893 resultados para Design of Experiments and Sample Surveys


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The objective of the research carried out in this report was to observe the first ever in-situ sonochemical reaction in the NMR Spectrometer in the megahertz region of ultrasound. Several reactions were investigated as potential systems for a sonochemical reaction followed by NMR spectroscopy. The primary problem to resolve when applying ultrasound to a chemical reaction is that of heating. Ultrasound causes the liquid to move and produces 'hot spots' resulting in an increase in sample temperature. The problem was confronted by producing a device that would counteract this effect and so remove the need to account for heating. However, the design of the device limited the length of time during which it would function. Longer reaction times were required to enable observations to be carried out in the NMR spectrometer. The fIrst and most obvious reactions attempted were those of the well-known ultrasonic dosimeter. Such a reaction would, theoretically, enable the author to simultaneously observe a reaction and determine the exact power entering the system for direct comparison of results. Unfortunately, in order to monitor the reactions in the NMR spectrometer the reactant concentrations had to be signifIcantly increased, which resulted in a notable increase in reaction time, making the experiment too lengthy to follow in the time allocated. The Diels-Alder Reaction is probably one of the most highly investigated reaction systems in the field of chemistry and it was this to which the author turned her attention. Previous authors have carried out ultrasonic investigations, with considerable success, for the reaction of anthracene with maleic anhydride. It was this reaction in particular that was next attempted. The first ever sonochemically enhanced reaction using a frequency of ultrasound in the megahertz (MHz) region was successfully carried out as bench experiments. Due to the complexity of the component reactants the product would precipitate from the solution and because the reaction could only be monitored by its formation, it was not possible to observe the reaction in the NMR spectrometer. The solvolysis of 2-chloro-2-methylpropane was examined in various solvent systems; the most suitable of which was determined to be aqueous 2-methylpropan-2-ol. The experiment was successfully enhanced by the application of ultrasound and monitored in-situ in the NMR spectrometer. The increase in product formation of an ultrasonic reaction over that of a traditional thermal reaction occurred. A range of 1.4 to 2.9 fold improvement was noted, dependent upon the reaction conditions investigated. An investigation into the effect of sonication upon a large biological molecule, in this case aqueous lysozyme, was carried out. An easily observed effect upon the sample was noted but no explanation for the observed effects could be established.

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Tne object of this research was to investigate the behaviour of birdcage scaffolding as used in falsework structures, assess the suitability of existing design methods and make recommendations for a set of design rules. Since excessive deflection is as undesirable in a structure as total collapse, the project was divided into two sections. These were to determine the ultimate vertical and horizontal load-carrying capacity and also the deflection characteristics of any falsework. So theoretical analyses were developed to ascertain the ability of both the individual standards to resist vertical load, and of the bracing to resist horizontal load.Furthermore a model was evolved which would predict the horizontal deflection of a scaffold under load using strain energy methods. These models were checked by three series of experiments. The first was on individual standards under vertical load only. The second series was carried out on full scale falsework structures loading vertically and horizontally to failure. Finally experiments were conducted on scaffold couplers to provide additional verification of the method of predicting deflections. This thesis gives the history of the project and an introduction into the field of scaffolding. It details both the experiments conducted and the theories developed and the correlation between theory and experiment. Finally it makes recommendations for a design method to be employed by scaffolding designers.

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This study identifies and investigates the potential use of in-eye trigger mechanisms to supplement the widely available information on release of ophthalmic drugs from contact lenses under passive release conditions. Ophthalmic dyes and surrogates have been successfully employed to investigate how these factors can be drawn together to make a successful system. The storage of a drug-containing lens in a pH lower than that of the ocular environment can be used to establish an equilibrium that favours retention of the drug in the lens prior to ocular insertion. Although release under passive conditions does not result in complete dye elution, the use of mechanical agitation techniques which mimic the eyelid blink action in conjunction with ocular tear chemistry promotes further release. In this way differentiation between passive and triggered in vitro release characteristics can be established. Investigation of the role of individual tear proteins revealed significant differences in their ability to alter the equilibrium between matrix-held and eluate-held dye or drug. These individual experiments were then investigated in vivo using ophthalmic dyes. Complete elution was found to be achievable in-eye; this demonstrated the importance of that fraction of the drug retained under passive conditions and the triggering effect of in-eye conditions on the release process. Understanding both the structure-property relationship between drug and material and in-eye trigger mechanisms, using ophthalmic dyes as a surrogate, provides the basis of knowledge necessary to design ocular drug delivery vehicles for in-eye release in a controllable manner.

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During the remediation of burial grounds at the US Department of Energy's (DOE's) Hanford Site in Washington State, the dispersion of contaminated soil particles and dust is an issue that is faced by site workers on a daily basis. This contamination problem is even more of a concern when one takes into account the semi-arid characteristics of the region where the site is located. To mitigate this problem, workers at the site use a variety of engineered methods to minimize the dispersion of contaminated soil and dust (i.e. use of water and/or suppression agents that stabilizes the soil prior to soil excavation, segregation, and removal activities). A primary contributor to the dispersion of contaminated soil and dust is wind soil erosion. The erosion process occurs when the wind speed exceeds a certain threshold value which depends on a number of factors including wind force loading, particle size, surface soil moisture, and the geometry of the soil. Thus under these circumstances, the mobility of contaminated soil and generation and dispersion of particulate matter are significantly influenced by these parameters. This dependence of soil and dust movement on threshold shear velocity, fixative dilution and/or application rates, soil moisture content, and soil geometry were studied for Hanford's sandy soil through a series of wind tunnel experiments, laboratory experiments and theoretical analysis. In addition, the behavior of plutonium (Pu) powder contamination in the soil was studied by introducing a Pu simulant (cerium oxide). The results showed that soil dispersion and PM10 concentrations decreased with increasing soil moisture. Also, it was shown that the mobility of the soil was affected by increasing wind velocity. It was demonstrated that the use of fixative products greatly decreased the amount of soil and PM10 concentrations when exposed to varying wind conditions. In addition, it was shown that geometry of the soil sample affected the velocity profile and calculation of roughness surface coefficient when comparing round and flat soil samples. Finally, threshold shear velocities were calculated for soil with flat surface and their dependency on surface soil moisture was demonstrated. A theoretical framework was developed to explain these dependencies.

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The presence of inhibitory substances in biological forensic samples has, and continues to affect the quality of the data generated following DNA typing processes. Although the chemistries used during the procedures have been enhanced to mitigate the effects of these deleterious compounds, some challenges remain. Inhibitors can be components of the samples, the substrate where samples were deposited or chemical(s) associated to the DNA purification step. Therefore, a thorough understanding of the extraction processes and their ability to handle the various types of inhibitory substances can help define the best analytical processing for any given sample. A series of experiments were conducted to establish the inhibition tolerance of quantification and amplification kits using common inhibitory substances in order to determine if current laboratory practices are optimal for identifying potential problems associated with inhibition. DART mass spectrometry was used to determine the amount of inhibitor carryover after sample purification, its correlation to the initial inhibitor input in the sample and the overall effect in the results. Finally, a novel alternative at gathering investigative leads from samples that would otherwise be ineffective for DNA typing due to the large amounts of inhibitory substances and/or environmental degradation was tested. This included generating data associated with microbial peak signatures to identify locations of clandestine human graves. Results demonstrate that the current methods for assessing inhibition are not necessarily accurate, as samples that appear inhibited in the quantification process can yield full DNA profiles, while those that do not indicate inhibition may suffer from lowered amplification efficiency or PCR artifacts. The extraction methods tested were able to remove >90% of the inhibitors from all samples with the exception of phenol, which was present in variable amounts whenever the organic extraction approach was utilized. Although the results attained suggested that most inhibitors produce minimal effect on downstream applications, analysts should practice caution when selecting the best extraction method for particular samples, as casework DNA samples are often present in small quantities and can contain an overwhelming amount of inhibitory substances.

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As the concept of renewable energy becomes increasingly important in the modern society, a considerable amount of research has been conducted in the field of organic photovoltaics in recent years. Although organic solar cells generally have had lower efficiencies compared to silicon solar cells, they have the potential to be mass produced via solution processing. A common polymer solar cell architecture relies on the usage of P3HT (electron donor) and PCBM (electron acceptor) bulk heterojunction. One of the main issues with this configuration is that in order to compensate for the high exciton recombination rate, the photoactive layer is often made very thin (on the order of 100 $%). This results in low solar cell photocurrents due to low absorption. This thesis investigates a novel method of light trapping by coupling surface plasmons at the electrode interface via surface relief gratings, leading to EM field enhancements and increased photo absorption. Experimental work was first conducted on developing and optimizing a transparent electrode of the form &'()/+,/&'() to replace the traditional ITO electrode since the azopolymer gratings cannot withstand the high temperature processing of ITO films. It was determined that given the right thickness profiles and deposition conditions, the MAM stack can achieve transmittance and conductivity similar to ITO films. Experimental work was also conducted on the fabrication and characterization of surface relief gratings, as well as verification of the surface plasmon generation. Surface relief gratings were fabricated easily and accurately via laser interference lithography on photosensitive azopolymer films. Laser diffraction studies confirmed the grating pitch, which is dependent on the incident angle and wavelength of the writing beam. AFM experiments were conducted to determine the surface morphology of the gratings, before and after metallic film deposition. It was concluded that metallic film deposition does not significantly alter the grating morphologies.

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As the concept of renewable energy becomes increasingly important in the modern society, a considerable amount of research has been conducted in the field of organic photovoltaics in recent years. Although organic solar cells generally have had lower efficiencies compared to silicon solar cells, they have the potential to be mass produced via solution processing. A common polymer solar cell architecture relies on the usage of P3HT (electron donor) and PCBM (electron acceptor) bulk heterojunction. One of the main issues with this configuration is that in order to compensate for the high exciton recombination rate, the photoactive layer is often made very thin (on the order of 100 $%). This results in low solar cell photocurrents due to low absorption. This thesis investigates a novel method of light trapping by coupling surface plasmons at the electrode interface via surface relief gratings, leading to EM field enhancements and increased photo absorption. Experimental work was first conducted on developing and optimizing a transparent electrode of the form &'()/+,/&'() to replace the traditional ITO electrode since the azopolymer gratings cannot withstand the high temperature processing of ITO films. It was determined that given the right thickness profiles and deposition conditions, the MAM stack can achieve transmittance and conductivity similar to ITO films. Experimental work was also conducted on the fabrication and characterization of surface relief gratings, as well as verification of the surface plasmon generation. Surface relief gratings were fabricated easily and accurately via laser interference lithography on photosensitive azopolymer films. Laser diffraction studies confirmed the grating pitch, which is dependent on the incident angle and wavelength of the writing beam. AFM experiments were conducted to determine the surface morphology of the gratings, before and after metallic film deposition. It was concluded that metallic film deposition does not significantly alter the grating morphologies.

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Le rapide déclin actuel de la biodiversité est inquiétant et les activités humaines en sont la cause directe. De nombreuses aires protégées ont été mises en place pour contrer cette perte de biodiversité. Afin de maximiser leur efficacité, l’amélioration de la connectivité fonctionnelle entre elles est requise. Les changements climatiques perturbent actuellement les conditions environnementales de façon globale. C’est une menace pour la biodiversité qui n’a pas souvent été intégrée lors de la mise en place des aires protégées, jusqu’à récemment. Le mouvement des espèces, et donc la connectivité fonctionnelle du paysage, est impacté par les changements climatiques et des études ont montré qu’améliorer la connectivité fonctionnelle entre les aires protégées aiderait les espèces à faire face aux impacts des changements climatiques. Ma thèse présente une méthode pour concevoir des réseaux d’aires protégées tout en tenant compte des changements climatiques et de la connectivité fonctionnelle. Mon aire d’étude est la région de la Gaspésie au Québec (Canada). La population en voie de disparition de caribou de la Gaspésie-Atlantique (Rangifer tarandus caribou) a été utilisée comme espèce focale pour définir la connectivité fonctionnelle. Cette petite population subit un déclin continu dû à la prédation et la modification de son habitat, et les changements climatiques pourraient devenir une menace supplémentaire. J’ai d’abord construit un modèle individu-centré spatialement explicite pour expliquer et simuler le mouvement du caribou. J’ai utilisé les données VHF éparses de la population de caribou et une stratégie de modélisation patron-orienté pour paramétrer et sélectionner la meilleure hypothèse de mouvement. Mon meilleur modèle a reproduit la plupart des patrons de mouvement définis avec les données observées. Ce modèle fournit une meilleure compréhension des moteurs du mouvement du caribou de la Gaspésie-Atlantique, ainsi qu’une estimation spatiale de son utilisation du paysage dans la région. J’ai conclu que les données éparses étaient suffisantes pour ajuster un modèle individu-centré lorsqu’utilisé avec une modélisation patron-orienté. Ensuite, j’ai estimé l’impact des changements climatiques et de différentes actions de conservation sur le potentiel de mouvement du caribou. J’ai utilisé le modèle individu-centré pour simuler le mouvement du caribou dans des paysages hypothétiques représentant différents scénarios de changements climatiques et d’actions de conservation. Les actions de conservation représentaient la mise en place de nouvelles aires protégées en Gaspésie, comme définies par le scénario proposé par le gouvernement du Québec, ainsi que la restauration de routes secondaires à l’intérieur des aires protégées. Les impacts des changements climatiques sur la végétation, comme définis dans mes scénarios, ont réduit le potentiel de mouvement du caribou. La restauration des routes était capable d’atténuer ces effets négatifs, contrairement à la mise en place des nouvelles aires protégées. Enfin, j’ai présenté une méthode pour concevoir des réseaux d’aires protégées efficaces et j’ai proposé des nouvelles aires protégées à mettre en place en Gaspésie afin de protéger la biodiversité sur le long terme. J’ai créé de nombreux scénarios de réseaux d’aires protégées en étendant le réseau actuel pour protéger 12% du territoire. J’ai calculé la représentativité écologique et deux mesures de connectivité fonctionnelle sur le long terme pour chaque réseau. Les mesures de connectivité fonctionnelle représentaient l’accès général aux aires protégées pour le caribou de la Gaspésie-Atlantique ainsi que son potentiel de mouvement à l’intérieur. J’ai utilisé les estimations de potentiel de mouvement pour la période de temps actuelle ainsi que pour le futur sous différents scénarios de changements climatiques pour représenter la connectivité fonctionnelle sur le long terme. Le réseau d’aires protégées que j’ai proposé était le scénario qui maximisait le compromis entre les trois caractéristiques de réseau calculées. Dans cette thèse, j’ai expliqué et prédit le mouvement du caribou de la Gaspésie-Atlantique sous différentes conditions environnementales, notamment des paysages impactés par les changements climatiques. Ces résultats m’ont aidée à définir un réseau d’aires protégées à mettre en place en Gaspésie pour protéger le caribou au cours du temps. Je crois que cette thèse apporte de nouvelles connaissances sur le comportement de mouvement du caribou de la Gaspésie-Atlantique, ainsi que sur les actions de conservation qui peuvent être prises en Gaspésie afin d’améliorer la protection du caribou et de celle d’autres espèces. Je crois que la méthode présentée peut être applicable à d’autres écosystèmes aux caractéristiques et besoins similaires.

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Targeted cancer therapy aims to disrupt aberrant cellular signalling pathways. Biomarkers are surrogates of pathway state, but there is limited success in translating candidate biomarkers to clinical practice due to the intrinsic complexity of pathway networks. Systems biology approaches afford better understanding of complex, dynamical interactions in signalling pathways targeted by anticancer drugs. However, adoption of dynamical modelling by clinicians and biologists is impeded by model inaccessibility. Drawing on computer games technology, we present a novel visualisation toolkit, SiViT, that converts systems biology models of cancer cell signalling into interactive simulations that can be used without specialist computational expertise. SiViT allows clinicians and biologists to directly introduce for example loss of function mutations and specific inhibitors. SiViT animates the effects of these introductions on pathway dynamics, suggesting further experiments and assessing candidate biomarker effectiveness. In a systems biology model of Her2 signalling we experimentally validated predictions using SiViT, revealing the dynamics of biomarkers of drug resistance and highlighting the role of pathway crosstalk. No model is ever complete: the iteration of real data and simulation facilitates continued evolution of more accurate, useful models. SiViT will make accessible libraries of models to support preclinical research, combinatorial strategy design and biomarker discovery.

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This paper presents the development and evaluation of PICTOAPRENDE, which is an interactive software designed to improve oral communication. Additionally, it contributes to the development of children and youth who are diagnosed with autism spectrum disorder (ASD) in Ecuador. To fulfill this purpose initially analyzes the intervention area where the general characteristics of people with ASD and their status in Ecuador is described. Statistical techniques used for this evaluation constitutes the basis of this study. A section that presents the development of research-based cognitive and social parameters of the area of intervention is also shown. Finally, the algorithms to obtain the measurements and experimental results along with the analysis of them are presented.

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We describe a new geometry for electrostatic actuators to be used in sensitive laser interferometers, suited for prototype and table top experiments related to gravitational wave detection with mirrors of 100 g or less. The arrangement consists of two plates at the sides of the mirror (test mass), and therefore does not reduce its clear aperture as a conventional electrostatic drive (ESD) would do. Using the sample case of the AEI-10 m prototype interferometer, we investigate the actuation range and the influence of the relative misalignment of the ESD plates with respect to the test mass. We find that in the case of the AEI-10 m prototype interferometer, this new kind of ESD could provide a range of 0.28 mu m when operated at a voltage of 1 kV. In addition, the geometry presented is shown to provide a reduction factor of about 100 in the magnitude of the actuator motion coupling to the test mass displacement. We show that therefore in the specific case of the AEI-10 m interferometer, it is possible to mount the ESD actuators directly on the optical table without spoiling the seismic isolation performance of the triple stage suspension of the main test masses.

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The aim of this thesis is to review and augment the theory and methods of optimal experimental design. In Chapter I the scene is set by considering the possible aims of an experimenter prior to an experiment, the statistical methods one might use to achieve those aims and how experimental design might aid this procedure. It is indicated that, given a criterion for design, a priori optimal design will only be possible in certain instances and, otherwise, some form of sequential procedure would seem to be indicated. In Chapter 2 an exact experimental design problem is formulated mathematically and is compared with its continuous analogue. Motivation is provided for the solution of this continuous problem, and the remainder of the chapter concerns this problem. A necessary and sufficient condition for optimality of a design measure is given. Problems which might arise in testing this condition are discussed, in particular with respect to possible non-differentiability of the criterion function at the design being tested. Several examples are given of optimal designs which may be found analytically and which illustrate the points discussed earlier in the chapter. In Chapter 3 numerical methods of solution of the continuous optimal design problem are reviewed. A new algorithm is presented with illustrations of how it should be used in practice. It is shown that, for reasonably large sample size, continuously optimal designs may be approximated to well by an exact design. In situations where this is not satisfactory algorithms for improvement of this design are reviewed. Chapter 4 consists of a discussion of sequentially designed experiments, with regard to both the philosophies underlying, and the application of the methods of, statistical inference. In Chapter 5 we criticise constructively previous suggestions for fully sequential design procedures. Alternative suggestions are made along with conjectures as to how these might improve performance. Chapter 6 presents a simulation study, the aim of which is to investigate the conjectures of Chapter 5. The results of this study provide empirical support for these conjectures. In Chapter 7 examples are analysed. These suggest aids to sequential experimentation by means of reduction of the dimension of the design space and the possibility of experimenting semi-sequentially. Further examples are considered which stress the importance of the use of prior information in situations of this type. Finally we consider the design of experiments when semi-sequential experimentation is mandatory because of the necessity of taking batches of observations at the same time. In Chapter 8 we look at some of the assumptions which have been made and indicate what may go wrong where these assumptions no longer hold.

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This thesis details the design and applications of a terahertz (THz) frequency comb spectrometer. The spectrometer employs two offset locked Ti:Sapphire femtosecond oscillators with repetition rates of approximately 80 MHz, offset locked at 100 Hz to continuously sample a time delay of 12.5 ns at a maximum time delay resolution of 15.6 fs. These oscillators emit continuous pulse trains, allowing the generation of a THz pulse train by the master, or pump, oscillator and the sampling of this THz pulse train by the slave, or probe, oscillator via the electro-optic effect. Collecting a train of 16 consecutive THz pulses and taking the Fourier transform of this pulse train produces a decade-spanning frequency comb, from 0.25 to 2.5 THz, with a comb tooth width of 5 MHz and a comb tooth spacing of ~80 MHz. This frequency comb is suitable for Doppler-limited rotational spectroscopy of small molecules. Here, the data from 68 individual scans at slightly different pump oscillator repetition rates were combined, producing an interleaved THz frequency comb spectrum, with a maximum interval between comb teeth of 1.4 MHz, enabling THz frequency comb spectroscopy.

The accuracy of the THz frequency comb spectrometer was tested, achieving a root mean square error of 92 kHz measuring selected absorption center frequencies of water vapor at 10 mTorr, and a root mean square error of 150 kHz in measurements of a K-stack of acetonitrile. This accuracy is sufficient for fitting of measured transitions to a model Hamiltonian to generate a predicted spectrum for molecules of interest in the fields of astronomy and physical chemistry. As such, the rotational spectra of methanol and methanol-OD were acquired by the spectrometer. Absorptions from 1.3 THz to 2.0 THz were compared to JPL catalog data for methanol and the spectrometer achieved an RMS error of 402 kHz, improving to 303 kHz when excluding low signal-to-noise absorptions. This level of accuracy compares favorably with the ~100 kHz accuracy achieved by JPL frequency multiplier submillimeter spectrometers. Additionally, the relative intensity performance of the THz frequency comb spectrometer is linear across the entire decade-spanning bandwidth, making it the preferred instrument for recovering lineshapes and taking absolute intensity measurements in the THz region. The data acquired by the Terahertz Frequency Comb Spectrometer for methanol-OD is of comparable accuracy to the methanol data and may be used to refine the fit parameters for the predicted spectrum of methanol-OD.

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The presence of inhibitory substances in biological forensic samples has, and continues to affect the quality of the data generated following DNA typing processes. Although the chemistries used during the procedures have been enhanced to mitigate the effects of these deleterious compounds, some challenges remain. Inhibitors can be components of the samples, the substrate where samples were deposited or chemical(s) associated to the DNA purification step. Therefore, a thorough understanding of the extraction processes and their ability to handle the various types of inhibitory substances can help define the best analytical processing for any given sample. A series of experiments were conducted to establish the inhibition tolerance of quantification and amplification kits using common inhibitory substances in order to determine if current laboratory practices are optimal for identifying potential problems associated with inhibition. DART mass spectrometry was used to determine the amount of inhibitor carryover after sample purification, its correlation to the initial inhibitor input in the sample and the overall effect in the results. Finally, a novel alternative at gathering investigative leads from samples that would otherwise be ineffective for DNA typing due to the large amounts of inhibitory substances and/or environmental degradation was tested. This included generating data associated with microbial peak signatures to identify locations of clandestine human graves. Results demonstrate that the current methods for assessing inhibition are not necessarily accurate, as samples that appear inhibited in the quantification process can yield full DNA profiles, while those that do not indicate inhibition may suffer from lowered amplification efficiency or PCR artifacts. The extraction methods tested were able to remove >90% of the inhibitors from all samples with the exception of phenol, which was present in variable amounts whenever the organic extraction approach was utilized. Although the results attained suggested that most inhibitors produce minimal effect on downstream applications, analysts should practice caution when selecting the best extraction method for particular samples, as casework DNA samples are often present in small quantities and can contain an overwhelming amount of inhibitory substances.^

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This paper revisits the design of L and S band bridged loop-gap resonators (BLGRs) for electron paramagnetic resonance applications. A novel configuration is described and extensively characterized for resonance frequency and quality factor as a function of the geometrical parameters of the device. The obtained experimental results indicate higher values of the quality factor (Q) than previously reported in the literature, and the experimental analysis data should provide useful guidelines for BLGR design.