Holographic sensors are photonic layered structures contained in analyte sensitive lms that upon illumination produce monochromatic reflections (λ). The present work reports the fabrication of oxygen and ammonia sensors in Nafi on membranes and hydrocarbon and volatile organic compound sensors in poly(dimethylsiloxane) (PDMS) films. A holographic recording technique was developed to suit these materials consisting of the in situ formation of nanoparticles of 18nm average diameter and their subsequent ordered ablation with a 300mJ laser. The wavelength of the monochromatic reflections depends principally on the refractive index of the resulting layers (n) and the separation between them (Λ). Changes in these parameters are generated by the analyte-sensor interactions and their magnitude can be correlated to the analyte concentration. The strength of these interactions is determined by the thermodynamic properties of the analytes, such as the cohesive energy density (δ^2), and this, was coupled with a photonic model for the prediction of the holographic response. After exposure to different concentrations of the analytes, the kinetics of the responses were determined and the lowest detection limits (LDL) established as follows: Hydrocarbons in PDMS holograms 1% (v/v) in 3s for a range of concentrations from 0-100%; ammonia in Nafi on holograms 0.16% in 100s in the 0-12.5% range; the LDL for oxygen sensing could not be determined although the response was recorded down to 12.5% and up to 100% in 100s. Holographic sensors show competitive responses comparable to commercially available gas sensors for biomedical diagnostics and industrial process monitoring because of their facile fabrication and their shared sensing platform allowing multiplexing.

Submitted by Eduarda Figueiredo (eduarda.ffigueiredo@ufpe.br) on 2015-03-06T15:09:52Z No. of bitstreams: 2 Helber_Tese_Digital.pdf: 17753634 bytes, checksum: 00c508d6a86f3bb67eb2a5c0b47d58b7 (MD5) license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) / Made available in DSpace on 2015-03-06T15:09:52Z (GMT). No. of bitstreams: 2 Helber_Tese_Digital.pdf: 17753634 bytes, checksum: 00c508d6a86f3bb67eb2a5c0b47d58b7 (MD5) license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) Previous issue date: 2012-08-06 / O controle orientado pela tensão é uma das técnicas mais usadas para a operação e o controle de quaisquer equipamentos conectados à rede elétrica através de um conversor eletrônico CC-CA, tais como: sistemas de geração de energia distribuída, sistemas de energia ininterrupta e filtros ativos. Por isso, a estimação rápida e precisa do ângulo de fase e por vezes da magnitude instantânea do vetor tensão de sequência positiva na frequência fundamental de uma rede elétrica é essencial para atingir bons desempenhos no controle daqueles sistemas. Então, o presente trabalho apresenta uma revisão de alguns dos principais métodos de sincronização encontrados na literatura, mostrando as vantagens e deficiências dos mesmos. Outrossim, dois novos métodos são concebidos nesta tese e comparados com os demais. As suas funcionalidades são corroboradas por meio de simulações e experimentos. Salienta-se que o enfoque é dado às técnicas empregadas em sistemas elétricos trifásicos.

Aujourd'hui, la gestion du risque en milieu profesionnel ainsi que l'évaluation de l'exposition aux polluants, tels que les Composés Organiques Volatils (COV) présents dans l'air deviennent une nécessité tant la qualité de l'air des lieux de travail peut être à l'origine de problèmes de santé ou de maladies professionnelles reconnues. Dans le but de répondre à ces exigences de sécurité, l'Université Claude Bernard Lyon 1 a institutionnalisé et développé une Cellule Analyse Hygiène Sécurité et Environnement en lien direct avec le service SHS préexistant. Cette cellule est chargée de la mise en place d'une méthodologie de surveillance de la qualité de l'air intérieur de l'ensemble des locaux de l'université (14 sites, environ 80 laboratoires) en accord avec le code du travail et de l'environnement. Afin de pouvoir assurer l'ensemble des analyses inhérentes aux lieux de travail, le SHS a défini 45 composés comme prioritaires ajoutés à la liste du SHS et portent à 93 le nombre de COV identifiés et quantifiés. La méthode de séparation et d'identification mise en place permet d'atteindre des limites de quantification largement inférieures aux VLCT et VLEP 8 heures fixées par la législation. Des campagnes de prélèvement ont pu ainsi être organisées en collaboration avec le SHS et être lancées au sein de l'université / Over the past 10 years, indoor air quality has become a real Health and Safety concern, especialty in the workplace, which has led to the legislation proposal of concentrations guidelines for pollutants such as Volatiles Organic Compounds (VOC). To comply with the Safety requirements, The Claude Bernard University Lyon 1 has institutionalized and developed an Environment, Health and Safety Unit (HSE Unit), to provide the analyses for the Health and Safety team (SHS). This specialist unit has developed a supervision methodology to control the indoor air quality in all the buildings of the university, including all the 80 research and training laboratories. In order to carry out the assessment, the SHS team defined 45 compounds classified as priority, according to their threshold limit values (TLV-TWA or TLV-STEL) to the workers. To this list of 45 VOC another list containing 48 VOC is added. Evaluation of the trapping capacity of each sorbent, for a mix containing 93 VOC has been studied. Moreover, separation and identification methods were developed and optimized allowing to reach a quantification limit lower than professional limit value exposure. Using these methods and the results of the trapping comparisons, different applications were implemented, such as sampling campaigns in different laboratories

EPDM and R-EPDM granules are used as infill on all of the artificial football fields in Uppsala. The aim of the study was to establish possible health risks related to the infill for players on artificial turf in Uppsala. Furthermore the aim was to investigate the possible ecotoxicological effect on surrounding waterways by the infill material. A comparative analysis concerning health and ecotoxicological effects for these materials was carried out. Eight different granules from the artificial turf in Uppsala was collected and analysed using TGA. The TGA results were modelled in two different scenarios to show possible air concentrations of 100-300 µg/m3 VOC over artificial football fields with EPDM granules. Calculations based on the tolerable daily dose of substances found in the granules were carried out. The conclusions of the study shows that the EPDM granules used today are safe from a health perspective. SBR granules from recycled tires does not constitute to any health risks either. The ecotoxicological risk for surrounding waterways is low. EPDM is less cost and energy efficient compared to SBR from recycled tires. Reduction of granular spill is very important from an environmental and cost point of view, regardless of the choice of material for artificial turf.

EPDM and R-EPDM granules are used as infill on all of the artificial football fields in Uppsala. The aim of the study was to establish possible health risks related to the infill for players on artificial turf in Uppsala. Furthermore the aim was to investigate the possible ecotoxicological effect on surrounding waterways by the infill material. A comparative analysis concerning health and ecotoxicological effects for these materials was carried out. Eight different granules from the artificial turf in Uppsala was collected and analysed using TGA. The TGA results were modelled in two different scenarios to show possible air concentrations of 100-300 µg/m3 VOC over artificial football fields with EPDM granules. Calculations based on the tolerable daily dose of substances found in the granules were carried out. The conclusions of the study shows that the EPDM granules used today are safe from a health perspective. SBR granules from recycled tires does not constitute to any health risks either. The ecotoxicological risk for surrounding waterways is low. EPDM is less cost and energy efficient compared to SBR from recycled tires. Reduction of granular spill is very important from an environmental and cost point of view, regardless of the choice of material for artificial turf.

L'oxydation des composés organiques émis dans l'atmosphère est progressive et conduit à la formation d'une multitude de composés organiques secondaires. Ces composés organiques secondaires (COS) peuvent être hydrosolubles et donc réagir dans la phase aqueuse atmosphérique. La communauté scientifique s'intéresse actuellement à l'impact environnemental de la réactivité de la matière organique atmosphérique en phase aqueuse. Des études récentes montrent par exemple que ces modifications pourraient entraîner une augmentation de la production d'aérosol organique secondaire (AOS). Pour explorer les effets de la réactivité aqueuse, une modélisation détaillée de la dissolution des COS et de leur oxydation aqueuse a été menée dans ce travail. Cette modélisation repose sur l'extension du générateur de schémas chimiques explicites GECKO-A (Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere).La fraction soluble des COS est peu connue. Il est donc nécessaire de la quantifier en fonction du contenu en eau liquide. GECKO-A permet de générer des schémas explicites d'oxydation en phase gazeuse. Pour intégrer la dissolution des composés organiques formés, leurs constantes de Henry ont été documentées. Le faible nombre de données disponibles (600) comparé au très grand nombre d'espèces secondaires formées (>103) demande d'estimer empiriquement la majorité des constantes de Henry. Nous avons eu recours à une méthode d'estimation de type structure-propriété développée au LISA, GROMHE (GROup contribution Method for Henry's law Estimates). Ceci a permis de décrire le transfert de masse de toutes les espèces solubles générées lors de l'oxydation de trois précurseurs d'intérêt atmosphérique : l'isoprène, l'octane et l'α-pinène. Pour un contenu en eau liquide typique d'un aérosol déliquescent, seule une très faible fraction des COS est dissoute. Cependant, nous avons montré qu'une proportion significative des COS est susceptible de se dissoudre dans une phase aqueuse nuageuse. La dissolution et la réactivité des COS issus de l'oxydation des composés à chaîne longue doivent donc être représentées dans les modèles. Pour décrire la réactivité aqueuse des composés organiques dissous, un module de réactivité aqueuse a été ajouté à GECKO-A. La génération des mécanismes d'oxydation aqueuse repose sur l'écriture d'un protocole d'oxydation systématique. En s'appuyant sur les connaissances disponibles, ce protocole définit les règles d'oxydation et d'estimation des constantes inconnues. Implémenté dans GECKO-A, il permet dorénavant d'écrire des schémas d'oxydation multiphasique explicites pour les composés organiques. Pour l'instant, les espèces précurseur sont limitées en longueur de chaîne carbonée à cause de la taille des schémas générés. Le traitement de l'octane et de l'α-pinène est par exemple impossible. Néanmoins, à partir du mécanisme généré pour l'isoprène, le modèle a été utilisé pour explorer l'impact de la réactivité aqueuse sous différentes conditions environnementales. La réactivité aqueuse modifie significativement la distribution du carbone entre les phases ainsi que la spéciation de la matière organique dans les deux phases. Nous avons en particulier montré une production importante de diacides carboxyliques, espèces régulièrement identifiées dans la phase particulaire lors de mesures de terrain. Le mécanisme généré permet pour la première fois d'identifier environ 360 voies de formation différentes pour l'acide oxalique / The atmospheric oxidation of organic compounds is progressive and leads to the formation of a myriad of secondary organic compounds. These secondary organic compounds (SOC) can be hydrosoluble and react in the atmospheric aqueous phase. The scientific community is currently interested in the environmental impact of the atmospheric organic matter aqueous phase reactivity. For example, recent studies show that these modifications could increase the secondary organic aerosol (SOA) production. In order to explore effects of the aqueous reactivity, this work consists of a detailed modeling study of the SOC dissolution and their aqueous oxidation. The modeling is based on the extension of the explicit chemical schemes generator GECKO-A (Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere).There is little known about the soluble fraction of SOC. It is thus needed to quantify it as a function of the liquid water content. GECKO-A enables the generation of explicit oxidation schemes for the gas phase. To integrate the dissolution of produced organic compounds, their Henry's law constants have been documented. The low number of available data (600) compared to the large number of formed secondary species (>103) requires the empirical estimate of the majority of Henry's law constants. We relied on an estimate method based on a structure-activity relationship developed at LISA, GROMHE (GROup contribution Method for Henry's law Estimates). This allowed us to describe the mass transfer of every soluble species generated during the oxidation of three precursors of atmospheric interest: isoprene, octane and α-pinene. For a liquid water content typical of a deliquescent aerosol, only a very small fraction of SOC is dissolved. However, we showed that a significant proportion of SOC could dissolve in a cloud aqueous phase. Dissolution and reactivity of SOC produced from the oxidation of long chain compounds need to be represented in models. In order to describe the aqueous reactivity of dissolved organic compounds, a aqueous reactivity module was added to GECKO-A. The generation of aqueous oxidation mechanisms is based on the writing of a systematic oxidation protocol. Supported by available knowledge, this protocol defines rules for oxidation and estimates of unknown constants. Implemented in GECKO-A, it now enables us to write multiphase explicit oxidation schemes for organic compounds. For now, precursor species are limit in the carbon skeleton length by the size of generated schemes. Treatment of octane and α-pinene is for example impossible. Nevertheless, from the mechanism generated for isoprene, the model has been used to explore the aqueous reactivity impact under different environmental conditions. Aqueous reactivity modifies significantly the carbon distribution between phases as well as the organic matter speciation in both phases. In particular, we showed an important production of carboxylic diacids, species that are regularly identified in the particulate phase during field measurements. For the first time, the generated mechanism allows the identification of approximately 360 different formation pathways for oxalic acid

There is limited scientific knowledge on the composition of human odor from different biological specimens and the effect that physiological and psychological health conditions could have on them. There is currently no direct comparison of the volatile organic compounds (VOCs) emanating from different biological specimens collected from healthy individuals as well as individuals with certain diagnosed medical conditions. Therefore the question of matching VOCs present in human odor across various biological samples and across health statuses remains unanswered. The main purpose of this study was to use analytical instrumental methods to compare the VOCs from different biological specimens from the same individual and to compare the populations evaluated in this project. The goals of this study were to utilize headspace solid-phase microextraction gas chromatography mass spectrometry (HS-SPME-GC/MS) to evaluate its potential for profiling VOCs from specimens collected using standard forensic and medical methods over three different populations: healthy group with no diagnosed medical or psychological condition, one group with diagnosed type 2 diabetes, and one group with diagnosed major depressive disorder. The pre-treatment methods of collection materials developed for the study allowed for the removal of targeted VOCs from the sampling kits prior to sampling, extraction and analysis. Optimized SPME-GC/MS conditions has been demonstrated to be capable of sampling, identifying and differentiating the VOCs present in the five biological specimens collected from different subjects and yielded excellent detection limits for the VOCs from buccal swab, breath, blood, and urine with average limits of detection of 8.3 ng. Visual, Spearman rank correlation, and PCA comparisons of the most abundant and frequent VOCs from each specimen demonstrated that each specimen has characteristic VOCs that allow them to be differentiated for both healthy and diseased individuals. Preliminary comparisons of VOC profiles of healthy individuals, patients with type 2 diabetes, and patients with major depressive disorder revealed compounds that could be used as potential biomarkers to differentiate between healthy and diseased individuals. Finally, a human biological specimen compound database has been created compiling the volatile compounds present in the emanations of human hand odor, oral fluids, breath, blood, and urine.

Metabolomics is a post genomic field of research concerned with the study of low molecular weight compounds within a biological system permitting the investigation of the metabolite differences between natural and perturbed systems (such as cells, organs and tissues). Rapid identification and discrimination of biological samples based upon metabolic differences and physiological status in microbiology, mammalian systems (particularly for disease diagnosis), plants and food science is highly desirable. Volatile organic compound (VOC) profiling is a novel area of research where the composition of the VOCs emitted by the biological samples can be correlated to its origin and physiological status. The aim of this project was to investigate the applicability of VOC profiling as a potential complementary tool within metabolomics.In this project the discrimination of bacteria using a novel gas phase separation method was investigated and the development of VOC-based profiling tools for the collections of VOCs emitted from biological samples was also studied. The optimisation and validation of a high throughput method for VOC analysis was achieved and this was used to assess wound healing.VOC metabolite profiling was further extended to the discrimination of S. typhimurium contaminated meat; the study was conducted in parallel with metabolite profiling analysis for the analysis of non-volatile small molecules. Finally, enhanced vibrational spectroscopic techniques were applied to the characterisation and screening of dye molecules in contaminated foodstuffs using Raman spectroscopy. This thesis clearly demonstrates that VOC metabolic profiling is a complementary tool within the metabolomics toolbox, one of its great attractions is that it permits the characterisation of biological samples in a rapid and non-invasive manner. The technique provides detailed chemical information regarding the VOC composition present above the headspace of the sample and can be used to understand its physiological status and biological origin. VOCs metabolite profiling will become a valuable tool for non-invasive analysis of many biological systems. Raman spectroscopy is a sensitive and non-destructive technique which can generate detailed chemical and structural information regarding the analyte under investigation with little or no sample preparation needed. The effect of the weak Raman signal can be significantly amplified by coupling the analyte molecule to surfaces of nanoparticles and demonstrated that it is ideal for analysing aqueous dye solutions in a quantitative manner.

L’objectif principal de ce travail de thèse est de contribuer au développement d’un outil de diagnostic miniaturisé permettant d’identifier et de quantifier une combinaison de composés organiques volatils (COVs) présents dans l’haleine et qui sont considérés comme des marqueurs chimiques du cancer du poumon. Les principaux verrous scientifiques de ce projet sont liés aux très faibles concentrations de ces composés cibles (de l’ordre de quelques ppb) et également à la présence de nombreux autres composés chimiques qui sont naturellement présents dans l’haleine. La voie de développement proposée dans ce projet est d’utiliser un micro-capteur résistif à base de SnO2 associé à un micro-préconcentrateur et une micro-colonne chromatographique afin d’aboutir à un dispositif sélectif et présentant des limites de détection très basses. Dans un premier temps, plusieurs adsorbants ont été caractérisés en vue d’être utilisés dans le micro-préconcentrateur afin de concentrer les marqueurs du cancer du poumon. Les résultats ont permis de sélectionner deux types de zéolites (DaY et NaY) ainsi que des microsphères de carbone W5. Par la suite, les unités de préconcentration et de séparation des COVs ont été développées en s’appuyant sur la technologie silicium/verre disponible en salle blanche. La dernière étape de cette étude a concerné l’évaluation des performances du système d’analyse alors assimilable à un micro-chromatographe en phase gazeuse. Après avoir déterminé les conditions optimales d’élution et de préconcentration des COVs, le système miniaturisé a permis d’analyser une haleine artificielle constituée de trois COVs présents à des concentrations proches des celles mesurées dans l’haleine (toluène (24 ppb), propanol (21 ppb) et o-xylène (5 ppb)) même en présence des interférents majeurs de l’haleine (vapeur d’eau et dioxyde de carbone). / The main goal of this research is to develop a miniaturized diagnostic equipment in order to identify some volatile organic compounds present in exhaled breath and referred as lung cancer biomarkers. The main scientific and technical obstacles of this project are linked to the very low concentrations of these chemical compounds and the presence of high concentrations of H2O and CO2 naturally present in exhaled breath. To address these issues, we suggest to use a SnO2-based gas sensor combined with a micro-preconcentrator and a chromatographic micro-column in order to engineer a low detection limit system. First, some specific adsorbents have been characterized with a view to concentrate chemical biomarkers trough the micro-preconcentrator. In accordance with research findings, two types of zeolites (DaY and NaY) and one type carbonaceous microspheres (W5) have been selected. Then micro-preconcentrators and chromatographic micro-columns have been developed on silicon wafers by using clean room facilities. The last step of this study was to evaluate the performances of the analytical device. After determining optimal elution and pre-concentration conditions of each VOCs, the miniaturized system achieved the analysis of an artificial breath constituted of toluene (24 ppb), 1-propanol (21 ppb) and o-xylene in presence of high concentrations of water vapors and carbon dioxide.

Content: Car industry is highly demanding for low emission parameters and despite remarkable results have been achieved since the last decade, the requests are day by day more sophisticated. The focus on emission is a severe task and requires the investigation on emissions on full-range and involves the expertise of multi and inter disciplinal competences. The leather industry is a clear key ring for car interior suppliers and it is also focusing on more sustainable processes and reducing the emission of pollutants to the environment, prompting the commitment of leather suppliers, tanneries, and chemical auxiliaries producers. From our perspective, in fact, one of the major problems that car interior producers are currently facing is the production of low-emitting leather, which requires special chemical auxiliaries to be achieved. In this context, our research has focused on the study of VOC volatile substances from car interiors, in particular on finishing systems, aiming at their reduction without losing the original performances of the finished leather article. Our investigation focused on full grain finished leathers, evaluating the contribution to the VOC emission from crust leather to the finished articles. A preliminary study showed that silicon compounds family brought an important contribution to the emission from a qualitative and quantitative perspective: these substances play a crucial role in terms of the final article performances (such as resistance), and quality. So, our investigation focused on innovative silicon-free auxiliary combination to give low VOC emission contribution from the leather compared with the same performances of the original silicon containing finishing. In order to evaluate the impact of the emissions, a series of analyses of the volatiles were performed: static headspace VDA 277 (and/or PV3341) analysis and active air sampling analysis GS 97014-3 type were performed, indicating that silicon contribution was very high in the emission. In addition, the quality of the leather was also assessed and characterised through standard automotive tests such as stick-slip, abrasion trials with Taber tester and Martindale machine, ball plate method, fogging test; rub fastness provided with Veslic tester (wet, dry, alcohol, gasoline), dry-rubbing trial with Gakushin tester. The set of result showed that standard leather containg silicon compounds on the finishing produced high VOC emission and high performance articles, thus contributing to VOC emission. Conversely, the novel finishing auxiliaries had low VOC emission, no silicons, yet high performance leather and therefore should be chosen from a more environmental point of view. Take-Away: Low VOC emission from novel leather finishing albeit high resistance leather.