No description available.

Intracavity Laser Absorption Spectroscopy (ICLAS) at IR wavelengths offers an opportunity for spectral sensing of low vapor pressure compounds. We report here an ICLAS system design based on a quantum cascade laser (QCL) at THz (69.9 m) and IR wavelengths (9.38 and 8.1 m) with an open external cavity. The sensitivity of such a system is potentially very high due to extraordinarily long effective optical paths that can be achieved in an active cavity. Sensitivity estimation by numerical solution of the laser rate equations for the THz QCL ICLAS system is determined. Experimental development of the external cavity QCL is demonstrated for the two IR wavelengths, as supported by appearance of fine mode structure in the laser spectrum. The 8.1 m wavelength exhibits a dramatic change in the output spectrum caused by the weak intracavity absorption of acetone. Numerical solution of the laser rate equations yields a sensitivity estimation of acetone partial pressure of 165 mTorr corresponding to ~ 200 ppm. The system is also found sensitive to the humidity in the laboratory air with an absorption coefficient of just 3 x 10-7 cm -1 indicating a sensitivity of 111 ppm. Reported also is the design of a compact integrated data acquisition and control system. Potential applications include military and commercial sensing for threat compounds such as explosives, chemical gases, biological aerosols, drugs, banned or invasive organisms, bio-medical breath analysis, and terrestrial or planetary atmospheric science.

The Department of Defense (DoD) has numerous sites that contain groundwater contaminated with 2,4,6-trinitrotoluene (TNT). The currently applied technologies for treating TNT contaminated waters are carbon adsorption and chemical oxidation. Carbon adsorption is a non-destructive technology, which could create future liability issues and is inefficient at relatively low TNT concentrations. On the other hand, application of chemical oxidation for the treatment of TNT contaminated water generates trinitrobenzene (TNB), a by-product of the incomplete oxidation of TNT. TNB is regulated as strictly as TNT. Additionally, over 70% of the reactor required treatment time for meeting target levels is due solely for TNB removal. This study evaluated the potential integration of zero-valent metallic species and advanced oxidation for the treatment of waters contaminated with TNT. The idea was to reduce treatment time, and thus, operational costs, when advanced oxidation is used as a stand-alone treatment technology by reducing TNT prior to oxidation. The use of zero-valent metals as the first treatment step transformed TNT into reduced organic compounds which were easily oxidized. The effectiveness of zinc, iron, nickel, copper, and tin as TNT reducing agents was evaluated. Zinc and iron were selected for further study based on their performance degrading TNT. Then, the reduction mechanism (pathway) and associated by-products of TNT reduction using zinc were examined using a zinc specimen manufactured by Sigma Corporation. Three amines were identified during reduction : 2-amino-4,6-dinitrotoluene, 4-amino-2,6-dinitrotoluene, and 2,4-diamino-toluene. Other intermediates were observed but not identified. Many of these reduction by-products adsorbed strongly onto the metal surface, significantly reducing the rate of TNT degradation during aging experiments. The aging of the metallic species was modeled using a power decay law parameter with the rate expression for TNT degradation. Corrosion promoters such as KCl addition, ozonation, and peroxone were evaluated as alternatives to reactivate zinc and iron to achieve steady TNT degradation. The addition of KCl performed significantly better than ozonation and peroxone. Furthermore, addition of KCl during the reduction step using iron or zinc generated organics that were successfully mineralized by ozonation or peroxone.

A family of novel large cage Tb-based TNT-EMFs Tb₃N@C_2n (40 ≤ n ≤ 44), and a family of novel dimetallic endohedral metalloazafullerenes with the molecular formula of M₂@C₇₉N (M=Y, Tb, and La), were for the first time systematically synthesized, isolated, and structurally characterized. The protocol developed in this thesis provides an effective and systematic method for the synthesis, purification, and characterization of TNT-EMFs and other novel EMFs. Structural information about this family of Tb-based TNT-EMFs strongly supports the TNT formation mechanism of TNT-EMFs. It also demonstrates for the first time that EMFs do not necessarily choose an IPR-obeying cage even if the IPR cages are available. At room temperature and in a non-polar organic solvent, the fluorescence of the hydrogenated product of Tb₃N@C₈₀ was for the first time successfully obtained based on the proposed idea: de-shielding the screen effect of the fullerene cage on the metal ions or clusters inside the fullerene cage. The structural characterization of Tb₂@C₇₉N using single crystal X-ray diffraction crystallography demonstrated that the fullerene cage of M₂@C₇₉N is an I_h eighty-atom cage. The presence of the N atom in the molecule was further confirmed by mass spectra of the ¹⁵N labeled samples. ESR data demonstrated that there is a single-electron bond between the two Y atoms in Y₂@C₇₉N molecules. Theoretical calculations showed for the first time that the single-electron bond is low-lying at the HOMO-2 orbital and thereby resulting in a large HOMO-LUMO gap. It is, in fact, this large HOMO-LUMO gap and the low-lying single-electron orbital (hidden at HOMO-2) that are jointly responsible for the stability of M2@C79N. The single-electron bonds are the longest metal-metal bond reported so far. The chromatographic retention behavior of TNT-EMFs was also systematically studied on 5PBB and 5PYE columns. Both experimental and theoretical data demonstrated that the 5PBB column is sensitive to a fullerene's predicted cage size but indifferent to its cage symmetry, while the 5PYE column is more sensitive to the density and distribution of Ï electrons in a fullerene cage. Therefore, the 5PYE column is more suitable for separating structural isomers. The combination of the 5PBB column in the first stage and the 5PYE column in the second provides a highly effective way for isolating specific isomers. / Ph. D.

Minor utgör ett hot mot civilbefolkningen men även personal i fredsfrämjande insatser riskerar att skadas av minorna under patruller i insatsområdet. Idag används minhunden i Försvarsmakten för att lokaliera minor i kombination med minpik och metalldetektor. Hunden har sina begränsningar och har under flera perioder varit på väg att fasas ut till förmån för tekniken. Minans doftbild, minhunden och den elektroniska nosen beskrivs och mynnar ut i en analys där för-/nackdelar presenteras och därefter diskuteras. Den militära nyttan i den militära kontexten, insats med undsättningsstyrka (MRT) utgör ramverk i uppsatsen. Vid en undsättningsinsats med MRT är det av största vikt att minorna kan lokaliseras, märkas ut och undvikas. Hunden har förmåga till lokalisering av minor vilket den elektroniska nosen Fido saknar. Minornas doftbild överlappar varandra. Fido kan inte särskilja minorna från varandra utan endast bekräfta förekomst i ett område vilket inte bidrar till den militära nyttan när en fri väg ska sökas fram till en skadeplats. / Landmines pose a threat to the civilian population but personnel in peacekeeping operations could also be harmed by landmines during patrols in the area. Today the Swedish Armed Forces use mine detection dogs to locate landmines. The mine detection dogs are used in combination with prodders and metal detectors. The dogs have their limitations and there have been several attempts to phase them out and replace them with technology. Substances detected by dogs and electronic noses, the mine detection dog and the electronic dog nose Fido are described and incorporated in an analysis where advantages/disadvantages are presented and then discussed. Military utility in a military context constitute the frame of the essay. The military context is an operation with a mine rescue team to rescue an injured person in a mine field. In a rescue operation with a mine rescue team the most important thing is to locate, mark and avoid the landmines. The dog can locate landmines but the electronic nose Fido cannot. The chemical signatures from the landmines overlap each other making it difficult for Fido to pinpoint the exact location. Fido can confirm the presence of landmines in an area which does not have military utility during mine rescue team operations to find a free path and rescue an injured person out from a minefield.

Les travaux présentés dans ce mémoire de thèse s’inscrivent dans le cadre des études liées aux dégâts sur les structures et les blessures subies par les personnes à la suite d’explosions de charges explosives en milieu confiné et semi-confiné. Afin de mener cette étude, des expériences sont réalisées à petite échelle en laboratoire et sont complétées par des simulations numériques. Les ondes de choc sont obtenues grâce à la détonation d’une charge explosive gazeuse composée de propane-oxygène en proportion stoechiométrique. L’étude consiste donc à réaliser des expériences à petite échelle en laboratoire afin d’apprécier les champs de pression obtenus à la suite de la détonation d’une charge explosive au sein de deux configurations différentes. La première représente un atelier pyrotechnique et la seconde met en jeu un entrepôt de stockage de bouteilles de gaz. Les résultats expérimentaux sont ensuite confrontés à des résultats obtenus par simulations numériques réalisées grâce au logiciel AUTODYN. En complément de ces deux configuration principales, une étude est menée sur l’identification des pics de surpressions réfléchis grâce à une approche expérimentale appelée paroi par paroi. Une étude est également menée sur la détermination d’une équivalence massique entre le TNT et le mélange gazeux utilisé pour les expériences. / The goal of this study is to investigate shock waves propagation, in a geometrically complex confined and semi-confined environment, consecutive to the detonation of a spherical explosive charge. In this objective, small scale experiments are conducted in laboratory and are completed with numerical analysis. Shock waves are generated thanks to spherical detonation of a gas mixture composed of propane-oxygen in stoechiometric proportion. Two main configurations are studied: the first represents a pyrotechnic workshop and the second is a warehouse containing gas cylinder. Experimental and numerical results are then compared. Complementary studies are realised to describe blast wave propagation inside a semi-confined volume thanks to a new experimental approach named wall by wall. Finally, in order to simulate TNT charges detonation by computational means, an important study is conducted to determine a mass equivalent between TNT and gas mixture.

Les travaux de thèse présentés dans ce mémoire s’inscrivent dans le cadre du projet ANR BARPPRO. Ce programme de recherche vise à étudier l’influence d’une barrière de protection face à une explosion en régime de détonation. L’objectif est d’établir des méthodes de calcul rapides de classement des zones d’effets pour aider les industriels au dimensionnement des barrières de protection. L’une à partir d’abaques, valable pour des configurations en géométrie 2D, sur des plages spécifiées de paramètres importants retenus, avec une précision de +/- 5%. L’autre à partir d’une méthode d’estimation rapide basée notamment sur les chemins déployés, valable en géométrie 2D et en géométrie 3D, mais dont la précision estimée est de +/- 30%. Afin d’y parvenir, l’étude s’appuie sur trois volets : expérimental, simulation numérique et analytique. La partie expérimentale étudie plusieurs géométries de barrière de protection à petites échelles pour la détonation d’une charge gazeuse (propane-oxygène à la stoechiométrie). Les configurations expérimentées servent à la validation de l’outil de simulation numérique constitué du solveur HERA et de la plateforme de calcul TERA 100. Des abaques d’aide au dimensionnement ont pu être réalisés à partir de résultats fournis par l’outil de simulation (3125 configurations de barrière de protection, TNT). L’étude des différents phénomènes physiques présents a également permis de mettre en place une méthode d’estimation rapide basée sur des relations géométriques, analytiques et empiriques. L’analyse de ces résultats a permis d’établir quelques recommandations dans le dimensionnement d’une barrière de protection. Les abaques et le programme d’estimation rapide permettent à un ingénieur de dimensionner rapidement une barrière de protection en fonction de la configuration du terrain et de la position de la zone à protéger en aval du merlon. / This thesis is a part of the ANR BARPPRO project. This research program studies this influence of the protection barrier during an explosion detonation. The goal of this project is to establish fast-computation methods of area classification effects to help the industrial to design the protection barrier on the SEVESO sites. One from abacus, for configurations in 2D geometry on specified parameters used, with an accuracy of +/- 5%. The other from a fast-running method based on broken lines for configurations in 2D and 3D geometries, but the accuracy is +/- 30%. This study includes three approaches: experimental, numerical simulation and analytical approaches. The experimental part studies several geometries of the protection barrier for a gaseous explosion (stoichiometric propane-oxygen mixture) at small scales. The experimental configurations used to validate the numerical simulation tool constituted of the HERA software and the TERA 100 supercomputer. The overpressure charts were able to generate from the numerical results (3125 configurations of the barrier for a TNT charge). The analysis of these results allows to establish different recommendations in the design of the protection barrier. The study of the different physical phenomena present has also helped to set up a fast-running method based on the geometrical, empirical and analytical relations. All these tools will enable an engineer to analyze and estimate the evolution of overpressure around the barrier as a function of the site’s dimensions.

At least 110 million landmines have been planted since the 1970s in about 70 nations, many of which remain in place today. Some risk of detection may be mitigated using currently available remote sensing techniques when vegetation is present. My study focused on using plants as phytosensors to detect buried explosives. I exposed three species representing different functional types (Cyperus esculentus (sedge), Ulmus alata (tree), Vitis labrusca (vine)) to 500 mg kg-1 of Composition B (Comp B; 60/40 mixture of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and 2,4,6-trinitrotoluene (TNT)), a commonly used explosive mixture, and measured functional traits and reflectance over a nine-week period. Cyperus esculentus was not a good indicator for the presence of explosive compounds. Comp B treatment woody species, U. alata and V. labrusca, exhibited changes in pigment content, leaf area, specific leaf area, dry leaf biomass, and canopy reflectance. The efficacy of plants as landmine detectors is species and/or functional group dependent.

La miocardiopatía hipertrófica (MCH) es una enfermedad primaria del miocardio causada por cambios genéticos. La MCH presenta hipertrofia cardíaca, desorganización de los miocitos e incremento de la matriz colágena intersticial que contribuyen al desarrollo de un amplio espectro de anomalías funcionales, incluyendo isquemia miocárdica, disfunción sistólica, insuficiencia cardíaca congestiva, arritmias y muerte súbita (MS).Los objetivos de este trabajo fueron:- Comparar los valores de los diferentes biomarcadores (estrés parietal, inflamación, daño endotelial, necrosis, fibrosis y remodelado tisular) entre pacientes con MCH y un grupo control de similares características. - Examinar el comportamiento de las concentraciones de los diferentes biomarcadores clasificando el grupo de pacientes según su capacidad funcional, atendiendo a los grupos de la escala NYHA.- Estudiar la asociación de cada biomarcador a las diferentes variables clínicas, asociación con las características demográficas y con las diferentes pruebas complementarias que estiman la severidad de la enfermedad.El aumento de las concentraciones de NT-proBNP en pacientes con MCH, sugiere la existencia de un aumento en la tensión de la pared del ventrículo y una mayor rigidez de la misma debido al depósito de tejido fibrótico. Se ha observado un marcado daño endotelial, como demuestra una media elevada del FvW en el grupo de pacientes. La presencia de necrosis de cardiomiocitos se corrobora, al resultar significativo un discreto aumento de concentraciones de TnThs en los sujetos con MCH. Entre los péptidos del colágeno estudiados, sólo el ICTP está aumentado en pacientes, sugiriendo que la degradación del colágeno tipo I jugaría un papel importante en el remodelado tisular extracelular que tiene lugar en la MCH. - Se observa una asociación entre los valores séricos de NT-proBNP, FvW, TnThs y GDF-15 con una peor capacidad funcional. Los valores de PCRhs obtenidos, aun encontrando asociación a peor capacidad funcional, sugieren que en la MCH no hay presencia de afección de carácter inflamatorio en su fisiopatología. Como conclusiones destacamos que: NT-proBNP se ha asociado al grado de fibrosis estimado mediante RTG. La concentración de FvW se ha relacionado con obstrucción y taquicardia ventricular no sostenida, no en cambio con el RTG. Sí se asocia el aumento de TnThs a más fibrosis, además de con disfunción sistólica, por lo que dicho incremento podría reflejar una pérdida continua de miocitos debido a un moderado rango de necrosis. Del grupo de péptidos estudiados del metabolismo del colágeno tipo I y III, no se han observado resultados concluyentes que expliquen un desequilibrio entre el remodelado tisular, destrucción y formación de tejido fibrótico miocárdico. / Hypertrophic cardiomyopathy (HCM) is a myocardial disease caused by genetic changes in genes encoding proteins of the sarcomere. HCM provides cardiac hypertrophy, myocyte disarray and increased interstitial collagen matrix, which contribute to the development of a broad spectrum of functional abnormalities, including myocardial ischemia, systolic dysfunction, congestive heart failure, arrhythmias and sudden cardiac death (SCD). Our aims were:- Compare the values of the different biomarkers (wall stress, inflammation, endothelial damage, necrosis, fibrosis and tissue remodeling) between HCM patients and a control group with similar characteristics.- Examine the behavior of the different biomarkers concentrations, classifying patients according to their functional capacity, attending to the NYHA scale groups. - To study the association of each biomarker to different clinical variables related with demographics and various complementary tests to estimate the severity ofthe disease.Results and conclusions: - Increased concentrations of NT-proBNP, suggest the existence of an increased wall tension and increased ventricular stiffness due to deposition of fibrotic tissue, in HCM patients. A marked endothelial damage has been observed, as evidenced elevated vWF levels in patients. The presence of a cardiomyocyte necrosis is confirmed in the slight but significant increase of hsTnT levels in HCM subjects. Among the studied collagen peptides, only the ICTP was increased in patients, suggesting that type I collagen degradation may play a role in extracellular tissue remodeling that takes place in the HCM. - There is an association between serum levels of NT-proBNP, vWF, hsTnT and GDF-15, with worse functional class. The hsCRP values obtained even were associated with worse functional capacity, not suggested the presence of an inflammatory condition in the HCM pathophysiology. - NT-proBNP was associated with the fibrosis degree estimated by LGE. vWF levels has been linked to obstruction and non-sustained ventricular tachycardia, whereas not with the LGE. Higher values of hsTnT was clearly related to an increased fibrosis in addition to systolic dysfunction, therefore this increase may reflect a continuous myocyte loss due to a moderate range of necrosis. In the group of collagen peptides studied of collagen type I and III metabolism, have been inconclusive results that could explain an imbalance between tissue remodeling, destruction and formation of myocardial fibrotic tissue.

Contamination of soils and groundwater with nitroaromatic compounds such as 2,4,6-trinitrotoluene (TNT) and dinitrotoluenes (DNTs) has drawn considerable attention due to widely distributed contamination sites and substantial efforts for cleanup. Two isomers of DNT, specifically 2,6-dinitrotoluene (2,6-DNT) and 2,4-dinitrotoluene (2,4-DNT), occur as soil and groundwater contaminants at former TNT production sites. The discovery of bacteria that use DNT isomers as electron donors has encouraged bioremediation at contaminated sites. Current work is extending the existing engineered bioremediation to naturally occurring in situ biodegradation and focuses on the application of natural attenuation (NA) as a remediation strategy for residual DNT at contaminated sites. More specifically this research evaluated factors influencing in situ bioremediation of DNTs and TNT in surface soils, vadose zones, and saturated medium. Applications involving surface soils and vadose zones investigated the potential of water infiltration to promote in situ bioremediation. Studies in saturated media were more applicable to NA. Factors that were also considered in studies conduced included: 1) the presence and distribution of degrading microbes in field soils (Barksdale, WI); 2) the dissolution and bioavailability of contaminants in historically contaminated soils; and 3) the effect of mixtures of contaminants (i.e., DNTs and TNT) on biodegradation processes. This research provided information useful for practitioners considering an in situ bioremediation NA as a remedial solution for contaminated sites. Under the condition simulating downflow of surface waters or rainwater, the rapid rate of DNT degradation could be facilitated by the availability of oxygen in the soil gas without concern of toxicity (i.e., nitrite evolution and pH drop) and addition of nutrients. As a result, in situ bioremediation or NA should be strongly considered as a remedial option for Barksdale soils and similar sites where relatively low concentrations of DNT isomers are present as contaminants. At TNT contaminated sites TNT was not mineralized by indigenous microorganisms despite oxidative biotransformation, and mixed culture capable of growth on DNT also could not develop the mineralization of TNT during DNT degradation. This suggests that the mixtures of contamination did not improve the potential for in situ TNT bioremediation.