Dermatophytes are a group of fungi, some of which can cause skin diseases in humans and animals due to their ability to degrade keratinized tissue. Representatives of this group also include strains from the Trichophyton benhamiae complex, known to cause dermatophytosis especially of small rodents and rabbits. In the last decade, one of four populations of this complex has spread epidemically across Europe among guinea pigs and their breeders. To answer the question what stands behind the successful spread of this population, the gene expression and production of volatile organic compounds of epidemic and non-epidemic populations of T. benhamiae was investigated. Gene expression of three strains from each population was studied during growth in liquid medium and on ex vivo mouse skin models prepared according to a newly optimized protocol. RNAseq and RT-qPCR methods were chosen for the gene expression analysis. Based on the literature and the results of RNAseq preliminary analysis, several genes were selected for which specific primers were designed. The spectra of the produced volatile organic compounds of the same strains growing on sheep wool in vials were analyzed by GC-MS. While non-epidemic populations did not differ in gene expression and production of volatile organic compounds, the...

Exposure to volatile organic compounds (VOCs) has critical health implications for developing fetuses and subsequently for infants and young children. Research has suggested that this ambient air pollutant can be found indoors in quantities that may be hazardous to human health. In low-income neighborhoods in New York City such as northern Manhattan and the South Bronx, where there are disproportionately high rates of asthma and asthma-related hospitalizations, high rates of indoor exposure to VOCs persist. Simultaneously, as mobile devices expand, applications on mobile devices may be used to educate parents of children who reside in these geographic regions about indoor VOC emission sources and subsequently how to reduce exposure.Therefore, this study sought to assess the role of mobile device applications in reducing household VOCs by assessing the feasibility of existing health applications on both Apple and Android OS mobile devices without the use of a household air monitoring unit. An online survey assessed awareness of VOCs and identified knowledge of both emission sources and reduction methods of household VOCs among a sample of (N = 57) parents/guardians residing in the Northern Manhattan and Southern Bronx regions with children under the age of 5. A series of focus groups were conducted among a subset of participants to assess the adaptability of a mobile application prototype that specifically targets the reduction of VOCs. Lastly, a preliminary mobile device application mockup was created with potential features. The key findings of this study included the following: (a) the author identified no existing mobile device applications that could be utilized as a method for VOC reduction without the use of a physical in-home air monitor; (b) while parents had some baseline awareness of VOCs, there were gaps within their knowledge of VOCs, particularly with emission sources; (c) the feasibility of this proposed application as a potential source of intervention for indoor VOC mitigation was apparent through parent willingness to explore its possible use, while providing ample recommendations for optimal mobile device application design; and (d) the exploratory mockup of the proposed mobile device application was generated with suggested features.

Dans l’atmosphère, les particules d’aérosol jouent un rôle clef sur le climat et, par leur action sur la qualité de l’air, ont un impact néfaste sur la santé publique. Ces particules sont composées d’un mélange complexe d’espèces inorganiques et organiques formées à partir d’une grande variété de sources. Si les sources et mécanismes de production des espèces inorganiques sont désormais relativement bien connus, la caractérisation de la fraction organique des aérosols est beaucoup plus complexe : elle est constituée d’aérosols organiques primaires, émis directement dans l’atmosphère, et d’aérosols organiques secondaires (AOS) produits par la conversion gaz-particules de Composés Organiques Volatils (COV). Afin de comprendre les processus de formation des aérosols organiques, des modèles tridimensionnels de chimie-transport sont mis en œuvre. Or, à ce jour, les concentrations en aérosols organiques observées dans l’atmosphère demeurent sous-estimées par ces modèles. L’objectif de cette thèse est d’étudier les différents processus de transport, d’émissions et de transformations chimiques intervenant dans la formation des aérosols organiques à partir du modèle de chimie-transport WRF-Chem (Weather Research and Forecasting – Chemistry). Les sorties du modèle ont été comparées à des mesures effectuées à la station du puy de Dôme au cours de trois situations correspondant à trois saisons (automne, hiver, été) durant lesquelles des masses d’air de diverses origines ont été échantillonnées. Ces mesures documentent les conditions météorologiques, les propriétés des espèces chimiques gazeuses et des particules d’aérosol. En particulier, les mesures fournies par un spectromètre de masse (AMS : Aerosol Mass Spectrometer), fournissent de informations détaillées sur la variabilité temporelle de la composition chimique des aérosols et notamment sur leur concentration en masse. Les comparaisons modèle/mesures ont montré que les variations saisonnières de la composition chimique des aérosols observées au puy de Dôme étaient bien capturées par le modèle. Cependant, il s’est avéré que les concentrations en aérosols organiques étaient fortement sous-estimées par le modèle et plus particulièrement lors de la situation d’été. La confrontation des origines des masses d’air simulées par le modèle WRF-Chem à celles déterminées par le modèle lagrangien HYSPLIT reconnu pour l’étude de la dispersion atmosphérique et l’analyse des variations de la localisation du sommet du puy de Dôme vis-à-vis de la couche limite atmosphérique ont mis en évidence que le transport était correctement reproduit par le modèle. Les mesures de gaz disponibles au puy de Dôme ont mis en évidence une forte sous-estimation des concentrations en COV d’origine anthropique simulées par le modèle. Des tests de sensibilité ont été réalisés sur les émissions de ces espèces pour restituer les niveaux de concentration observés. Les émissions et les rendements en AOS des COV d’origine anthropique implémentés dans la paramétrisation VBS dédiée aux aérosols organiques dans le modèle ont pu être modifiés afin de reproduire les niveaux de concentration en aérosols organiques observés au puy de Dôme. / In the atmosphere, aerosol particles play a key role on both climate change and human health due to their effect on air quality. These particles are made of a complex mixture of organic and inorganic species emitted from several sources. Although the sources and the production mechanisms for inorganic species are now quite well understood, the characterization of the organic fraction is much more difficult to study. Indeed, particulate organic matter comes from primary organic aerosols directly emitted to the atmosphere and secondary organic aerosols (SOA), which are formed from gas-to-particle conversion of Volatile Organic Compounds (VOC). Three-dimensional chemistry-transport models are developed to better understand the organic aerosol formation processes. However, these models underestimate the organic aerosol concentrations. The aim of this thesis is to study the transport, the emissions and the chemical transformations involved in the formation of the organic aerosols using the WRF-Chem chemistry-transport model (Weather Research and Forecasting – Chemistry; Grell .et al., 2005). Model outputs are compared to measurements performed at the puy de Dôme station (France) during three campaigns. These measurements allow for characterizing various air masses and different seasonal behaviours (in autumn, winter and summer). The station hosts many probes for controlling meteorological parameters, gas phase species and aerosol properties. In particular, a mass spectrometer (AMS: Aerosol Mass Spectrometer) provides detailed time evolution of the chemical composition and mass concentration of the particulate matter. The comparisons between model results and observations have shown that seasonal variations of the aerosol chemical composition are captured by the WRF-Chem model. However, the organic aerosols mass concentrations are strongly underestimated and this underestimation is more important for the polluted summer case. The calculated origins of air masses are comparable to the results of the lagrangian model HYSPLIT currently used for atmospheric dispersion. The top of the puy de Dôme is observed to be either in the boundary layer or above depending on the season and these observations are correctly reproduced by the WRF-Chem model. As the anthropogenic VOC concentrations are underestimated by WFR-Chem model, sensitivity tests on the anthropogenic VOC emissions and SOA yields, used in the VBS secondary organic aerosols parameterisation, are done to better reproduce the organic aerosol concentrations observed at the puy de Dôme station.

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Indiana University-Purdue University Indianapolis (IUPUI) / Solid phase micro-extraction is a powerful and versatile technique, well-suited to the analysis of numerous samples of forensic interest. The exceptional sensitivity of the SPME platform, combined with its adaptability to traditional GC-MS systems and its ability to extract samples with minimal work-up, make it appropriate to applications in forensic laboratories. In a series of research projects, solid phase micro-extraction was employed for the analysis of explosives, commercial tire treatments, and entomological specimens. In the first project, the volatile organic compounds emanating from two brands of pseudo-explosive training aids for use in detector dog imprinting were determined by SPME-GC-MS, and the efficacy of these training materials was tested in live canine trials. In the second project, the headspace above various plasticizers was analyzed comparative to that of Composition C-4 in order to draw conclusions about the odor compound, 2- ethyl-1-hexnaol, with an eye toward the design of future training aids. In the third, automobile tires which had participated in professional race events were analyzed for the presence of illicit tire treatments, and in the fourth, a novel SPME-GC-MS method was developed for the analysis of blowfly (Diptera) liquid extracts. In the fifth and final project, the new method was put to the task of performing a chemotaxonomic analysis on pupa specimens, seeking to chemically characterize them according to their age, generation, and species.

The aim of this thesis was to elaborate the issue of the decomposition of volatile organic compounds in the Gliding Arc plasma discharge at atmospheric pressure. Technologies based on nonthermal plasma could offer a good alternative to conventional techniques for the decomposition of volatile organic compounds, such as thermal and catalytic oxidation. Gliding Arc discharge (GidArc) is a widely exploited nonthermal plasma source used for many industrial applications, such as air-pollution control. The energy efficiency, reaction selectivity or production of specific species may be achieved in this kind of plasma, and thus for various chemical processes it can be much more effective then in conventional techniques. Presented experiments are linked to the previous results published in diploma thesis, which gave us the basics for construction of new reactor and optical emission spectroscopy measurements have been done to characterize the plasma. Toluene (aromatic, unsaturated), cyclohexane (aromatic, saturated) and hexane (aliphatic, saturated) were used as the model compounds for these experiments in the concentration range from hundreds to thousands ppm. Results focused on the electrical parameters of the reactor were carried out, with the aim to operate the system at a lower energy cost. In order to get the time-resolved diagnostics of the moving plasma channel, the evolution of the plasma channel was recorded continuously by using a high-speed video camera. In next part of the work, some results concerning generation of low molecular products like nitric oxide, nitrogen dioxide, hydrogen and carbon monoxide on the discharge conditions are presented. In combustion process, undesirable mixture of toxic highmolecular by-products can be formed. Samples were therefore analysed in gas chromatograph linked to mass spectrometer, to characterize the chemical transformation pathway of VOC in plasma.

The first part of the work is aimed to the study of changes of electrical properties of substituted phthalocyanines under the influence of humidity. Thin films were prepared by spin coating technique. During the influenece of humidity electrical conductivity increases. Sorption and desorption and the changes in electrical properties under the repated humidity exposure were investigated as well. Impedance spectroscopy was used for the studies. The second part of this work consists of optical studies and changes of optical parametrsunder the influence of different alcohols (methanol, ethanol, 2-propanol) exposures. The investigated samples were prepared by vacuum evaporation a glow-discharge-induced sublimation. The changes of optical reflectances of the films upon exposure to alcoholvapour-containg atmospheres were studied as a function of alcohol concetration and exposure time.

Maize (Zea mays) is an important agricultural crop frequently targeted by pests that pose a threat to plant development and survival. To deal with this problem, maize generates a wide variety of responses to attack by pests, from activation of woundresponse pathways to the release of volatile compounds. Several maize lines have been developed that show resistance to one common pest, the larvae of the fall armyworm (Spodoptera frugiperda). Analysis of the volatiles released by the resistant and susceptible lines in the presence and absence of the fall armyworm was conducted using SPME coupled to GC/MS. Caryophyllene, a commonly released plant volatile, was identified in the resistant line. In the susceptible line, caryophyllene was detected in smaller quantities or not at all. The results of a preference study demonstrated that fall armyworm larvae show a statistically significant preference for yellow-green whorl tissue from the susceptible over the resistant line.

Biogenic volatile organic compounds (VOCs) react with Cl and OH radicals and the resulting radicals combine with oxygen to form peroxy radicals RO2. Organic peroxy radicals can then react with NO to form NO2, a precursor of tropospheric ozone. The work presented here explored the initial reaction between Cl and thujone, a VOC emitted by Great Basin sagebrush. The rate constant for the reaction of thujone + Cl at 296 K was measured with the method of relative rates with FTIR for detection of reactants. LEDs were used to photolyze Cl2 to generate Cl in the reaction cell. Thujone was also photolyzed by the LEDs and therefore the relative rates model was revised to account for this photolysis. With toluene as the reference compound, the rate constant for thujone + Cl at 296 K is 2.62 ± 1.90 × 10-12 molecules-1 s-1, giving an atmospheric lifetime of 0.5--2.6 minutes for thujone. Cline et al. showed that the rate of the self-reaction of HO2CH2CH2O2 (β-HEP) increases in the presence of water vapor. This enhancement has a strong temperature dependence with a greater enhancement observed at colder temperatures. The observed rate enhancement has been attributed to the formation of a β-HEP--H2O complex. In this work, the equilibrium constant for the formation of the β-HEP--H2O complex was calculated by ab initio calculations. Given the energy available at room temperature, the complex will populate three local minimum geometries and β-HEP will populate two local minimum geometries. The partition function for each of these geometries was calculated and used to calculate the equilibrium constant for complex formation as a function of temperature. Based on these computational results, the observed temperature dependence for the rate enhancement can be attributed to the strong temperature dependence for the rate constant of the reaction of β-HEP--H2O + β-HEP rather than the temperature dependence of complex formation.

<p> Volatile organic compounds (VOCs) are byproducts of metabolic processes that can be uniquely dysregulated by various medical conditions and are expressed in biological samples. Therefore, VOCs expressed in breath, urine and other sample types may be utilized for noninvasive, rapid, and accurate diagnostics in a point-of-care setting. Currently, the most common methods for VOC detection include gas chromatography-mass spectrometry (GC-MS) and electronic noses (E-noses) that integrate nanosensors. Both methods present important advantages and challenges that allow their implementation for different applications. While GC-MS can be used to directly identify VOCs in complex matrices, it is a non-portable and high-cost instrument. On the other hand, E-noses are portable and user-friendly VOC detectors, but they do not allow for direct VOC identification or quantification. Among different VOC rich sample types, breath offers the advantage of being a virtually limitless source of endogenous biomarkers that can be implemented for noninvasive VOC detection.</p> <p><br></p> <p>The presented thesis focuses on the optimization of the operating parameters (heater and sensor voltages) of a metal oxide (MOX) sensor and breath sampling techniques (sensor casing, breath fractionation, and exhalation volume) for their implementation in exhaled VOC analysis. In parallel, an in-house feature extraction algorithm was developed and implemented for the optimization of a MOX sensor composed of a tin oxide (SnO2) sensing layer. The optimized sensor parameters (heater voltage equal to 2 V and sensor voltage equal to 0.8 V) and breath sampling protocol (24 L of whole breath analyzed using the in-house sensor casing design) were tested with exhaled breath samples from distinct volunteers which could be successfully separated with 100% accuracy. The sensor response also showed a high degree of intrasubject reproducibility (RSD < 6%). Additionally, the sensor performance was further validated under ambient conditions, and sensor degradation was studied over the course of 3 months. Finally, sensor response to synthetic VOC profiles and individual VOC standards was explored. Optimized SnO2 sensors distinguished between VOC mixtures regardless of variations in relative humidity (RH) levels. Furthermore, the characteristic sensor response to VOC standards indicates that the sensors are most sensitive toward isopropanol by a factor of 1.15 in 45% RH and a factor of 3.58 in 85% RH relative to isoprene. </p> <p><br></p> <p>To translate the potential of MOX sensors to point-of-care biomedical applications, there first exists the need to establish a reference of sensor baseline signals corresponding to exhaled breath samples from healthy individuals. SnO2 sensors and breath sampling methods were implemented for the collection of individual samples from 109 relatively healthy volunteers. 10 of these volunteers provided 9 additional samples over the course of six months. In parallel, exhaled breath samples were also analyzed by GC-MS to comprehensively profile VOCs present in the samples. The results from these experiments not only aid in the identification of the healthy breath signal baseline but also allow the exploration of VOC reproducibility over time. High variation between samples from distinct volunteers was observed, but samples longitudinally collected across volunteers could not be distinguished, alluding to the existence of a universal range of sensor signals that could describe the composition of exhaled breath from healthy subjects. Finally, results were compared with relevant confounding variables to better understand how VOCs are impacted by an array of factors that are not directly correlated to disease diagnosis. Sensor signals were significantly elevated in breath samples from male volunteers compared to samples from female subjects (p-value = 0.044). Interestingly, isoprene signals resulting from the GC-MS analysis were also higher in male subjects relative to females. No other relationships were identified between sensor signals and the confounding variables of interest. </p> <p><br></p> <p>Future work would require a deeper understanding of sensor degradation and life cycle, along with sensor testing using a broader range of individual VOC standards and more complex VOC profiles. Additionally, further comparison between sensor signal and GC-MS signal of relevant VOC biomarkers present in breath would be beneficial. Nonetheless, the presented be leveraged in future investigations aiming to identify biomarkers for different medical conditions. Finally, the findings disclosed in the deposited thesis suggest the ability of a SnO2 nanosensor array to be implemented for breath analysis, providing a noninvasive, easy to use, and reliable diagnostic device in a point-of-care setting. </p>