La miniaturisation et la complexification croissante des composants microélectroniques induit une sensibilisation et une fragilisation accrue des composants vis-à-vis des contaminations présentes dans les zones de productions appelées “salles blanches”. Dans ces espaces, le contrôle actuel de la contamination organique n’est pas suffisant puisqu’il ne permet pas d’éviter la contamination de surface des plaquettes de silicium et des optiques des robots de production utilisés pour la photolithographie. Un contrôle accru des concentrations des contaminants organiques dans les atmosphères des salles blanches devient donc nécessaire et de nouvelles méthodes analytiques doivent être développées et validées. Dans le cadre de ce travail, des méthodes d’analyse ont été développées et validées afin de disposer d’une gamme d’outils permettant un suivi rigoureux des contaminations. Ces outils permettent d’identifier et de quantifier les contaminations surfaciques des plaquettes de silicium par des composés organiques semi-volatils (phtalates et organophosphorés) mais aussi de déterminer les concentrations de composés organiques volatils présents dans l’atmosphère des salles blanches. Ces méthodes font appel aux technologies du WOS/ATD-GC-MS « Wafer Outgassing System/Automated Thermal Desorber–Gas Chromatography–Mass Spectrometry » et de la DART-ToF-MS « Direct Analysis in Real Time-Time of Flight–Mass Spectrometry » pour les analyses de surfaces et au PTR-ToF-MS « Proton Transfer Reaction – Time of Flight - Mass Spectrometry » pour l’analyse de l’atmosphère. / The recent advances in the miniaturization and complexification of microelectronic components induce an increase in the sensitivity of these components regarding the organic contamination present in the production zone called “clean room”. Although, the control of organic contamination in the clean room is very rigorous it does not avoid the contamination of silicon wafer surfaces and robot lenses used in the photolithography process. The later implies that new analytical methodologies should be developed and validated. In this work, analytical methods were developed and validated in order to have a panel of tools which allows careful monitoring of organic contaminants. These tools allow the identification and quantitation of the contamination of silicon wafer surface by semi-volatiles organic compounds (phthalates and organophosphates) and the determination of volatile organic compounds concentrations in the clean room atmosphere. These methods uses the WOS/ATD-GC-MS « Wafer Outgassing System/Automated Thermal Desorber–Gas Chromatography–Mass Spectrometry » technology and the DART-ToF-MS « Direct Analysis in Real Time-Time of Flight–Mass Spectrometry » technology for wafer surface analysis and the PTR-ToF-MS « Proton Transfer Reaction – Time of Flight - Mass Spectrometry » technology for gas-phase analysis.

L'évaluation de l'inertie des matières plastiques au contact de denrées alimentaires est régie par le règlement européen N°10/2011. Au Liban, l'absence de législations relatives à l'usage des matières en plastiques a conduit à des emballages non contrôlés au niveau de la production et du stockage, ce qui peut induire un risque sanitaire pour le consommateur. L'objectif de ce travail a été d'apprécier les phénomènes de migration des contaminants du PET vers l'eau. Pour cela, l'analyse de certains migrants potentiels a été initiée tels que des COV et des SV afin de vérifier la conformité de leur teneur par rapport aux LMA dans les règlementations internationales. Le dosage des aldéhydes dans l'eau a été effectué par dérivation avec la 2,4-DNPH, suivie d'une étape de préconcentration sur une cartouche en C18, puis séparation et quantification par HPLC-UV. L'analyse des composés SV a été réalisée par SPME-GC-FID sur une fibre en PDMS/DVB. L'analyse des BTEX et du styrène a été réalisée par HS-Trap-GC-FID. Ces méthodes ont été validées conformément à la norme NF T 90-210 avec des LQ inférieures aux LMA. L'analyse des COV dans l'eau embouteillée et dans le PET a été réalisée par HSTrap- GC-MS. La présence de FA, d'AA, de DEP et des BTEX dans l'eau embouteillée en PET a été confirmée. Il a été mis en évidence que la température et l'exposition solaire influencent la migration des aldéhydes. Les concentrations d'AA trouvées après incubation à 40ºC ne sont pas négligeables et peuvent modifier les propriétés organoleptiques de l'eau. L'analyse du PET montre la présence des hydrocarbures, des aldéhydes, des alcools, et des cétones / The inertness’ value of plastics that are on contact with foodstuffs is governed by the European rule N°10/2011. In Lebanon, the lack of the Rules and Regulations of plastics’ usage led for a non-controlled packing in production as in storage, which will cause a sanitary risk to the consumer and to the population. The purpose of this research was to appreciate the migration’s phenomena of contaminants from the PET to the water. For this, there was an analysis of potential migrants such as VOC and SV to verify their tenor’s conformity relative to the MCL in international regulations. The aldehydes’ dosage in the water was performed by the derivation with the 2,4-DNPH, followed by a concentration on a C18 cartridge, then separation and quantification was done by HPLC-UV. The SV compounds’ analysis was realized by SPME-GC-FID method on a PDMS / DVB fiber. The BTEX and the styrene’s analysis was done by HS-trap-GC-FID method. These methods were validated in accordance with standard NF T 90-210 with a LQ less than the MCL. The volatile compounds in the bottled water and in the PET were analyzed by HS-trap-GC-MS method. The presence of FA, AA, DEP and BTEX in the bottled water with the PET was confirmed. It was highlighted that temperature and sun exposition influence the aldehydes’ migration. The acetaldehyde’s concentration after incubation at 40ºC wasn’t negligible and can modify the water’s organoleptic properties. The PET’s analyze reveals the presence of hydrocarbons, aldehydes, alcohols and ketones

Les huiles essentielles extraites de plantes aromatiques, médicinales et à parfum, sont utilisées depuis des millénaires pour leurs propriétés médicinales ou olfactives. Pour des raisons de rentabilité, les distributeurs sont contraints à réduire leur coût au maximum et à commercialiser des huiles essentielles au plus bas prix. Certains ont recours à la fraude et proposent, des essences de qualité inférieure sous la dénomination produits naturels de haute qualité. Il existe des normes (AFNOR, pharmacopées) qui doivent être respectées. Mais leur seule application est souvent limitée. Cette étude a donc permis une nette amélioration du contrôle de la naturalité des huiles essentielles de citrus, et lavande. La connaissance des compositions moléculaires des volatiles et des polymethoxyflavones (citron), l'étude énantiomérique de molécules cibles telles que l'alpha-pinène, le sabinène (citrus), le linalol et l’acétate de linalyle (bergamote et lavande), les analyses isotopiques du carbone 13, deutérium, des linalol, acétate de linalyle (bergamote et lavande), citral, acétate de géranyle (citron) ainsi que les analyses isotopiques du deutérium et azote 15 du N-méthyle anthranilate de méthyle (mandarine) sont les analyses permettant la mise en évidence de nombreux types de fraudes. Pour une méthodologie efficace, les analyses en composante principale et discriminante ont été indispensables. Elles ont permis l’identification d’échantillons fraudés via l’étude des volatiles. Les analyses chirales et isotopiques permettent l'identification d'échantillon plus “ finement ” adultérés ou de mieux comprendre les processus de fraude / Essential oils extract from aromatics, medicinal and perfume plants, are used since ancient times for their medicinal or olfactory properties. They are quite expensive, and owing to the actual growing demand for getting high quality materials at lowest prices, fraudulent essential oils are frequently found on the market. In order to fight this problem, norms exist (AFNOR, pharmacopeas) which have to be respected. However those techniques are often limited. This work allowed great improves in the quality control of citrus and lavender essential oils. The knowledge of the chemical composition of volatiles and polymethoxy-flavones (lemon), of the chirale ratios of alpha-pinene, le sabinene (citrus), linalool et linalyl acetate (bergamot et lavender), isotope ratio analyses of carbon 13, deuterium, of linalool, linalyl acetate (bergamot et lavender), citral, geranyl acetate (lemon) as wall as isotope ratio analyses of deuterium of nitrogen 15 du Nmethyl anthranilate de methyl (mandarin) permitted the detection of various type of frauds. In order to have an efficient methodology, principal component and discriminant analyses have been proved indispensables. It allowed the identification of fraudulent samples via volatiles molecules study. Chirale analysis and isotope ratio highlight frauds on more “discrete” adulterated samples or a better understanding of adulteration’s process

<p>U ovoj doktorskoj disertaciji je uspe&scaron;no izvr&scaron;eno izolovanje&nbsp;opijatnih alkaloida iz humanih biolo&scaron;kih uzoraka (moždanog&nbsp;tkiva, krvi, urina i žuči) kao i biolo&scaron;kih uzoraka&nbsp;<br />eksperimentalnih životinja (moždanog tkiva i krvi) primenom&nbsp;postupka čvrsto-tečne ekstrakcije (SPE-Solid Phase Extraction).&nbsp;Modifikovan je postupak za kvalitativnu i kvantitativnu GC-MS&nbsp;(Gas Chromatography-Mass Spectrometry) analizu biolo&scaron;kih&nbsp;<br />uzoraka.&nbsp;Utvrđena je distribucija opijatnih alkaloida: morfina, kodeina,&nbsp;acetilkodeina, 6-acetilmorfina i heroina u humanim biolo&scaron;kim&nbsp;uzorcima moždanog tkiva (moždanoj kori, moždanom stablu,&nbsp;amigdali i bazalnim jedrima), pri čemu je najveći sadržaj&nbsp;<br />opijata određen u moždanoj kori i bazalnim jedrima,&nbsp;podjednako kod mu&scaron;kih i ženskih osoba.&nbsp;Utvrđena je distribucija opijatnih alkaloida: morfina, kodeina,&nbsp;acetilkodeina, 6-acetilmorfina i heroina u biolo&scaron;kim uzorcima&nbsp;moždanog tkiva (moždanoj kori, moždanom &nbsp;stablu, amigdali i&nbsp;bazalnim jedrima) i krvi eksperimentalnih životinja (pacova), u&nbsp;<br />različitim vremenskim periodima (5, 15, 45 i 120 minuta) od&nbsp;tretiranja životinja heroinom.&nbsp;Najveći sadržaj opijata je određen u moždanoj kori i bazalnim&nbsp;jedrima, podjednako kod mužjaka i ženki pacova ali u različitim&nbsp;vremenskim periodima. U uzorcima krvi je najveći sadržaj&nbsp;opijata određen u istom vremenskom periodu kod životinja oba&nbsp;pola, pri čemu su kod mužjaka određene znatno veće vrednosti&nbsp;koncentracija, &scaron;to ukazuje na bržudistribuciju opijata iz krvi u&nbsp;mozak kod ženki u &nbsp;odnosu na mužjake pacova.&nbsp;Utvrđeno je da je distribucija opijata u humanom moždanom&nbsp;tkivu kod pripadnika suprotnih polova kao i moždanom tkivu&nbsp;mužjaka i ženki pacova (nakon 120 minuta od tretiranja&nbsp;heroinom), identična.&nbsp;Ispitivanjem uticaja opijata &nbsp;na markere oksidativnog stresa u&nbsp;jetri eksperimentalnih životinja suprotnih polova, utvrđeno je&nbsp;smanjenje aktivnosti enzima: katalaze (CAT), glutation-peroksidaze (GSH- Px), peroksidaze (Px) i ksantin-oksidaze&nbsp;(XOD).</p> / <p>Opiate alkaloids were successfully isolated from human biological samples (brain tissue, blood, urine, and bile) as well as from biological samples of experimental animals (brain tissue and blood) by applying procedure of solid-phase extraction (SPE). A modified procedure was worked out for qualitative and quantitative analysis of biological samples by gas chromatography-mass spectrometry (GC-MS). The distribution of opiate alkaloids:morphine, codeine, acetylcodeine, 6-acetylmorphine, and heroine in human biological samples of brain tissue (cortex, brain stem, amigdala and basal nuclei) was established, showing the highest content of opiates &nbsp; in the cortex and basal nuclei, equal with male and female persons. It was established how the opiatealkaloids: morphine codeine, acetylcodeine, 6-acetylmorphine&nbsp; and heroine are distributed in biological samples of brain tissue (cortex, brain stem, amigdala and basal nuclei) and blood of experimental animals&nbsp; (rats) in different time periods (5, 15, 45 and 120 min) after the animal treatment with&nbsp;heroine. The highest content of opiates was found in the cortex and basal nuclei,&nbsp;equal in the male and female rats, but in different time periods. In blood samples, the highest content of opiates was measured in the same period with animals of both sexes, the concentration in the males being significantly higher, indicating a faster passage of the opiates from blood to brain in the female compared to male rats.&nbsp;Identical distribution of opiates was found in human brain tissue of both male and female subjects as in rats of both sexes (120 min after treatment with heroine).&nbsp;Study of the effect of opiates on the markers of oxidative stress in the liver of tested animals of opposite sexes showed a lowered activity of the following enzymes: &nbsp;catalase (CAT), glutathion-peroxidase (GSH-Px), peroxidase (Px) and xanthine-xidase &nbsp;(XOD).</p>

Demosponges of the order Verongida such as Ianthella basta exhibit skeletons containing spongin, a collagenous protein, and chitin. Moreover, Verongida sponges are well known to produce bioactive brominated tyrosine derivatives. We recently demonstrated that brominated compounds do not only occur in the cellular matrix but also in the skeletons of the marine sponges Aplysina cavernicola and I. basta. Further investigations revealed the amino acid composition of the skeletons of A. cavernicola including the presence of several halogenated amino acids. In the present work, we investigated the skeletal amino acid composition of the demosponge I. basta, which belongs to the Ianthellidae family, and compared it with that of A. cavernicola from the Aplysinidae family. Seventeen proteinogenic and five non-proteinogenic amino acids were detected in I. basta. Abundantly occurring amino acids like glycine and hydroxyproline show the similarity of I. basta and A. cavernicola and confirm the collagenous nature of their sponging fibers. We also detected nine halogenated tyrosines as an integral part of I. basta skeletons. Since both sponges contain a broad variety of halogenated amino acids, this seems to be characteristic for Verongida sponges. The observed differences of the amino acid composition confirm that spongin exhibits a certain degree of variability even among the members of the order Verongida.

Dans le but d’évaluer la contamination des atmosphères intérieures et extérieures induite par les usages non agricoles de pesticides, deux approches complémentaires ont été mises en oeuvre : l’utilisation de capteurs passifs de type Tenax TA pour réaliser des prélèvements d’air, et l’utilisation de cheveux employés comme biomarqueurs d’exposition. Des campagnes de mesures ont été menées sur plusieurs sites à la suite de traitements de désherbage ou de désinsectisation ainsi quedans des logements. Les échantillons d’air et de cheveux ont été extraits respectivement par thermodésorption et par extraction solide-liquide, avant d’être analysés en chromatographie gazeuse couplée à la spectrométrie de masse (GC-MS). Une augmentation du niveau de contamination de l’air extérieur et intérieur et l’existence de transferts entre ces deux milieux ont pu être observées après l’application de pesticides. Dans les logements, des pesticides actuellement employés mais aussi des pesticides interdits et persistants ont été détectés. Plusieurs pesticides ont également été détectés dans les cheveux, mais l’exposition humaine à ces derniers n’a pas pu toujours être corrélée à une contamination de l’air. / In order to evaluate indoor and outdoor air contamination resulting from non-agricultural uses of pesticides, two complementary approaches were applied: passive samplers based on Tenax TA used for air sampling and hair used as biomarkers of exposure. Sampling campaigns were conducted on several sites after weeding and pest control treatments as well as in accommodations. Air samples and hair samples were respectively extracted by thermal desorption and solid-liquid extraction prior to their analysis by gas chromatography combined with mass spectrometry (GC-MS). An increase of the indoor and outdoor air contamination levels and the existence of transfers between these two environments could be observed after pesticides applications. In accommodations, pesticides currently used and banned but persistent ones were detected. Several pesticides were also detected in hair samples but human exposure to these pesticides cannot be correlated with air contamination in all cases.

Depuis le 11 juillet 2013, date d’application du Règlement cosmétique (CE) No 1223/2009, les metteurs sur le marché sont dans l’obligation de mentionner sur leurs produits la Date de Durabilité Minimale (DDM), ou si celle-ci excède 30 mois, la Période Après Ouverture (PAO). L’estimation de ces dates n’est pas encadrée réglementairement. Cosmetics Europe, l’Agence nationale de sécurité du médicament et des produits de santé, le Comité scientifique pour la sécurité du consommateur ou encore la Commission Européenne proposent des lignes directrices, mais les conditions d’étude pour la détermination de la DDM et de la PAO restent encore à l’appréciation de la personne responsable de la commercialisation du produit. L’objectif de ce travail était d’étudier les conditions nécessaires à la mise en place d’un protocole de mesure de la stabilité d’émulsions cosmétiques, permettant de déterminer la DDM du produit de manière fiable et rapide. Pour cela, une approche expérimentale sur une émulsion représentative de l’industrie cosmétique a été menée. L’évolution des paramètres organoleptiques, physico-chimiques et microbiologiques a été évaluée, en accéléré (température augmentée) et en temps réel. Une approche statistique a montré que les propriétés sensorielles évoluent différemment en fonction de la température et du matériau dans lequel l’émulsion est stockée. L’établissement d’un modèle de correspondance entre le vieillissement en conditions réelles et en conditions accélérées a pu être proposé pour certains paramètres physico-chimiques. Les études de microbiologie se sont tout d’abord concentrées sur la validation d’une méthode commerciale, alternative au dénombrement des germes aérobies totaux encadré par la norme ISO 21149, pour une application dans le domaine cosmétique. Après validation, la méthode a été utilisée comme un outil simple, rapide et économique pour le suivi de la stabilité microbiologique de l’émulsion de référence. La dégradation des conservateurs et de l’antioxydant présents dans la formule de référence a été suivie par chromatographie en phase gazeuse couplée à la spectrométrie de masse (GC-MS). Ce suivi a permis de mettre en évidence l’effet probable de la lumière sur la dégradation des actifs de l’émulsion. A ces tests ont été associés une stratégie analytique visant à étudier la photostabilité de l’émulsion. Les études ont porté sur deux molécules : l’acide déhydroacétique et l’alpha-tocophérol. La stratégie a permis de caractériser les mécanismes impliqués dans les réactions de photodégradation. La chromatographie en phase gazeuse couplée à la spectrométrie de masse multi-étapes (GC-MSn) et la chromatographie en phase liquide couplée à la spectrométrie de masse haute résolution en tandem (LC-HR-MS/MS) ont été utilisées pour la séparation et l'identification structurale des photoproduits. La détection des photoproduits majoritaires dans l’émulsion de référence, après irradiation UV-visible, montre la possible formation des photoproduits dans une matrice complexe de type émulsion huile/eau. Les résultats des tests de toxicité, in silico et/ou in vitro, ont démontré l’importance de prendre en compte la formation éventuelle de photoproduits dans l’évaluation de la sécurité d’un produit cosmétique. / According to Cosmetic Regulation 1223/2009, implemented in July 2013, the manufacturer must mention the Date of Minimum Durability (DMD), or if DMD exceeds 30 months, the Period After Opening (PAO) on the product packaging. At the present time, no text regulates the procedures applicable to the validation of a DMD or a PAO. Some guidelines are published by Cosmetics Europe, the National Agency for the safety of medicines and health products, the Scientific Committee for consumer safety, or the European Commission; but the evaluation remains at the discretion of the person responsible for marketing the product. In this context, this work proposes recommendations to establish a stability protocol in order to quickly determine the DMD. Experimental approaches on an emulsion representative of the major category in the cosmetics industry have been established. Organoleptic, physicochemical and microbiological stabilities were evaluated. The emulsion stability has been tested in accelerated conditions and in real time. A statistical approach has been proposed to evaluate the product shelf life according to its organoleptic properties. The sensory properties of the cosmetic emulsion changed differently depending on the temperature and the material in which it has been stored. A mathematical correlation between the results of studies under normal and those obtained under accelerated conditions has been proposed for some parameters. A microbiological study focused on the validation of a commercially available method, alternative to total count of aerobic microorganisms, normed by the ISO 21149 for cosmetic application. Once validated, this method has been used as an economical, quick and easy tool to evaluate the microbiological stability of cosmetic emulsions. Gas chromatography coupled with mass spectrometry was used to follow the degradation of antioxidant and preservatives. To take into account the photostability of the emulsion, an analytical strategy was proposed to identify the mechanisms involved in phototransformation reactions. The study focused on two molecules: dehydroacetic acid and alpha-tocopherol. Both gas chromatography coupled with tandem mass spectrometry (GC-MS/MS) and liquid chromatography coupled with ultrahigh resolution mass spectrometry (LC-UHR-MS) were used for the separation and the structural identification of photoproducts. The main photoproducts were detected in the reference emulsion after UV-visible irradiation, thus showing the possible formation of photoproducts in a complex oil/water emulsion. Both in silico and in vitro toxicity tests highlighted the need for taking into account the potential formation of photoproducts in the safety evaluation of a cosmetic product.

Auf Basis moderner unabhängiger Analysenmethoden wurden selektive und spezifische Analysenverfahren für die Analytik von Phenolen, unter besonderer Berücksichtigung der Alkylphenole entwickelt, optimiert und teilweise validiert. Es wurden Verfahren für die Hochleistungs-Flüssigchromatographie - Massenspektrometrie (HPLC-MS), Hochleistungs-Flüssigchromatographie - Kernmagnetische Resonanzspektrometrie (HPLC-NMR), Gaschromatographie - Massenspektrometrie (GC-MS) und Kapillarelektrophorese (CE) entwickelt. Die HPLC-MS wurde mit den Atmosphärendrucktechniken "Electrospray Ionization" (HPLC-ESI-MS) und "Atmospheric Pressure Chemical Ionization" (HPLC-APCI-MS) eingesetzt. Die Gaschromatographie wurde in Kopplung zu einem hochauflösenden Massenspektrometer (GC-HRMS) und in Kopplung zu einem niederauflösenden Quadrupol-Spektrometer (GC-LRMS) verwendet. Mit der Kapillarelektrophorese wurden Verfahren in den Modi "Kapillar-Zonen-Elektrophorese (CZE) und "Micellare Electrokinetische Chromatographie (MEKC) mit verschiedenen internen Anreicherungstechniken ("Stacking") entwickelt. Für die Validierung des MEKC-Verfahrens mit interner Anreicherung ("Direktes-MEKC-Stacking") wurde ein Ringversuch organisiert und durchgeführt. Anhand von representativen Modellgemischen wurden die Verfahren geprüft und miteinander verglichen. Die Modellgemische sind reproduzierbar herstellbar; ihre Stabilität und Homogenität wurde abgesichert, so daß sie als synthetische Referenzmaterialien zur laborinternen Qualitätssicherung, zur Methodenbewertung und zum Laboratoriumsvergleich eingesetzt werden können. Anhand von charakteristischen Kenngrößen wie Bestimmungsgrenzen, Selektivität, Zeitaufwand, Kosten und Meßunsicherheiten wurden die Verfahren auf ihre Eignung als Standard- bzw. Referenzverfahren bewertet. Die Verfahren der HPLC-NMR, HPLC-ESI-MS, HPLC-APCI-MS und GC-HRMS können mit unterschiedlichem Einsatzbereich als Referenzverfahren für die Analytik von Phenolen eingesetzt werden. Die GC-HRMS ist dabei das leistungsstärkste Referenzverfahren. Die Verfahren der GC-LRMS und CE ("Direktes-MEKC-Stacking") sind als Standardverfahren geeignet und besitzen alle Voraussetzungen um auch als Normverfahren für die Analytik von Phenolen eingeführt zu werden. / Different selective and specific analysis procedures were developed for the determination of phenol derivatives, in particular alkylphenols, in environmental relevant matrices using High-Performance Liquid Chromatography - Mass Spectrometry (HPLC-MS), High-Performance Liquid Chromatography- Nuclear-Magnetic Resonance Spectrometry (HPLC-NMR), Gas Chromatography- Mass Spectrometry (GC-MS) and Capillary Electrophoresis (CE). HPLC-MS was used with atmospheric pressure ionization techniques, Electrospray Ionization (HPLC-ESI-MS) and Atmospheric Pressure Chemical Ionization (HPLC-APCI-MS). Analysis procedures for GC-MS were developed for a high resolution mass spectrometer (GC-HRMS) and a low resolution benchtop quadrupole mass spectrometer (GC-LRMS). CE was used in the Capillary Zone Electrophoresis (CZE) and Micellar Electrokinetic Chromatography (MEKC) mode with different internal stacking techniques. The MEKC procedure with internal stacking (called "Direct-MEKC-Stacking") was validated by an interlaboratory comparison test. These procedures were tested and optimized using representative model mixtures and the most efficient then validated. The model mixtures were produced reproducably and their stability and homogeneity were demonstrated for the application as synthetic reference materials, e.g. for internal laboratory control, quality assurance or method development. The different analysis procedures were categorized as standard- or reference procedures on the basis of characteristic properties, e.g. detection limits, selectivity, analysis time, cost and uncertainty. HPLC-NMR, HPLC-ESI-MS, HPLC-APCI-MS, GC-HRMS can be used as reference procedures for different fields of use. Best performance can be reached with GC-HRMS. GC-LRMS and "Direct-MEKC-Stacking" can be used as standard procedures for the analysis of phenol derivatives and they fulfill all conditions for their implementation in standardization.

To release energy from chemically stored energy in the biomass was the new investigation in recent years. Utilizing of biomass for this purpose occur in two different ways, directly by burning (combustion) the biomass and indirectly by pyrolysis process which will convert the biomass to three main products, bio- tar, bio- char and synthetic gas. Biomass contains different amount of inorganic compound, especially alkali metals which causes some diverse impacts on combustion, pyrolysis and gasification process such as corrosion, agglomeration and fouling problems. This project aims to investigate the effect of K2CO3 on the pyrolysis and gasification processes of three different types of fuel; wood pellets, forest residue pellets and synthetic waste pellets at three different temperatures, 750 °C, 850 °C and 900 °C respectively. The purpose of this work to study and clarify the influence of K2CO3 on char yield, tar yield and tar compositions and the gasification rate and the reactivity of different fuels char. The pyrolysis process was carried out in a fluidized bed reactor during 2 minutes and the products were tar, char and synthetic gas. In this project interested in char and tar only. Char yield calculated and the results shows the char yield increase with increasing of [K2CO3]. While the tar analysis carried on GC- MS instrument at HB to study the tar yield and compositions. The results showed that potassium carbonate has not so much effect on tar yield and its composition. The last part was gasified the char in TGA with steam and CO2 as oxidizing media to study the influence of [K2CO3] on gasification rate and the reactivity of char samples at different temperatures. The result showed the [K2CO3] has inhibitory effect on gasification rate and the reactivity.

Metabolomics as a field has been used to track changes and perturbations in the human body by investigating metabolite profiles indicating the change of metabolite levels over time and in response to different challenges. In this thesis work, the main focus was on applying multiplatform-metabolomics to study the human metabolome following exposure to perturbations, such as diet (in the form of a challenge meal) and exhaust emissions (air pollution exposure in a controlled setting). The cutting-edge analytical platforms used for this purpose were nuclear magnetic resonance (NMR), as well as gas chromatography (GC) and liquid chromatography (LC) coupled to mass spectrometry (MS). Each platform offered unique characterization features, allowing detection and identification of a specific range of metabolites. The use of multiplatform-metabolomics was found to enhance the metabolome coverage and to provide complementary findings that enabled a better understanding of the biochemical processes reflected by the metabolite profiles. Using non-targeted analysis, a wide range of unknown metabolites in plasma were identified during the postprandial stage after a well-defined challenge meal (in Paper I). In addition, a considerable number of metabolites were detected and identified in lung lavage fluid after biodiesel exhaust exposure compared to filtered air exposure (in Paper II). In parallel, using targeted analysis, both lung lavage and plasma fatty acid metabolites were detected and quantified in response to filtered air and biodiesel exhaust exposure (in Paper III and IV). Data processing of raw data followed by data analysis, using both univariate and multivariate methods, enabled changes occurring in metabolites levels to be screened and investigated. For the initial pilot postprandial study, the aim was to investigate the plasma metabolome response after a well-defined meal during the postprandial stage for two types of diet. It was found that independent of the background diet type, levels of metabolites returned to their baseline levels after three hours. This finding was taken into consideration for the biodiesel exhaust exposures studies, designed to limit the impact of dietary effects. Both targeted and non-targeted approaches resulted in important findings. For instance, different metabolite profiles were detected in bronchial wash (BW) compared to bronchoalveolar lavage (BAL) fluid with mainly NMR and LC-MS. Furthermore, biodiesel exhaust exposure resulted in different metabolite profiles as observed by GC-MS, especially in BAL. In addition, fatty acid metabolites in BW, BAL, and plasma were shown to be responsive to biodiesel exhaust exposure, as measured by a targeted LC-MS/MS protocol. In summary, the new analytical methods developed to investigate the responsiveness of the human plasma and lung lavage metabolome proved to be useful in an analytical perspective, and provided important biological findings. However, further studies are needed to validate these results. / Metabolomik har använts för att spåra förändringar och störningar i kroppens funktioner genom undersökning av metabolit-profiler. I detta avhandlingasarbete har huvudfokus varit på tillämpning av flera olika analytiska plattformar för metabolomikstudier av det mänskliga metabolomet efter exponering för olika kost och avgasutsläpp från biodieselbränsle. De sofistikerade analytiska plattformarna som användes för detta ändamål var kärnmagnetisk resonans (NMR), samt gaskromatografi (GC) och vätskekromatografi (LC) kopplat till masspektrometri (MS). Varje plattform erbjöd unika karakteriseringsmöjligheter med detektion och identifiering av specifika grupper av metaboliter. Användningen av multipattformmetabolomik förbättrade täckningen av metabolomet och genererade kompletterande resultat som möjliggjorde en bättre förståelse av de biokemiska processer som reflekteras av metabolitprofilerna. Med hjälp av breda analyser har ett stort antal okända metaboliter i plasma identifierats under den postprandial fasen efter en väldefinerad måltid (i Paper I). Dessutom har ett stort antal metaboliter påvisats och identifierats i lungsköljvätska efter exponering av biodieselavgaser jämfört med kontollexponering med filtrerad luft (i Paper II). Parallellt med dessa breda analyser har också riktade analyser genomförts av både lungsköljvätska och plasma. Därigenom har bioaktiva lipider detekterats och kvantifieras efter avgasexponering och resultaten har jämförts med filtrerad luft som kontrollexponering (Paper III och IV). Processning av rådata följt av dataanalys, med både univariata och multivariata metoder möjliggjorde screening och fördjupad undersökning av förändringen i metabolitnivåer. I den första pilotstudien av postprandiala nivåer var syftet att undersöka responsen i plasmametabolomet efter en väldefinierad måltid under den postprandiala fasen vid två olika typer av kost. Resultaten visade att oberoende av kosten, så återvände metabolitnivåerna till sina baslinjenivåer tre timmar efter måltiden. Detta togs i beaktande vid exponeringsstudierna för biodieselavgaser, som designades så att dietens inverkan minimerades. Både breda och riktade analyser resulterade i viktiga resultat. Exempelvis så detekterades olika metabolitprofiler i bronkiell sköljvätska (BW) jämfört med bronkoalveolär sköljvätska (BAL), speciellt med NMR och LC-MS. Dessutom resulterade avgasexponering i förändrade metabolitprofiler, observerade med GC-MS, särskilt i BAL. Dessutom uppvisade fettsyrametaboliter i BW, BAL och plasma förändrade halter efter avgasexponering, uppmätt genom en riktad LC-MS/MS-analys. Sammanfattningsvis så visade sig de nya metoderna som utvecklats för att undersöka  förändringar i metabolithalterna i plasma och lungsköljvätska fungera väl ur ett analytiskt perspektiv och resulterade i viktiga biologiska fynd. Fördjupade studier behövs dock för att validera resultaten.