acid capped nickel selenide quantum dots (MSA-NiSe2 QDs) aptasensor for the detection of BNP. The poly-dispersed MSA-NiSe2 QDs were synthesized via an inexpensive, simple and reproducible aqueous microwave assisted irradiation method. The prepared MSA-NiSe2 QDs were characterized by Ultraviolet spectroscopy (UV-Vis), X-ray Diffraction (XRD), Fourier Transform Infrared spectroscopy (FTIR), High Resolution Transmission/Scanning Electron Microscopy (HR TEM/SEM) and Small Angle X-ray Scattering (SAXSpace). The electrochemical properties of the MSA-NiSe2 QDs were investigated by Cylic Voltammetry (CV) and Electrochemical Impedance Spectroscopy (EIS). HR-TEM revealed the formation of small sized MSA-NiSe2 QDs about 4 nm in diameter which was complemented by SAXSpace. UV-Vis studies showed absorption peaks in the ultraviolet region (100-400 nm) confirming the small size of these QDs as well confirming the direct and indirect bandgap of the QDs. XRD confirmed that the QDs are crystalline and belong to the bulk cubic MSA-NiSe2 QDs phase. FTIR studies confirmed the successful capping of MSA on the QDs due to the disappearance of the thiol peak at 2652 cm-1. Electrochemical studies revealed that the MSA-NiSe2 QDs showed good electrochemical properties on screen printed carbon electrodes (SPCE) which allowed them to be used as a mediating platform between the aptamer and SPCE. The successful detection of BNP was achieved by an incubation process between the aptamer drop coated on the MSA-NiSe2 QDs/SPCE surface overnight. The response of the MSA-NiSe2 QDs based aptasensor towards different concentrations of BNP was studied by differential pulse voltammetry (DPV). DPV showed a good linearly with correlation coefficient of R2 = 0.98. DPV also showed a high sensitivity (0.4513 μA/ pg/mL) towards detecting BNP with a detection limit of 11.93 pg/ml. The value of 11.93 pg/ml falls within the negative predictive value range of 10-100 pg/ml for early-stage diagnosis of BNP.
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Badjatya, Vaibhav. "TUNABLE LASER INTERROGATION OF SURFACE PLASMON RESONANCE SENSORS." UKnowledge, 2009. http://uknowledge.uky.edu/gradschool_theses/588.
Full textAbstract:
Surface plasmons are bound TM polarized electromagnetic waves that propagate along the interface of two materials with real dielectric constants of opposite signs. Surface plasmon resonance (SPR) sensors make use of the surface plasmon waves to detect refractive index changes occurring near this interface. For sensing purposes, this interface typically consists of a metal layer, usually gold or silver, and a liquid dielectric. SPR sensors usually measure the shift in resonance wavelength or resonance angle due to index changes adjacent to the metal layer. However this restricts the limit of detection (LOD), as the regions of low slope (intensity vs. wavelength or angle) in the SPR curve contain little information about the resonance. This work presents the technique of tunable laser interrogation of SPR sensors. A semiconductor laser with a typical lasing wavelength of 650nm was used. A 45nm gold layer sputtered on a BK7 glass substrate served as the sensor. The laser wavelength is tuned to always operate in the region of highest slope by using a custom-designed LabVIEW program. It is shown that the sensitivity is maximized and LOD is minimized by operating around the region of high slope on the SPR curve.
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Gilder, Jason R. "Computational methods for the objective review of forensic DNA testing results." Wright State University / OhioLINK, 2007. http://rave.ohiolink.edu/etdc/view?acc_num=wright1183999841.
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Ngwanya, Olwethu. "Molecularly imprinted polymers for detection of volatile organics associated with fuel combustion." University of the Western Cape, 2018. http://hdl.handle.net/11394/6363.
Full textAbstract:
Magister Scientiae - MSc (Chemistry)Pollutants such as polycyclic aromatic hydrocarbons (PAHs) are known for their toxic effects which may lead to the cause of degenerative diseases in both humans and animals. PAHs are widespread in the environment, and may be found in water, food, automotive industry and petrochemical industries to name but a few sources. Literature reports have highlighted industrial workplace exposure to PAHs as a leading cause for development of cancer in workers. Particularly, workers in the petrochemical industry are adversely affected and the incidence of skin and lung cancer in this population group is high. The United States of America in its guidelines developed by environmental protection agency (EPA) has identified 18 PAHs as priority pollutants. Among these are anthracene, benzo[a]pyrene and pyrene which have been selected as the focal point of this study due to their significance in the petrochemical industry. Due to the carcinogenic and mutagenic properties reported in literature for certain PAHs, there have been monitoring procedures taken in most countries around the world. The commonly used analytical methods for the detection of PAHs from industrial samples are high performance liquid chromatography (HPLC) coupled to fluorescence detection, membrane filtration, ozonation and reverse osmosis. Analysis of PAHs from the petrochemical industry is typically performed by HPLC method as well as sono-degredation in the presence of oxygen and hydrogen peroxide.
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Gutierrez, Arenas Omar. "Sensitivity, Noise and Detection of Enzyme Inhibition in Progress Curves." Doctoral thesis, Uppsala universitet, Institutionen för naturvetenskaplig biokemi, 2006. http://urn.kb.se/resolve?urn=urn:nbn:se:uu:diva-6886.
Full textAbstract:
Starting with the development of an enzymatic assay, where an enzyme in solution hydrolysed a solid-phase bound peptide, a model for the kinetics of enzyme action was introduced. This model allowed the estimation of kinetic parameters and enzyme activity for a system that has the peculiarity of not being saturable with the substrate, but with the enzyme. In a derivation of the model, it was found that the sensitivity of the signal to variations in the enzyme concentration had a transient increase along the reaction progress with a maximum at high substrate conversion levels. The same behaviour was derived for the sensitivity in classical homogeneous enzymatic assays and experimental evidence of this was obtained. The impact of the transient increase of the sensitivity on the error structure, and on the ability of homogeneous end-point enzymatic assays to detect competitive inhibition, came into focus. First, a non-monotonous shape in the standard deviation of progress curve data was found and it was attributed to the random dispersion in the enzyme concentration operating through the transient increase in the sensitivity. Second, a model for the detection limit of the quantity Ki/[I] (the IDL-factor) as a function of the substrate conversion level was developed for homogeneous end-point enzymatic assays. It was found that the substrate conversion level where the IDL-factor reached an optimum was beyond the initial velocity range. Moreover, at this optimal point not only the ability to detect inhibitors but also the robustness of the assays was maximized. These results may prove to be relevant in drug discovery for optimising end point homogeneous enzymatic assays that are used to find inhibitors against a target enzyme in compound libraries, which are usually big (>10000) and crowded with irrelevant compounds.
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Gursoy, Gonenc. "Neural Network Based Online Estimation Of Maneuvering Steady States And Control Limits." Master's thesis, METU, 2010. http://etd.lib.metu.edu.tr/upload/12612147/index.pdf.
Full textAbstract:
This thesis concerns the design and development of neural network based predictive algorithms to predict approaching aircraft limits. Therefore, approximate dynamics of flight envelope parameters such as angle of attack and load factor are constructed using neural network augmented dynamic models. Then, constructed models are used to predict steady state responses. By inverting the models and solving for critical controls at the known envelope limits, critical control inputs are calculated as well. The performance of the predictor algorithm
is then evaluated with a different neural network online adaptation law which uses a stack of recorded data. It is shown that using a stack of recorded data online, constructed models become much more representative of limit parameter dynamics compared to adaptation using instantaneous measured data only. The benefits of recording data online and using it for weight adaptation are presented in the scope of dynamic trim and control limit predictions.
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Somerse, Vernon Sydwill. "Mercaptobenzothiazole-on-Gold Biosensor Systems for Organophosphate and Carbamate Pesticide Compounds." Thesis, University of the Western Cape, 2007. http://etd.uwc.ac.za/index.php?module=etd&action=viewtitle&id=gen8Srv25Nme4_1006_1264535891.
Full textAbstract:
This study firstly reports the development, characterisation, and application of thick-film acetylcholinesterase (AChE) biosensors based on a gold electrode modified with a mercaptobenzothiazole (MBT) self-assembled monolayer and either poly(omethoxyaniline) (POMA) or poly(2,5-dimethoxyaniline) (PDMA) in the presence of polystyrene(4-sulphonic acid) (PSSA). The Au/MBT/POMA-PSSA/AChE and Au/MBT/PDMA-PSSA/AChE biosensors were then applied to successfully detect standard organophosphorous and carbamate pesticides in a 0.1 M phosphate buffer, 0.1 M KCl (pH 7.2) solution. Secondly, it reports the construction of the Au/MBT/PANI/AChE/PVAc thick-film biosensor for the determination of certain organophosphate and carbamate pesticide solutions in selected aqueous organic solvent solutions.
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Engström, Adam. "Metal mobility during metamorphism and formation of orogenic gold deposits: Insights from the Dalradian of Scotland." Thesis, Stockholms universitet, Institutionen för geologiska vetenskaper, 2013. http://urn.kb.se/resolve?urn=urn:nbn:se:su:diva-92297.
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Orogenic gold deposits occur within metamorphic belts throughout the world and have through time represented the source for over 25% of the world’s gold production. Although orogenic gold deposits are of great economic importance, controversies exist on the subject of fluid and metal sources and there have been few studies of gold´s distribution and mobility outside of large economic deposits. Research made by Pitcairn et al. (2006), on the Mesozoic Otago and Alpine schists of New Zealand, observed systematic depletion of Au and a suite of 6 associated elements with increasing metamorphic grade. This depletion was identical to the suite of elements enriched in the Otago gold deposits and provided strong evidence that orogenic gold deposits form due to metamorphic processes. The mobilization of metals was attributed to the recrystallization of sulfide minerals during prograde metamorphism causing dehydration and release of metal-rich metamorphic fluids. This thesis is part of a larger project aimed at testing the “Otago model” in a classic metamorphic terrain: The Dalradian metamorphic belt of Scotland. Rocks in the study are from the southern higlands group and the Appin and Argyll group which range in metamorphic grade from chlorite zone greenschist facies to sillimanite zone amphibolite facies. Three main aspects, which supplement earlier research, are addressed in this study: 1) Investigation of the sulfide paragenesis at Loch Lomond and Stonehaven was carried out to map the evolution of sulfides with metamorphic grade and the possible relations to the distribution of gold. Using SEM scanning to quantify the abundance of different sulfide minerals together with previous data on the Glen Esk region, a complex sulfide evolution pattern for the Dalradian Supergroup is identified. The sulfide evolution describes the same changes in texture and chemistry as observed in the Otago Schists but is made complex by the difference in geological evolution for the different regions. 2) Reinvestigation of the higher grade zones of Glen Esk (staurolite to sillimanite) was carried out as samples from the previous study were very weathered. Results from ultralow detection limit methods (HG-AFS and a gold detection method developed by Pitcairn et al. 2006) showed significant systematic depletion of Au and As with metamorphic grade. From chlorite to sillimanite zone average values of Au and As were showed to decrease by 65% and 88% respectively. Furthermore, a suite of 10 major and 12 trace elements were analyzed using ICP methods showing no trends of systematic depletion with increased metamorphic grade. 3) Investigation of Pb-Ag Veining and vein samples from each of the metamorphic index mineral zones in the Glen Esk area was carried out to identify fluid composition and ore mineralogy. Using microthermometry and Raman laser spectroscopy two distinct fluids were identified. The first type is a H2O-CO2-N2-salt fluid of low salinity (0-15 weight percent NaCl equivalent) and medium temperature (150 to 250 °C) locally containing minor amounts of CH4. It is found in the veins from the mineral index zones of Glen Esk and was formed in the ductile regime most likely related to late stage metamorphic devolatilization released during Caledonian uplift of the Dalradian. Pb-Ag veins from the locality of Hardhill host the second fluid type which was formed in the brittle regime accompanied by brecciation as a high salinity (15 to 20 weight percent NaCl equivalent) low temperature (70-140°C) H2O-salt fluid with calcic composition was precipitated. This fluid bears much resemblance to Carboniferous calcic brines responsible for economic base-metal precipitation with widespread occurrence in southwest Scotland and Northern Ireland. Results of this thesis show many similarities with the Otago study, with a connection between metal mobility and metamorphic grade, providing support for the dehydration model as a viable mechanism for the generation of orogenic gold deposits.
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HUNTER, TINA D. "Gibbs Sampling and Expectation Maximization Methods for Estimation of Censored Values from Correlated Multivariate Distributions." University of Cincinnati / OhioLINK, 2008. http://rave.ohiolink.edu/etdc/view?acc_num=ucin1212157899.
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Pipes, Latisha C. "Detection of Illicit Drug Use in Blood: A Validation Study of Solid Phase Extraction Coupled with Liquid Chromatography and Tandem Mass Spectrometry." Bowling Green State University / OhioLINK, 2020. http://rave.ohiolink.edu/etdc/view?acc_num=bgsu1587613608312474.
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Rabus, David. "Résonateurs à ondes élastiques de volume à modes harmoniques élevés (HBARs) pour mesures gravimétriques : application à la détection de gaz." Thesis, Besançon, 2013. http://www.theses.fr/2013BESA2038/document.
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Le besoin d’appareils compacts et autonomes dédiés à la détection d’espèces chimiques pour des analyses de terrain est d’actualité dans un contexte international en rapide mutation (agroalimentaire, développement durable, sécurité, etc.). La thèse présentée au sein de ce manuscrit, financée par la Délégation Générale de l’Armement, développe de nouvelles solutions de capteurs résonants à ondes élastiques de volume à modes harmoniques élevés (HBARs) pour la détection de gaz et plus particulièrement de composés explosifs. Ces résonateurs de très haute compacité se composent d’un transducteur reporté ou déposé sur une cavité résonante multimode, produisant un spectre de raies modulant sa propre réponse fréquentielle. De nature dipolaire, ces résonateurs permettent toutefois la mise au point de quadripôles par couplage latéral de modes mis à profit dans nos travaux. L’étude théorique du comportement de résonateurs à base de niobate de lithium aminci et reporté sur quartz ou fondés sur un empilement de nitrure d’aluminium et de silicium a permis de déterminer les propriétés gravimétriques spécifiques de chaque combinaison de matériaux et des modes associés. Des méthodes de calibrage en phase liquide et gazeuse sont proposées pour valider l’analyse théorique et permettre le choix de la structure la mieux adaptée à une configuration expérimentale donnée. Les résultats obtenus, comparés à ceux d’une microbalance à ondes guidées sur quartz, mettent en évidence les forces (compacité, cinétique chimique réduite, nature multi-physique des mesures) et faiblesses (sensibilité gravimétrique imposant des structures d’épaisseur inférieure à 100 μm) de notre solution face à cette référence. Nous avons également développé une électronique de traitement en boucle ouverte des informations issues de nos dispositifs, permettant des modes de détection rapide ou de haute précision (quelques milli-degrés de variation de phase). L’électronique dédiée a pour vocation de fournir la flexibilité nécessaire au suivi de nombreux modes à diverses fréquences fixes et de s’affranchir des temps longs de balayage en fréquence des analyseurs de réseaux généralistes. Une version à8 voies permet enfin la manipulation de plusieurs capteurs ou l’étude en parallèle des modes de 2 HBARs, donnant ainsi lieu à un système multi-physique efficace associé à des capteurs capables de sonder plusieurs grandeurs dans un volume de très petite dimension (quelques mm3). La limite de détection est déterminée par le bruit de phase de l’oscillateur local. Le système ainsi réalisé est exploité pour la détection de gaz mais aussi pour le pilotage de grandeurs physiques telles que la température ou la viscosité (milieux aqueux) dans différents contextes expérimentauxThe demand for compact and autonomous systems devoted to field detection of gaseous compounds is still persisting in arapidly changing international context (food-processing, sustainable development, security, and so on). The thesis reportedin this manuscript, supported by the Délégation Générale de l’Armement, develops new resonant sensor solutions basedon high overtone bulk acoustic waves (so-called HBARs) for chemical compound detection and more specifically explosivesubstances. These high compactness resonators are built using a transducer bound or deposited onto a resonant cavity,yielding a comb spectrum modulating its own frequency response. They are used generally as dipoles, but a quadrupolestructure allowing for transverse mode coupling has been particularly used for our developments. A theoretical study ofthe behaviour of these devices based on lithium niobate-on-quartz or qluminum nitride-on-silicon material stack has beenachieved to determine the gravimetric properties of these configurations accounting for their mode specificities. Variouscalibration techniques have been implemented to confirm the theoretical analysis and to define the most appropriate structurefor a given application. The produced results have been compared to those of a quartz guided-wave micro-balance toemphasize the strength (compactness, reduced chemical kinetics, multiphysics measurements) and weakness (gravimetricsensitivity requiring device thickness less than 100 μm) of our devices. An embedded signal processing electronics alsohas been developed to treat the information provided by our sensors, offering fast or accurate (millidegree range) detectionprotocols. The dedicated electronics aims at providing the flexibility needed to track multiple modes at variaous fixed frquencieswhile getting rid of the long sweep time of general purpose network analyzers. A eight-channel version of thissystem has been set to process several sensor in parallel or to monitor several modes of two HBAR sensors for effectivemuti-physics measurements in a reduced analysis domain (a few cubic mm). Phase noise is the limiting factor determiningthe detection limit. The system has been deployed for gas detection as well as for monitoring other physical parameters suchas temperature or viscosity under various experimental condition including fluid media
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Ntshongontshi, Nomaphelo. "Molecularly imprinted polymer sensor systems for environmental estrogenic endocrine disrupting chemicals." University of the Western Cape, 2018. http://hdl.handle.net/11394/6241.
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Philosophiae Doctor - PhD (Chemistry)There is growing concern on endocrine disrupting compounds (EDCs). The presence of drugs in water supplies was first realized in Germany in the early 1990s when environmental scientists discovered clofibric acid. Clofibric acid has the ability to lower cholesterol in ground water below a water treatment plant. Endocrine disrupting compounds can be defined as those chemicals with the ability to alter daily functioning of the endocrine system in living organisms. There are numerous molecules that are regarded or referred to as EDCs such as but not limited to organochlorinated pesticides, industrial chemicals, plastics and plasticizers, fuels, estrogens and many other chemicals that are found in the environment or are in widespread use. 17?- estradiol is the principal estrogen found in mammals during reproductive years. Estriol is produced in large quantities during pregnancy. 17?-estradiol is the strongest, estriol the weakest. Estriol is water soluble, estrone and estradiol are not. Although estrogen is produced in women they are also at risk of over exposure to estrogen. Pesticides are extensively used today in agricultural settings to prevent and control pests. Various pesticides, including banned organochlorines (OCs) and modern non-persistent pesticides, have shown the ability to disrupt thyroid activity, disturbing the homeostasis of the thyroid system. Because these EDCs have adverse effects on health of both human and wildlife, it is imperative to develop viable costeffective analytical methods for the detection of these EDCs in complicated samples and at very low concentrations. Very high selectivity towards particular compounds is a very important property for the suitability of a detection method. This is because these compounds mostly coexist in complex matrices which makes the detection of a specific compound very challenging. It is paramount to develop highly sensitive and selective methods for the detection of these estrogens and phosphoric acid-based pesticides at trace levels.
2021-08-31
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Mahmood, Rahimi. "Karatärisering av XRF-mätning med 120kV röntgenrör." Thesis, Mittuniversitetet, Institutionen för elektronikkonstruktion, 2021. http://urn.kb.se/resolve?urn=urn:nbn:se:miun:diva-42590.
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Syftet med denna undersökning är att utvärdera en XRFmätuppställning som använder högre spänning påröntgenröret än konventionella XRF-instrument. Iutvärderingen uppskattas Limit Of Detection (LOD) påtungmetaller genom att använda XRF-metoden, där dettestades olika filter, vinklar och rörspänning och derasinverkan på provet.Metaller med hög densitet kallas för tungmetaller. Vissatungmetaller är livsnödiga men vissa är skadliga för bådemänniskor och naturen. Några exempel på dessa tungmetallerär kvicksilver, kadmium och bly, vilka är farliga grundämnensom människor kan få i sig via föda.Vid utförande av denna undersökning användes enröntgenkälla (30-120keV) som var kopplad till mjukvaransom skickade fotonenergi och ström. En spektrometer med CdTe-detektor användes för att mäta energin på fotonerna från provet. Detektorn var kopplad till mjukvara där det uppmätt spektra kunde observeras och energitopparnas intensitet kunde avläsas. Topparnas intensitet kan härledas tillprovets samansättning. Sedan uppskattades LOD förproverna. Den teknik som jag har studerat ger möjlighet till bättre mätresultat än konventionella XRFutrustningar. Detta eftersom högre rörspänning gör att K-linjerna, inte bara L-linjerna, för tungmetaller kan avläsas
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Schelin, Lina. "Spatial sampling and prediction." Doctoral thesis, Umeå universitet, Institutionen för matematik och matematisk statistik, 2012. http://urn.kb.se/resolve?urn=urn:nbn:se:umu:diva-53286.
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This thesis discusses two aspects of spatial statistics: sampling and prediction. In spatial statistics, we observe some phenomena in space. Space is typically of two or three dimensions, but can be of higher dimension. Questions in mind could be; What is the total amount of gold in a gold-mine? How much precipitation could we expect in a specific unobserved location? What is the total tree volume in a forest area? In spatial sampling the aim is to estimate global quantities, such as population totals, based on samples of locations (papers III and IV). In spatial prediction the aim is to estimate local quantities, such as the value at a single unobserved location, with a measure of uncertainty (papers I, II and V). In papers III and IV, we propose sampling designs for selecting representative probability samples in presence of auxiliary variables. If the phenomena under study have clear trends in the auxiliary space, estimation of population quantities can be improved by using representative samples. Such samples also enable estimation of population quantities in subspaces and are especially needed for multi-purpose surveys, when several target variables are of interest. In papers I and II, the objective is to construct valid prediction intervals for the value at a new location, given observed data. Prediction intervals typically rely on the kriging predictor having a Gaussian distribution. In paper I, we show that the distribution of the kriging predictor can be far from Gaussian, even asymptotically. This motivated us to propose a semiparametric method that does not require distributional assumptions. Prediction intervals are constructed from the plug-in ordinary kriging predictor. In paper V, we consider prediction in the presence of left-censoring, where observations falling below a minimum detection limit are not fully recorded. We review existing methods and propose a semi-naive method. The semi-naive method is compared to one model-based method and two naive methods, all based on variants of the kriging predictor.
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Guo, Jing. "MULTI-MODE SELF-REFERENCING SURFACE PLASMON RESONANCE SENSORS." UKnowledge, 2013. http://uknowledge.uky.edu/ece_etds/13.
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Surface-plasmon-resonance (SPR) sensors are widely used in biological, chemical, medical, and environmental sensing. This dissertation describes the design and development of dual-mode, self-referencing SPR sensors supporting two surface-plasmon modes (long- and short-range) which can differentiate surface binding interactions from bulk index changes at a single sensing location. Dual-mode SPR sensors have been optimized for surface limit of detection (LOD). In a wavelength interrogated optical setup, both surface plasmons are simultaneously excited at the same location and incident angle but at different wavelengths. To improve the sensor performance, a new approach to dual-mode SPR sensing is presented that offers improved differentiation between surface and bulk effects. By using an angular interrogation, both surface plasmons are simultaneously excited at the same location and wavelength but at different angles. Angular interrogation offers at least a factor of 3.6 improvement in surface and bulk cross-sensitivity compared to wavelength-interrogated dual-mode SPR sensors.
Multi-mode SPR sensors supporting at least three surface-plasmon modes can differentiate a target surface effect from interfering surface effects and bulk index changes. This dissertation describes a tri-mode SPR sensor which supports three surface plasmon resonance modes at one single sensing position, where each mode is excited at a different wavelength. The tri-mode SPR sensor can successfully differentiate specific binding from the non-specific binding and bulk index changes.
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HUANG, HE. "REDUCTION OF PERCHLORATE BY ZERO VALENT IRON." University of Cincinnati / OhioLINK, 2005. http://rave.ohiolink.edu/etdc/view?acc_num=ucin1131047520.
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Trolise, Rodrigo Matias. "Desenvolvimento de metodologia para funcionalizar superfícies de ouro com biomoléculas. Construção de biosensor para detecção de citocromo c." Universidade de São Paulo, 2010. http://www.teses.usp.br/teses/disponiveis/46/46131/tde-12042011-135130/.
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Neste trabalho estão apresentadas novas estratégias para funcionalizar superfícies de ouro baseadas na sustentação de bicamadas lipídicas em superfícies de sensores de imagem por Ressonância de Plasmons de Superfície (SPRi) e a construção de um biosensor para detecção de citocromo c. SPRi é uma técnica ótica de gravimetria em tempo real. Por meio de medidas de variações de índice de refração (n) próximas a uma interface, a adsorção e desorção de moléculas podem ser mensuradas. Inicialmente testamos várias estratégias para encontrar um suporte adequado que se ligasse na superfície de ouro e que oferecesse sustentação e estabilidade para a bicamada de fosfolipídeo biotinilado. Estudos de FT-IR e MEV mostraram que a quitosana facilita a formação de uma bicamada íntegra de fosfolipídeos, de tal modo, que a mesma alcança valores de espessura próximos àqueles previstos, ~ 34,5 Å. Além disso, mostramos que esse sistema apresenta vantagens perante outros modelos, tais como, (poli-lisina/fosfolipídeos) e (tiol hidrofóbico/fosfolipídeo). Utilizando-se o complexo químico biotina/estreptoavidina conseguimos imobilizar o anticorpo anti cit c na bicamada, mantendo-o afastado da superfície de ouro. A construção do biosensor foi acompanhada com experimentos de SPRi. O limite de detecção de citocromo c atingido foi de 10-11mol/L. Um sensor construído somente com BSA e anticorpo anti cit c apresentou sensibilidade semelhante. Esta sensibilidade é em torno de três ordens de grandeza superior aos experimentos de imunoblotting usualmente utilizados para detecção de cit c. A principal limitação deste biosensor, tal como de outros imunoensaios, está intimamente ligada às vantagens e desvantagens dos anticorpos como ferramentas analíticas.In this work we developed new strategies to functionalize gold surfaces based on the support of lipid bilayers on the surfaces of surface plasmon resonance imaging sensors (SPRi) and the construction of a biosensor for detection of cytochrome c. SPRi is an optical gravimetric real time technique. Through measurements of changes in refractive index (n) in close proximity to an interface, the adsorption and desorption of molecules can be measured. Initially we tested several strategies for finding a suitable medium that would adsorb on the gold surface and also support and stabilize a biotinylated phospholipid bilayer. Studies of FT-IR and SEM showed that chitosan induces the formation of an intact phospholipid bilayer, so that it reaches thickness values close to those expected, ~ 34.5 Å. Furthermore, we showed that this system has advantages in relation to other models, such as (poli-lisine/phospholipids) and (thiol hydrophobic / phospholipid). Using the chemical complex biotin/streptavidin anti cyt c antibody could be immobilized in the bilayer, keeping it away from the gold surface. The construction of the biosensor was accompanied with SPRi experiments. The limit of detection of cytochrome c was achieved from 10-11mol / L. A sensor built only with BSA and anti cyt c showed similar sensitivity. This sensitivity is about three orders of magnitude higher than the immunoblotting experiments commonly used for detection of cyt c. The main limitation of this biosensor, like in other immunoassays, is linked to the advantages and disadvantages of antibodies as analytical tools.
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Mappa, Charlotte. "Exploration de nouveaux concepts pour les analyses quantitatives et fonctionnelles de microbiotes modèles d'intérêt dual." Thesis, Montpellier, 2018. http://www.theses.fr/2018MONTT055.
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La détection et l’identification de micro-organismes pathogènes est un réel enjeu de santé public tant au niveau alimentaire, que clinique ou d’intérêt national tel qu’illustré en biodéfense. Dans tous ces domaines, il est important d‘avoir des méthodes d’identification et de détection qui soient à la fois rapide, sensible et robuste. Cette thèse a pour objectif de contribuer au développement d’une approche rapide d’identification de micro-organismes sans a priori par spectrométrie de masse en tandem. Cette approche innovante, appelée phylopeptidomique, repose sur l’alliance de la peptidomique, i.e. analyse à large échelle des peptides provenant de la digestion enzymatique d’un échantillon biologique, et de la phylogénie des organismes cellulaires. Après extraction des protéines présentes dans l’échantillon à ausculter, des peptides sont générés et analysés par spectrométrie de masse en tandem. La déconvolution des signaux MS/MS à l’aide du logiciel « µOrg.ID » développé en propre au laboratoire permet d’identifier et quantifier les organismes présents dans l’échantillon en fonction des organismes indexés dans les bases de données. L’étude du protéome de Bacillus atrophaeus, agent simulant de l’anthrax, sous forme sporulée et végétative a permis d’illustrer une méthode d’identification de biomarqueurs protéiques permettant de déterminer le ratio entre les deux formes dans un échantillon. La limite de détection de la phylopeptidomique dans des échantillons purs et des échantillons en mélange équimolaire a été établie sur des bactéries modèles d’intérêts médical et environnemental. La limite de détection de spores de Bacillus atrophaeus en présence de 14 matrices interférentes (alimentaires, environnementales et autres) a permis de mettre en évidence les avantages et limitations de l’approche. Enfin, un mélange artificiel standardisé de 24 organismes a été développé afin d’évaluer les outils de bio-informatique en métaprotéomiqueThe detection and identification of pathogenic microorganisms is a real public health issue for the food industry and the clinics or national interest as illustrated in the biodefense field. Thus, it is important to have identification and detection methods that are fast, sensitive and robust. This PhD thesis aims at contributing to the development of a rapid approach to identify microorganisms without any a priori by tandem mass spectrometry. This innovative approach, called phylopeptidomics, is based on the combination of peptidomics, i.e. large scale analysis of peptides derived from the enzymatic digestion of a biological sample, and the phylogeny of cellular organisms. After extraction of the proteins from the sample of interest, peptides are generated and analyzed by tandem mass spectrometry. The deconvolution of MS/MS signals using the "μOrg.ID" software developed in the laboratory enables the identification and quantification of organisms present in the sample according to the organisms indexed in generalist databases. The study of the proteome of Bacillus atrophaeus, a simulant agent of anthrax, in sporulated and vegetative form, has provided an illustration of a new method of identification of protein biomarkers, which allows determining the ratio between both forms. The limit of detection of phylopeptidomics in pure samples and equimolar mixtures was established with model bacteria of medical and environmental interests. The limit of detection of B. atrophaeus spores in the presence of 14 interfering matrices (food, environmental and others) has highlighted the advantages and limitations of the approach. Finally, a standardized artificial mixture of 24 organisms was developed in order to evaluate bioinformatics tools in metaproteomics
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Shafiullah, Syed N. "On the role of correspondence noise in human visual motion perception. A systematic study on the role of correspondence noise affecting Dmax and Dmin, using random dot kinematograms: A psychophysical and modelling approach." Thesis, University of Bradford, 2008. http://hdl.handle.net/10454/4280.
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One of the major goals of this thesis is to investigate the extent to which correspondence noise, (i.e., the false pairing of dots in adjacent frames) limits motion detection performance in random dot kinematograms (RDKs). The performance measures of interest are Dmax and Dmin i.e., the largest and smallest inter-frame dot displacement, respectively, for which motion can be reliably detected. Dmax and threshold coherence (i.e., the smallest proportion of dots that must be moved between frames for motion to be reliably detected) in RDKs are known to be affected by false pairing or correspondence noise. Here the roles of correspondence noise and receptive field geometry in limiting performance are investigated. The range of Dmax observed in the literature is consistent with the current information-limit based interpretation. Dmin is interpreted in the light of correspondence noise and under-sampling. Based on the psychophysical experiments performed in the early parts of the dissertation, a model for correspondence noise based on the principle of receptive field scaling is developed for Dmax. Model simulations provide a good account of psychophysically estimated Dmax over a range of stimulus parameters, showing that correspondence noise and receptive field geometry have a major influence on displacement thresholds.
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Kunnil, Joseph. "Identification Studies of Bacillus Spores Using Fluorescence Spectroscopy." Thesis, University of Canterbury. Physics and Astronomy, 2005. http://hdl.handle.net/10092/1311.
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Fluorescence spectroscopy was examined as a potential technique for identifying aerosol particles like bacterial spores. This technique was used for laboratory measurements on some common biological agent simulants. We have measured the intrinsic steady-state fluorescence emission spectra as a function of the excitation wavelength for several bacterial spores (washed and unwashed) in dry and aqueous suspensions at room temperature using excitation wavelengths from 200 to 600 nm. These measurements were compared to those of common, naturally occurring biological components like fungal spores and pollen and non spore samples like ovalbumin. The spectra of samples were combined into fluorescence profiles or fluorescence fingerprints. Different substrates were used for collection and detection of spores. Each bacterium produces a unique in vitro fluorescence profile when measured in dried and aqueous suspension and exhibits a strong maximum in its fluorescence emission spectrum near 330-340 nm. The fluorescence profiles were reproducible. The complexity of microorganisms made the interpretation of their spectral signature a difficult task. Principal components analysis (PCA) and cluster analysis were done as a data reduction technique for detection and identification from different backgrounds. PCA illustrates that linear combination of detected fluorescence intensities, which are present in different ratios in each of samples studied, can be used to discriminate biological agent simulants from other biological samples. The hydration effects, washing effects and the role of tryptophan on spore fluorescence were also investigated. The emission spectra of the dried spores showed a maximum near 330 nm, suggesting a hydrophobic environment for its tryptophan residues. The aqueous solution of tryptophan showed fluorescence shifted to 360 nm and in ethanol solution the maximum was shifted to 340 nm, suggesting a rather more polar average location of the tryptophan. To find the limit of detection we measured the quantum efficiency (QE) of a few samples. We concluded that spectroscopy techniques coupled with effective interpretation models are applicable to biological simulants agents. Index Heading: Bacteria; Spores; Identification; Fluorescence; Fluorescence Quantum Efficiency; Principal Components Analysis; Cluster Analysis.
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Shafiullah, Syed Nadeemullah. "On the role of correspondence noise in human visual motion perception : a systematic study on the role of correspondence noise affecting Dmax and Dmin, using random dot kinematograms : a psychophysical and modelling approach." Thesis, University of Bradford, 2008. http://hdl.handle.net/10454/4280.
Full textAbstract:
One of the major goals of this thesis is to investigate the extent to which correspondence noise, (i.e., the false pairing of dots in adjacent frames) limits motion detection performance in random dot kinematograms (RDKs). The performance measures of interest are Dmax and Dmin i.e., the largest and smallest inter-frame dot displacement, respectively, for which motion can be reliably detected. Dmax and threshold coherence (i.e., the smallest proportion of dots that must be moved between frames for motion to be reliably detected) in RDKs are known to be affected by false pairing or correspondence noise. Here the roles of correspondence noise and receptive field geometry in limiting performance are investigated. The range of Dmax observed in the literature is consistent with the current information-limit based interpretation. Dmin is interpreted in the light of correspondence noise and under-sampling. Based on the psychophysical experiments performed in the early parts of the dissertation, a model for correspondence noise based on the principle of receptive field scaling is developed for Dmax. Model simulations provide a good account of psychophysically estimated Dmax over a range of stimulus parameters, showing that correspondence noise and receptive field geometry have a major influence on displacement thresholds.
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Duarte, Flávia Moreno. "Capacidade olfatória e gustativa na doença de Parkinson e nas doenças neurodegenerativas corticais." Universidade Federal de Goiás, 2014. http://repositorio.bc.ufg.br/tede/handle/tede/3911.
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Smell and taste are often impaired by neurodegenerative diseases, however, they have never been studied in association in individuals with cortical and subcortical neurodegenerative diseases in Brazil. This study aimed to evaluate the olfactory and gustative capacity of Parkinson’s disease (PD) individuals, comparing them to a group of subjects with cortical neurodegenerative diseases (CND) and to a control group. It was a cross-sectional study, with convenience sampling. PD individuals were recruited at the Reference Center of Movement Disorders of Clínicas Hospital at the Federal University of Goiás (Centro de Referência em Transtornos do Movimento do Hospital das Clínicas da Universidade Federal de Goiás) (n=80), CND patients were referred from a private clinic of Goiânia (n=20) and the control individuals, at the same age group of PD patients, neurodegenerative disease-free, came from several areas of Clínicas Hospital (n=40). Socio-demographic and clinical data were collected through direct interview and the use of a structured questionnaire including the following variables: gender, age, skin color, schooling, disease duration and stage and life habits. Olfactory capacity was assessed through Sniffin’ Sticks test (odor threshold, discrimination and identification) and gustative capacity through threshold and recognition test of the five basic tastes (sweet, savory, bitter, acid and umami). In order to test the association of olfactory and gustative capacity among the groups, Fisher’s exact test was used. For the comparison of detection and recognition thresholds’ means of basic tastes ANOVA and Kruskal-Wallis were used. PD and CND individuals presented, respectively, 93.8 % and 100 % olfactory compromising and only 15 % of control group individuals presented olfactory reduction, demonstrating statistically significant differences (p<0.001). There were also differences both in detection thresholds as in recognition thresholds of basic tastes among the groups (p<0.001), except for recognition threshold of acid taste (p= 0.088) and umami (p=0.153). Regarding gustative capacity, 53.8 % of PD patients, 50 % of CND individuals and 35 % of control group subjects presented no altered identification of basic tastes, however, there were no significant differences among the groups (p=0.150). It can be concluded that olfactory and gustative capacity in individuals with neurodegenerative diseases, both cortical and subcortical, is compromised and, consequently, presents itself as an important marker of these diseases.
Olfato e paladar estão frequentemente prejudicados nas doenças neurodegenerativas, contudo, nunca foram estudados conjuntamente em indivíduos com doenças neurodegenerativas corticais e subcorticais no Brasil. Este estudo teve como objetivo avaliar a capacidade olfatória e gustativa de indivíduos com doença de Parkinson (DP), comparando-os com um grupo de indivíduos com doenças neurodegenerativas corticais (DNC) e um grupo controle. O desenho do estudo foi transversal, com amostragem por conveniência. Os indivíduos com DP foram recrutados no Centro de Referência em Transtornos do Movimento do Hospital das Clínicas da Universidade Federal de Goiás (n=80), os pacientes com DNC encaminhados de uma clínica particular de Goiânia (n=20) e os controles, da mesma faixa etária do grupo DP, sem doenças neurodegenerativas foram oriundos das diversas áreas do Hospital das Clínicas (n=40). Dados sociodemográficos e clínicos foram coletados por meio de entrevista direta e uso de questionário estruturado abordando as variáveis: gênero, idade, cor da pele, escolaridade, duração e estágio da doença e hábitos de vida. Avaliou-se a capacidade olfatória por meio do teste Sniffin’ Sticks (limiar, discriminação e identificação de odores) e a capacidade gustativa por meio do teste de limiar e de reconhecimento dos cincos gostos básicos (doce, salgado, amargo, ácido e umami). Para testar a associação, da capacidade olfatória e gustativa entre os grupos, utilizou-se teste exato de Fisher. Para comparação de médias dos limites de detecção e de reconhecimento dos gostos básicos utilizou-se ANOVA e Kruskal-Wallis. Os indivíduos com DP e DNC apresentaram, respectivamente, 93,8 % e 100 %, de comprometimento no sentido do olfato e apenas 15 % dos indivíduos controles apresentaram redução no sentido do olfato, com diferenças significativas (p<0,001). Houve também diferenças tanto nos limites de detecção como nos limites de reconhecimento dos gostos básicos entre os grupos (p<0,001), exceto para o limite de reconhecimento do gosto ácido (p= 0,088) e do gosto umami (p=0,153). Em relação à capacidade gustativa, 53,8 % dos pacientes com DP, 50 % dos indivíduos do grupo DNC e 35 % dos indivíduos do grupo controle apresentaram alterações na identificação dos gostos básicos, porém não houve diferenças significativas entre os grupos (p=0,150). Conclui-se que a capacidade olfatória e gustativa em indivíduos com doenças neurodegenerativas, tanto corticais quanto subcorticais, estão comprometidas e, consequentemente, apresentam-se como um marcador importante dessas doenças.
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Feleni, Usisipho. "Quantum dots-amplified electrochemical cytochrome P450 phenotype sensor for tamoxifen, a breast cancer drug." University of the Western Cape, 2017. http://hdl.handle.net/11394/5505.
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Philosophiae Doctor - PhDBreast cancer is regarded as the most common cancer in South Africa and its rate of occurrence is increasing. About one in every 31 South African women are at the risk of developing breast cancer and early diagnosis and treatment guarantee 90% survival rate. Tamoxifen is the drugs of choice for the treatment of all stages of breast cancer. The drug binds with estrogen receptor (ER) to minimize the transcription of estrogen dependent genes. However, nearly 50% of ER-positive breast cancer patients either become resistant or fail to respond to tamoxifen resulting in a serious clinical challenge in breast cancer management. The Grand Health Challenges of South Africa includes the development of cost effective diagnostic systems suitable for early detection of diseases and drug resistivity for timely invention and better patient management.
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Sidwaba, Unathi. "Electrochemical poly(ProDOT) dendritic DNA aptamer biosensor for signalling interferon gamma (IFN-ɣ) TB biomarker." University of the Western Cape, 2017. http://hdl.handle.net/11394/5507.
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Philosophiae Doctor - PhDTuberculosis (TB) is an infectious disease that, despite all efforts devoted towards its eradication, remains a threat to many countries including South Africa. Current diagnostic assays do offer better performance than the conventional sputum smear microscopy and tuberculin skin tests. However, these assays have been proven to be affected by various factors including the condition of an individual's immune system and vaccination history. By far, electrochemical biosensors are amongst the currently investigated techniques to address the shortcomings associated with these diagnostics.
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Gach, Olivier. "Algorithmes mémétiques de détection de communautés dans les réseaux complexes : techniques palliatives de la limite de résolution." Phd thesis, Université du Maine, 2013. http://tel.archives-ouvertes.fr/tel-01037937.
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Les réseaux complexes, issus de relevés de terrain d'origines trèsvariées, en biologie, science de l'information ou sociologie,présentent une caractéristique remarquable dénommée structurecommunautaire. Des groupes, ou communautés, à l'intérieur duréseau, ont une cohésion interne forte et des liens entre eux plusfaibles. Sans connaissance a priori du nombre de communautés, ladifficulté réside dans la caractérisation d'un bon partitionnement encommunautés. La modularité est une mesure globale de qualité departitionnement très utilisée qui capture les contraintes de cohésioninterne forte et de liens externes faibles. Elle transforme le problèmede détection de communautés en problème d'optimisationNP-difficile. Elle souffre d'un défaut, la limite de résolution, qui tendà rendre indétectables les très petites communautés d'autant plusque le réseau est grand. L'algorithme le plus efficace pour optimiserla modularité, dit de Louvain, procède par fusion de communautés.Cette thèse s'attache à modifier cet algorithme pour qu'il réalisemajoritairement des fusions pertinentes, qui n'aggravent pas lalimite de résolution, en utilisant une condition de fusion. De plus, enl'associant à un algorithme mémétique, les partitions proposéessont très proches des partitions attendues pour des graphesgénérés par un modèle qui reproduit les caractéristiques desréseaux complexes. Enfin, cet algorithme mémétique réduitfortement l'inconsistance de solution, défaut de la modularité selonlequel deux partitions trouvées à partir d'un examen des noeudsdans un ordre aléatoire, pour le même graphe, peuvent êtrestructurellement très différentes, rendant leur interprétation délicate.