Innovative method for carbon dioxide determination in human postmortem cardiac gas samples using headspace-gas chromatography-mass spectrometry and stable labeled isotope as internal standard.

A novel approach to measure carbon dioxide (CO2) in gaseous samples, based on a precise and accurate quantification by (13)CO2 internal standard generated in situ is presented. The main goal of this study was to provide an innovative headspace-gas chromatography-mass spectrometry (HS-GC-MS) method applicable in the routine determination of CO2. The main drawback of the GC methods discussed in the literature for CO2 measurement is the lack of a specific internal standard necessary to perform quantification. CO2 measurement is still quantified by external calibration without taking into account analytical problems which can often occur considering gaseous samples. To avoid the manipulation of a stable isotope-labeled gas, we have chosen to generate in situ an internal labeled standard gas ((13)CO2) on the basis of the stoichiometric formation of CO2 by the reaction of hydrochloric acid (HCl) with sodium hydrogen carbonate (NaH(13)CO3). This method allows a precise measurement of CO2 concentration and was validated on various human postmortem gas samples in order to study its efficiency.

Multilayer perceptron with local constraint as an emerging method in spatial data analysis

The use of Geographic Information Systems has revolutionalized the handling and the visualization of geo-referenced data and has underlined the critic role of spatial analysis. The usual tools for such a purpose are geostatistics which are widely used in Earth science. Geostatistics are based upon several hypothesis which are not always verified in practice. On the other hand, Artificial Neural Network (ANN) a priori can be used without special assumptions and are known to be flexible. This paper proposes to discuss the application of ANN in the case of the interpolation of a geo-referenced variable.

Investigation of Postmortem Gases: A Forensic Imaging and Analytical Chemistry Approach

Background: Distinguishing postmortem gas accumulations in the body due to natural decomposition and other phenomena such as gas embolism can prove a difficult task using purely Multi-Detector Computed Tomography (MDCT). The Radiological Alteration Index (RAI) was created with the intention to be able to identify bodies undergoing the putrefaction process based on the quantity of gas detected within the body. The flaw in this approach is the inability to absolutely determine putrefaction as the origin of gas volumes in cases of moderate alteration. The aim of the current study is to identify percentage compositions of O2, N2, CO2 and the presence of gases such as H2 and H2S within these sampling sites in order to resolve this complication. Materials and methods: All cases investigated in our University Center of Legal Medicine are undergoing a Post-Mortem Computed Tomography (PMCT)-scan before external examination or autopsy as a routine investigation. In the obtained images, areas of gas were characterized as 0, I, II or III based on the amount of gas present according to the RAI (1). The criteria for these characterizations were dependent of the site of gas, for example thoracic and abdominal cavities were graded as I (1 - 3cm gas), II (3 - 5cm gas) and III (>5cm gas). Cases showing gaseous sites with grade II or III were selected for this study. The sampling was performed under CT-guidance to target the regions to be punctured. Luer-lock PTFE syringes equipped with a three-way valve and needles were used to sample the gas directly (2). Gaseous samples were then analysed using gas chromatography coupled to a thermal conductivity detector (GC-TCD). The components present in the samples were expressed as a percentage of the overall gas present. Results: Up to now, we have investigated more than 40 cases using our standardized procedure for sampling and analysis of gas. O2, N2 and CO2 were present in most samples. The following distributions were found to correlate to gas origins of gas embolism/scuba diving accidents, trauma and putrefaction: ? Putrefaction → O2 = 1 - 5%; CO2 > 15%; N2 = 10 - 70%; H2 / H2S / CH4 variable presence ? Gas embolism/Scuba diving accidents → O2 and N2= varying percentages; CO2 > 20% ? Trauma → O2 = small percentage; CO2 < 15%; N2 > 65% H2 and H2S indicated levels of putrefaction along with methane which can also gauge environmental conditions or conditions of body storage/burial. Many cases showing large RAI values (advanced alteration) did reveal a radiological diagnosis which was in concordance with the interpretation of the gas composition. However, in certain cases (gas embolism, scuba divers) radiological interpretation was not possible and only chemical gas analysis was found to lead to the correct diagnosis, meaning that it provided complementary information to the radiological diagnosis. Conclusion: Investigation of postmortem gases is a useful tool to determine origin of gas generation which can aid the diagnosis of the cause of death. Levels of gas can provide information on stage of putrefaction and help to perform essential medico-legal diagnosis such as vital gas embolism.

Intestinal content detection in capsule endoscopy using robust features

This work covers two aspects. First, it generally compares and summarizes the similarities and differences of state of the art feature detector and descriptor and second it presents a novel approach of detecting intestinal content (in particular bubbles) in capsule endoscopy images. Feature detectors and descriptors providing invariance to change of perspective, scale, signal-noise-ratio and lighting conditions are important and interesting topics in current research and the number of possible applications seems to be numberless. After analysing a selection of in the literature presented approaches, this work investigates in their suitability for applications information extraction in capsule endoscopy images. Eventually, a very good performing detector of intestinal content in capsule endoscopy images is presented. A accurate detection of intestinal content is crucial for all kinds of machine learning approaches and other analysis on capsule endoscopy studies because they occlude the field of view of the capsule camera and therefore those frames need to be excluded from analysis. As a so called “byproduct” of this investigation a graphical user interface supported Feature Analysis Tool is presented to execute and compare the discussed feature detectors and descriptor on arbitrary images, with configurable parameters and visualized their output. As well the presented bubble classifier is part of this tool and if a ground truth is available (or can also be generated using this tool) a detailed visualization of the validation result will be performed.

Theoretical aspects of graph models for MANETs

We survey the main theoretical aspects of models for Mobile Ad Hoc Networks (MANETs). We present theoretical characterizations of mobile network structural properties, different dynamic graph models of MANETs, and finally we give detailed summaries of a few selected articles. In particular, we focus on articles dealing with connectivity of mobile networks, and on articles which show that mobility can be used to propagate information between nodes of the network while at the same time maintaining small transmission distances, and thus saving energy.

Sistemes lidar (radar laser) d'ona contínua i baixa potència per a la detecció i mesura de concentració de gasos amb resolució espacial

The present project has performed the study and development of a new technique for the detection of gases with range resolution. This technique called FMCW-lidar is a technique that evolves from the FMCW-radar technique to be applied to lidar systems. Moreover, it takes advantage of the appearance of spectral absorption lines because of the interaction between light and gases to tune the light wavelength of a laser emitter with one of this spectral lines and then detects the backscattered light and analyzes it in order to obtain gas concentration measurements. The first part of the project consisted in the analysis of the WMS technique which is a technique for the in-situ measurement of gases. A complete theoretical analysis has been performed and some experiments have been carried out in order to test the technique and to validate its application to an FMCW-modulated system for the detection of gases. The second part of the project consisted in the analysis of the lidar FMCW technique for solid target detection and its extension to continuous media. The classical form of this technique has been analyzed for a distributed medium and a filtering effect has been found which prevents the accurate acquisition of the medium response. A modification of the technique has been proposed and a validation via simulations and some experiments has been carried on. After performing these tests, a novel system is proposed to be developed and tested in order to perform the indicated gas detection with range resolution.

Diseño y desarrollo de un equipo de caracterización de ISFET para la medida de analitos iónicos

En este proyecto se desarrolla una unidad de medida para investigar la cuantificación de la concentración de analitos iónicos en análisis clínico mediante sensores ISFET. Para su desarrollo se precisa de un elemento que simule el comportamiento de un ISFET por lo que también se desarrolla un simulador de ISFET. Para realizar la unidad de medida se diseñan unos circuitos SMU que permiten polarizar en tensión y medir la corriente de cada terminal de un ISFET y del electrodo de referencia que actúa de puerta. El simulador se realiza con un MOSFET de la misma geometría que el ISFET y dos generadores de tensión programables. Desarrollados y validados los circuitos correspondientes, obtenemos unos excelentes resultados en el simulador que se revela de gran utilidad para la puesta en marcha de la unidad de medida, la cual ofrece unos resultados bastante buenos, si bien se aprecian ciertas corrientes de fuga que no permiten alcanzar toda la exactitud que se pretendía. Ello es debido a los circuitos impresos que deberán ser mejorados hasta conseguir la exactitud deseada. Sin embargo pueden darse por válidos los circuitos de medida diseñados.

Aspectos metabólicos y multivitamínicos del maíz

La deficiencia de vitamina A causa 2.2 millones de muertes al año. Por tanto, investigadores intentan elevar el contenido de β-caroteno y otros carotenoides en cereales mediante la ingeniería genética. Mi trabajo consistió en analizar carotenoides en maíz y callos de arroz transgénico con el fin de indentificar y cuantificar estos pigmentos y además analizar la ruta metabólica de los mismos. Por tal motivo, desarrollaré una técnica analítica por HPLC y UHPLC que me permitió separar la mezcla de carotenoides. Estas moléculas se detectaton utilizando un detector de arreglo de diodos y masas. Con éste último se probaron distintas técnicas de ionización (ESI, APCI y APPI) para encontrar la mejor técnica que ionizara carotenos y xantófilas. Además se hallaron transiciones para identificar a cada uno de los carotenoides. Para mostrar la confiabilidad del método analítico, realicé la validación del mismo y determiné factores importantes que influyen en el análisis de carotenoides, como por ejemplo, su estabilidad química. Para analizar la ruta metabólica de los carotenoides, se realizaron distintos experimentos, entre ellos, introducir distintas combinaciones de genes en el maíz y arroz que permitieran entender cuáles eran las enzimas importantes que permitían la acumulación de carotenoides. También se analizó la biosíntesis de carotenoides a distintas etapas del desarrollo de la semilla de maíz, desde los 15 días después de la polinización (DAP) hasta los 60 DAP y su estabilidad química a lo largo de todo este período. Finalmente, se profundizó en la identificación de nuevos carotenoides encontrados en las muestras, como los oxo-carotenoides (utilizados en la industria como colorantes). Para llevar acabo su identificación, se realizaron pruebas químicas, se determinaron sus espectros visibles y sus fragmentos por masas.   

Echolocation calls of the bats of Trinidad, West Indies: is guild membership reflected in echolocation signal design?

Time-expanded echolocation calls were recorded from 29 species of Neotropical bats in lowland moist tropical forest in Trinidad, West Indies with three aims (I) to describe the echolocation calls of the members of a diverse Neotropical bat community, especially members of the family Phyllostomidae, whose calls are not well documented (2) to investigate whether multivariate analysis of calls allows species and foraging guilds to be identified and (3) to evaluate the use of bat detectors in surveying the phyllostomids of Neotropical forests. The calls of 12 species of the family Phyllostomidae are described here for the first time and a total of 29 species, belonging to five families (Emballonuridae, Mormoopidae, Phyllostomidae, Molossidae and Vespertilionidae) were recorded Quadratic discriminant function analysis (DFA) was used to obtain classification rates for each one of 11 individual species and for six guilds (based on diet, foraging mode and habitat) comprising 26 species Overall classification rates were low compared to similar studies conducted in the Palaeotropics We suggest that this may be due to a combination of ecological plasticity for certain species and a loose relationship between echolocation call shape, fine-grained resource partitioning and resource acquisition in phyllostomids

Ultra-high pressure liquid chromatography-mass spectrometry for plant metabolomics: a systematic comparison of high-resolution quadrupole-time-of-flight and single stage Orbitrap mass spectrometers.

The response of Arabidopsis to stress caused by mechanical wounding was chosen as a model to compare the performances of high resolution quadrupole-time-of-flight (Q-TOF) and single stage Orbitrap (Exactive Plus) mass spectrometers in untargeted metabolomics. Both instruments were coupled to ultra-high pressure liquid chromatography (UHPLC) systems set under identical conditions. The experiment was divided in two steps: the first analyses involved sixteen unwounded plants, half of which were spiked with pure standards that are not present in Arabidopsis. The second analyses compared the metabolomes of mechanically wounded plants to unwounded plants. Data from both systems were extracted using the same feature detection software and submitted to unsupervised and supervised multivariate analysis methods. Both mass spectrometers were compared in terms of number and identity of detected features, capacity to discriminate between samples, repeatability and sensitivity. Although analytical variability was lower for the UHPLC-Q-TOF, generally the results for the two detectors were quite similar, both of them proving to be highly efficient at detecting even subtle differences between plant groups. Overall, sensitivity was found to be comparable, although the Exactive Plus Orbitrap provided slightly lower detection limits for specific compounds. Finally, to evaluate the potential of the two mass spectrometers for the identification of unknown markers, mass and spectral accuracies were calculated on selected identified compounds. While both instruments showed excellent mass accuracy (<2.5ppm for all measured compounds), better spectral accuracy was recorded on the Q-TOF. Taken together, our results demonstrate that comparable performances can be obtained at acquisition frequencies compatible with UHPLC on Q-TOF and Exactive Plus MS, which may thus be equivalently used for plant metabolomics.

Elaboració d'un protocol basat en XML per a una xarxa de sensors

La progressiva reducció de dimensió i cost en els dispositius electrònics, la dràstica retallada de consum elèctric i la independència de què això els dota han fet créixer en els últims temps l'interès de les comunitats científiques i tecnològiques per les xarxes sense fils de petits dispositius. Per altra banda, l'XML (eXtensible Markup Language) és un metallenguatge extensible que ha esdevingut un estàndard per a l'intercanvi d'informació estructurada entre diferents plataformes. L'objectiu d'aquest treball és explorar les possibilitats que pot oferir la introducció de l'XML en les xarxes de sensors amb l'elaboració d'un protocol de comunicació basat en aquest llenguatge i demostrar la transparència en el canvi de plataforma. Per fer-ho, es disposa de dos dispositius amb capacitat de comunicació sense fils equipats amb detectors de temperatura, lluminositat, efecte Hall i nivell de càrrega de la bateria. El projecte constarà de dues parts: una, més extensa, dedicada al desenvolupament del programari per a aquests dispositius, encarregat de obtenir les lectures dels diferents sensors i emetre-les per la xarxa utilitzant el llenguatge XML, i una altra, per recollir aquesta informació present a la xarxa, interpretar-la, salvar-la en una base de dades i exposar-la al món en una plana web. El programari dels dispositius sensors s'escriurà en llenguatge nesC dins el sistema tinyOS que és el sistema operatiu que equipen. La part d'explotació de les dades es desenvoluparà sota la plataforma .NET de Microsoft.

Major influencing factors of indoor radon concentrations in Switzerland.

PURPOSE: In Switzerland, nationwide large-scale radon surveys have been conducted since the early 1980s to establish the distribution of indoor radon concentrations (IRC). The aim of this work was to study the factors influencing IRC in Switzerland using univariate analyses that take into account biases caused by spatial irregularities of sampling. METHODS: About 212,000 IRC measurements carried out in more than 136,000 dwellings were available for this study. A probability map to assess risk of exceeding an IRC of 300 Bq/m(3) was produced using basic geostatistical techniques. Univariate analyses of IRC for different variables, namely the type of radon detector, various building characteristics such as foundation type, year of construction and building type, as well as the altitude, the average outdoor temperature during measurement and the lithology, were performed comparing 95% confidence intervals among classes of each variable. Furthermore, a map showing the spatial aggregation of the number of measurements was generated for each class of variable in order to assess biases due to spatially irregular sampling. RESULTS: IRC measurements carried out with electret detectors were 35% higher than measurements performed with track detectors. Regarding building characteristics, the IRC of apartments are significantly lower than individual houses. Furthermore, buildings with concrete foundations have the lowest IRC. A significant decrease in IRC was found in buildings constructed after 1900 and again after 1970. Moreover, IRC decreases at higher outdoor temperatures. There is also a tendency to have higher IRC with altitude. Regarding lithology, carbonate rock in the Jura Mountains produces significantly higher IRC, almost by a factor of 2, than carbonate rock in the Alps. Sedimentary rock and sediment produce the lowest IRC while carbonate rock from the Jura Mountains and igneous rock produce the highest IRC. Potential biases due to spatially unbalanced sampling of measurements were identified for several influencing factors. CONCLUSIONS: Significant associations were found between IRC and all variables under study. However, we showed that the spatial distribution of samples strongly affected the relevance of those associations. Therefore, future methods to estimate local radon hazards should take the multidimensionality of the process of IRC into account.

Accuracy profile validation of a new method for carbon monoxide measurement in the human blood using headspace-gas chromatography-mass spectrometry (HS-GC-MS).

The aim of our study was to provide an innovative headspace-gas chromatography-mass spectrometry (HS-GC-MS) method applicable for the routine determination of blood CO concentration in forensic toxicology laboratories. The main drawback of the GC/MS methods discussed in literature for CO measurement is the absence of a specific CO internal standard necessary for performing quantification. Even if stable isotope of CO is commercially available in the gaseous state, it is essential to develop a safer method to limit the manipulation of gaseous CO and to precisely control the injected amount of CO for spiking and calibration. To avoid the manipulation of a stable isotope-labeled gas, we have chosen to generate in a vial in situ, an internal labeled standard gas ((13)CO) formed by the reaction of labeled formic acid formic acid (H(13)COOH) with sulfuric acid. As sulfuric acid can also be employed to liberate the CO reagent from whole blood, the procedure allows for the liberation of CO simultaneously with the generation of (13)CO. This method allows for precise measurement of blood CO concentrations from a small amount of blood (10 μL). Finally, this method was applied to measure the CO concentration of intoxicated human blood samples from autopsies.

Probabilistic sonar scan matching for an AUV

This paper proposes MSISpIC, a probabilistic sonar scan matching algorithm for the localization of an autonomous underwater vehicle (AUV). The technique uses range scans gathered with a Mechanical Scanning Imaging Sonar (MSIS), the robot displacement estimated through dead-reckoning using a Doppler velocity log (DVL) and a motion reference unit (MRU). The proposed method is an extension of the pIC algorithm. An extended Kalman filter (EKF) is used to estimate the robot-path during the scan in order to reference all the range and bearing measurements as well as their uncertainty to a scan fixed frame before registering. The major contribution consists of experimentally proving that probabilistic sonar scan matching techniques have the potential to improve the DVL-based navigation. The algorithm has been tested on an AUV guided along a 600 m path within an abandoned marina underwater environment with satisfactory results