Blood ethanol is a widely accepted marker for recent ethanol intake (within the last 4-6 h). However, the rapid elimination of ethanol from the body nearly always makes it impossible to assess ethanol ingestion beyond the most recent 6-8h. But serum fatty acid ethyl ester (FAEE) is detectable in the blood both when ethanol is presented and long after ethanol has been removed from the circulation. For this FAEE should be better marker for prior ethanol intake.

Cette thèse s'inscrit dans le contexte de la Chaire Industrielle Bioplastiques, financé par MINES ParisTech et cinq entreprises partenaires : Arkema, L'Oréal, Nestlé, PSA Peugeot-Citroën et Schneider Electric, qui vise à développer de nouveaux matériaux biosourcés durables. L'objectif global de la thèse est de trouver de nouvelles propriétés à une ancienne famille de plastiques biosourcés – les esters de cellulose – en les mélangeant avec une polyoléfine. Nous avons débuté l'étude par une étape de screening qui nous a permis de caractériser l'ester de cellulose retenu (acétobutyrate de cellulose ou CAB) et de définir l'objectif de la thèse : améliorer la résistance au choc du CAB en y ajoutant une phase polyoléfinique finement dispersée. Le CAB est, en effet, particulièrement fragile : sa résilience est inférieure à 2 kJ/m² lors d'un choc Charpy entaillé. Pour diminuer la taille de nodules de la phase dispersée et la distance qui les sépare, deux approches ont été utilisés. Premièrement, plusieurs mélanges de CAB et de polyéthylènes (PE) de densités différentes ont été préparés par mélangeur interne. Des compatibilisants maléisés ont été utilisés pour diminuer la tension interfaciale entre les phases. Les tailles des nodules, mesurées par microscopie électronique à balayage se sont classées suivant les rapports de viscosité et d'élasticité (PE/CAB), mesurés par rhéométrie dynamique. La résilience de ces mélanges a été augmentée par rapport au CAB mais n'a pas dépassé 6 kJ/m². Dans la seconde approche, des polyoléfines fonctionnalisées (maléisées) ont été utilisées comme unique phase dispersée. La fonctionnalité accrue a permis d'améliorer l'adhésion interfaciale. La taille des nodules et leur espacement ont été considérablement réduits. Les mélanges sélectionnés ont été préparés par extrusion bi-vis et les éprouvettes de résistance au choc ont été préparées par injection. Pour quelques formulations, une longueur moyenne de ligaments de matrice (séparant deux nodules voisins) particulièrement petite (0,1 µm) a permis d'atteindre la transition fragile-ductile du matériau et une résilience supérieure à 60 kJ/m². / This work has been funded by the Industrial Chair in Biopalstics, financed by MINES ParisTech and fives industrial partners: Arkema, L'Oréal, Nestlé, PSA Peugeot-Citroën and Schneider Electric, whose objective is to develop new durable biobased materials. The aim of this thesis is to find new properties for an old-fashioned biobased plastic – cellulose esters – by blending with polyolefins. We started the project with a screening of the cellulose ester (cellulose acetate butyrate or CAB) properties. Thus, we were able to define the goal of the project: improving impact resistance of CAB by adding a finely dispersed polyolefin phase. Indeed, CAB is very brittle: its notched Charpy resilience is below 2 kJ/m². To decrease the size and the spacing of dispersed phase nodules, we developed two different approaches. First, several blends between CAB and polyethylenes (PE) with various densities have been prepared by internal mixer. Maleinated compatibilizers have been used to decrease interfacial tension between phases. Nodules sizes, measured from scanning electron microscope images ranked according to the viscosity and elasticity ratios (PE/CAB). Those ratios have been measured by dynamic rheometry. Blends resilience increased compared to CAB but did not exceed 6 kJ/m². In the second approach, functionalized (maleinated) polyolefins have been used as a single dispersed phase. Increased functionality led to improved interfacial adhesion. Nodules size and their spacing have been significantly decreased. Selected blends were prepared by twin-screw extrusion and impact bars were injected. For some formulations, a small (near 0.1 µm) mean matrix ligaments thickness (distance between two neighboring nodules) was obtained and led to the brittle-ductile transition of the material, with a resilience higher than 60 kJ/m².

Several types of antibiotics (roxarsone, virginiamycin, and bacitracin) are widely included in poultry feed to improve animal growth yields. Most of the antibiotics are excreted in manure which is subsequently applied to soils. One concern with this practice is that antibiotics may affect several microbially-mediated nutrient cycling reactions in soils that influence crop productivity and water quality. The main objectives of this study were to determine the effects of livestock antibiotics on nitrification, denitrification, and microbial community composition in soils along a topographic gradient. These objectives were addressed in a series of lab experiments by monitoring changes in inorganic N species and ester-linked fatty acid methyl ester profiles after exposing soil microorganisms collected from different topographic positions to increasing levels of antibiotics. It was discovered that roxarsone and virginiamycin inhibited nitrification and soil microbial growth and also influenced microbial community composition, but only at levels that were much higher than expected in poultry litter-applied soils. Bacitracin did not affect nitrification, microbial growth, or microbial community composition at any concentration tested. None of the antibiotics had a strong affect on denitrification. Thus, it is unlikely that soil, water, or air quality would be significantly impacted by the antibiotics contained in poultry litter.

Unga med normbrytande beteende löper en relativt hög risk för en långvarig negativ utveckling. För att förhindra detta krävs tidiga effektiva insatser som i sin tur kräver tillförlitliga bedömningsinstrument som identifierar risker och behov hos unga med, eller i riskzonen för normbrytande beteende. Just detta är syftet med ESTER-bedömning. Föreliggande studies syfte var att undersöka interbedömarreliabiliteten av ESTER-bedömning inklusive en ny kandidatskala för riskfaktorerna . Två oberoende bedömare genomförde ESTER-bedömningar på journalmaterial tillhörande 30 tvångsomhändertagna flickor, 15-20 år. Resultaten visar en spridning mellan bristfällig till mycket bra interbedömarreliabilitet på de 19 risk- och skyddsfaktorerna i ESTER-bedömning, med få fall av total oenighet mellan bedömarna. En jämförelse mellan den befintliga skalan och kandidatskalan visade marginella skillnader. Vidare forskning av interbedömarreliabilitet för ESTER-bedömning bör testa skalorna var för sig och inkludera intervjuer som informationskälla. / Youths with normbreaking behavior is at higher risk for a negative development. To prevent this, there is a need for reliable assessments that can identify risk and need for youths with, or at risk for normbreaking behavior. This is the purpose of ESTER-assessment. This study evaluated the inter-rater reliability of two different scales in ESTER-assessment. Two independent judges conducted ESTER-assessment on case files of 30 institutionalized girls, aged 15-20 years. The results revealed poor to excellent agreement and few cases of total disagreements. The two different scales showed a minimal difference. In further research of the inter-rater reliability of ESTER-assessment there is a need for testing the two scales separately and to include interviews as a source of information.

Ester liquids including both natural ester and synthetic ester are being considered as potential alternatives to mineral oil, due to their better environmental performance and for some liquids their higher fire point. Although these liquids have been widely used in distribution and traction transformers, it is still a significant step to adopt ester liquids in high-voltage power transformers because the high cost and severe consequence of a factory test failure and the high level of safety and reliability required in service for these units, tend to lead to a cautious approach to any step change in technology. Lightning impulse strength as basic insulation level is of importance for insulation design of power transformers and lightning impulse test is commonly required in the factory routine tests for high-voltage power transformers, so this thesis is aimed to investigate the electrical performances including pre-breakdown and breakdown of natural ester and synthetic ester under impulse voltage. Two types of field geometry were considered in the study, one is sphere-sphere configuration which represents the quasi-uniform fields inside a transformer and another is strongly non-uniform point-plane configuration which represents the situation of a defect or a source of discharge. In quasi-uniform field study, standard breakdown tests were carried out under negative lightning and switching impulse voltages. Influence of various testing methods on the measured lightning breakdown voltage was studied and the 1% lightning withstand voltage was obtained based on Weibull distribution fitting on the cumulative probability plot built up using the approximately 1000 impulse shots. As for strongly non-uniform field study, streamer propagation and breakdown event in ester liquids either with or without pressboard interface were investigated at various gap distances under both positive and negative lightning impulse voltages. A relationship between the results under lightning impulse and previously published results under step voltage was built up to predict the lightning breakdown voltage of ester liquids at very large gaps. The results indicated that impulse strengths of ester liquids for both breakdown and withstand in a quasi-uniform field, are comparable to those of mineral oil. In a strongly non-uniform field, streamers in ester liquids propagate faster and further, than in mineral oil at the same voltage level. Thus breakdown voltages of ester liquids are generally lower than those of mineral oil, which could be as low as 40% at a large gap distance of approximately 1000 mm. Introduction of parallel pressboard interface has no influence on the streamer propagation and thus does not weaken the breakdown voltage, but it tends to reduce the acceleration voltage particularly for mineral oil under positive polarity. Last but not least, a unique phenomenon of secondary reverse streamer (SRS) was observed in ester liquids, which occurs subsequently and well after the extinction of the primary streamer (PS) propagation within a single shot of impulse voltage and has the reverse polarity to the PS. The formation mechanism of SRS is explained mainly due to the reverse electric field induced by the residual space charges left by the PS.

Résumé confidentiel / Confidential abstract

Lipid transfer inhibitor protein (LTIP) is an important regulator of cholesteryl ester transfer protein function. We report the development of an immunoassay for LTIP and its use to quantify LTIP in plasma of varying lipid contents. A rabbit antibody against bacterially produced recombinant LTIP detected two LTIP isoforms in plasma differing in carbohydrate content. This antibody was used in a competitive, enzyme-linked immunoassay that uses partially purified LTIP bound to microtiter plates. To optimize LTIP immunoreactivity, plasma samples required preincubation in 1% Tween-20 and 0.5% Nonidet P-40. In normolipidemic plasma, LTIP averaged 83.5 mg/ml. LTIP was 31% higher in males than in females. LTIP was positively associated with HDL cholesterol in normolipidemic males but not in females. In hypertriglyceridemic males, LTIP was only 56% of control values, whereas in hypertriglyceridemic females, LTIP tended to increase. Additionally, in males with normal cholesterol and triglyceride (TG) ≤ 200 mg/dl, LTIP varied inversely with plasma TG. Overall, we have confirmed the negative association between plasma TG levels and LTIP previously suggested by a small data set, but now we demonstrate that this effect is seen only in males. The mechanisms underlying this gender-specific response to TG, and why LTIP and HDL levels correlate in males but not in females, remain to be determined.

Les hydrogels injectables et auto-réparants suscitent un intérêt particulier dans les domaines de l'ingénierie tissulaire et de la médecine régénératrice. En raison de la nature dynamique de leurs réticulations, ces gels peuvent être pré-formés dans des seringues, extrudés sous cisaillement et s’auto-réparer spontanément après arrêt de la déformation mécanique. Au vu du potentiel que peuvent offrir les polymères fonctionnalisés par des acides boroniques pour la fabrication de gels covalents réversibles, nous avons développé des hydrogels injectables d’acide hyaluronique (HA) réticulés par des liaisons esters boronates pour des applications esthétiques et biomédicales. Pour élaborer de tels gels avec des propriétés optimisées, nous avons exploré l’effet de la nature du dérivé d’acide boronique ainsi que du motif saccharidique greffés sur le HA sur les propriétés rhéologiques dynamiques des gels. Parmi les différents dérivés d'acide boronique, le benzoboroxole (BOR) a été choisi en plus de l'acide phénylboronique (PBA) pour complexer différents motifs saccharidiques greffés sur le HA. Comparé au PBA, le dérivé BOR est, en effet, capable de se complexer de manière plus efficace à pH neutre et avec une plus grande variété de composés saccharidiques, en particulier les glycopyranosides. Cette étude a démontré que les propriétés rhéologiques dynamiques des assemblages de HA formés par complexation des unités de BOR ou PBA avec les différents sucres sont étroitement liées à la dynamique des échanges moléculaires et à la thermodynamique des pontages. En outre, nous avons également établi pour la première fois la possibilité d’obtenir des hydrogels de HA auto-réticulants à pH physiologique via des interactions multivalentes entre les unités de BOR greffées sur le HA et des groupements diols se répétant sur la chaîne polysaccharidique. Outre le BOR, la capacité de son homologue cyclique à six chaînons, la benzoxaborine, et d’un nouveau dérivé original similaire à ce composé a été explorée en tant que nouveaux sites de complexation de saccharides pour la formation de réseaux de HA réversibles. Compte-tenu des propriétés injectables, d'auto-réparation et de réponse à différents stimuli démontrées par ces nouveaux hydrogels de HA, ces biomatériaux apparaissent comme des candidats prometteurs pour de nombreuses applications innovantes dans le domaine biomédical, notamment pour l'ingénierie tissulaire et la thérapie cellulaire. / Injectable and self-healing hydrogels have recently drawn great attention in the fields of tissue engineering and regenerative medicine. Such gels can be pre-formed into syringes, be extruded under shear stress and show rapid recovery when the applied stress is removed due to the dynamic nature of their crosslinks. Given the exciting potential benefit of using boronic acid-containing polymers to construct dynamic covalent hydrogels, we explored this attractive strategy to design injectable boronate-crosslinked hydrogels based on hyaluronic acid (HA) for aesthetic and other biomedical applications. To design hydrogels with optimized properties, we investigated the effect of the nature of the boronic acid moiety as well as the sugar molecule grafted onto the HA backbone on the gel properties. Among arylboronic acid derivatives, benzoboroxole (BOR) was selected in addition to phenylboronic acid (PBA) as the binding site for sugar moieties grafted on HA. This choice was based on the efficient binding capability of BOR at neutral pH compared to PBA, and on its ability to complex glycopyranosides. With this study, we demonstrated that the dynamic rheological properties of the HA networks based on BOR- or PBA-saccharide complexation are closely linked to the molecular exchange dynamics and thermodynamics of the small molecule crosslinkers. Besides, we also established for the first time the feasibility of self-crosslinking HA hydrogels with extremely slow dynamics at physiological pH through multivalent interactions between BOR derivatives grafted on HA and diols from the polysaccharide chains. Finally, in addition to BOR, we demonstrated the unprecedented capacity of its six-membered ring homologue, benzoxaborin, and a new original benzoxaborin-like derivative as new carbohydrate binding sites for the formation of reversible HA networks. Taking into account the injectable, self-healing and stimuli-responsive properties showed by these new HA hydrogels, these biomaterials appear as promising injectable scaffolds for many innovative applications in the biomedical field, including in tissue engineering and cell therapy.

abstract: The lifetime of a transformer is essentially determined by the life of its insulation system which is a time function of the temperature defined by its thermal class. A large quantity of studies and international standards have been published indicating the possibility of increasing the thermal class of cellulose based materials when immersed in natural esters which are superior to traditional mineral oils. Thus, a transformer having thermally upgraded Kraft paper and natural ester dielectric fluid can be classified as a high temperature insulation system. Such a transformer can also operate at temperatures 20C higher than its mineral oil equivalent, holding additional loading capability without losing life expectancy. This thesis focuses on evaluating the use of this feature as an additional capability for enhancing the loadability and/or extending the life of the distribution transformers for the Phoenix based utility - SRP using FR3 brand natural ester dielectric fluid. Initially, different transformer design options to use this additional loadability are compared allowing utilities to select an optimal FR3 filled transformer design for their application. Yearlong load profiles for SRP distribution transformers, sized conventionally on peak load demands, are analyzed for their oil temperatures, winding temperatures and loss of insulation life. It is observed that these load profiles can be classified into two types: 1) Type-1 profiles with high peak and high average loads, and 2) Type-2 profiles with comparatively low peak and low average load. For the Type 1 load profiles, use of FR3 natural ester fluid with the same nominal rating showed 7.4 times longer life expectation. For the Type 2 load profiles, a new way of sizing ester filled transformers based on both average and peak load, instead of only peak load, called “Sustainable Peak Loading” showed smaller size transformers can handle the same yearly peak loads while maintaining superior insulation lifespan. It is additionally possible to have reduction in the total energy dissipation over the year. A net present value cost savings up to US$1200 per transformer quantifying benefits of the life extension and the total ownership cost savings up to 30% for sustainable peak loading showed SRP distribution transformers can gain substantial economic savings when the distribution transformer fleet is replaced with FR3 ester filled units. / Dissertation/Thesis / Envirotemp FR3 Fluid Brochure / Envirotempe FR3 Fluid Data Sheet / Masters Thesis Electrical Engineering 2018

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