Förfrågan efter nya och mer avancerade applikationer är en pågående process vilket leder till en konstant utveckling av nya material. För att förstå relationen mellan en applikations egenskaper och dess sammansättning krävs full förståelse och kontroll över materialets uppbyggnad. En sådan kontroll över uppbyggnaden hos material hittas i en undergrupp till dendritiska polymerer som kallas dendrimerer. I den här doktorsavhandlingen belyses nya metoder för att framställa dendrimer med hjälp av selektiva kemiska reaktioner. Sådana selektiva reaktioner kan hittas inom konceptet klickkemi och har i detta arbete kombinerats med traditionell anhydrid- och karbodiimidmedierad kemi. Denna avhandling diskuterar en accelererad tillväxtmetod, dendrimerer med inre och yttre reaktiva grupper, simultana reaktioner och applikationer baserade på dessa dendritiska material. En accelererad tillväxtmetod har utvecklats baserad på AB2- och CD2-monomerer. Dessa monomerer tillåter tillväxt av dendrimerer utan att använda sig av skyddsgruppkemi eller aktivering av ändgrupper. Detta gjordes genom att kombinera kemoselektiviteten hos klickkemi tillsammans med traditionell syraklorid kopplingar. Dendrimerer med inre alkyn- eller azidfunktionalitet syntetiserades genom att använda AB2C-monomerer. Den dendritiska tillväxten skedde med hjälp av karbodiimidmedierad kemi. Monomererna som användes bär på en C-funktionalitet, alkyn eller azid, och på så sätt byggs får interiören i de syntetiserade dendrimeren en inneburen aktiv funktionell grupp. Ortogonaliteten hos klickkemi användes för att sammanfoga monomerer till en dendritisk struktur. Traditionell anhydridkemi- och klickemireaktioner utfördes samtidigt och på så sätt kunde dendritiska strukturer erhållas med färre antal uppreningssteg. En ljusemitterande dendrimer syntetiserades genom att koppla azidfunktionella dendroner till en alkynfunktionell cyclenkärna. Europiumjoner inkorporerades i kärnan varpå dendrimerens fotofysiska egenskaper analyserades. Mätningarna visade att den bildade triazolen hade en sensibiliserande effekt på europiumjonen. Termiska studier på några av de syntetiserade dendrimerer utfördes för att se om några av dem kunde fungera som templat vid framställning av isoporösa filmer. / The need for new improved materials in cutting edge applications is constantly inspiring researchers to developing novel advanced macromolecular structures. A research area within advanced and complex macromolecular structures is dendrimers and their synthesis. Dendrimers consist of highly dense and branched structures that have promising properties suitable for biomedical and electrical applications and as templating materials. Dendrimers provide full control over the structure and property relationship since they are synthesized with unprecedented control over each reaction step. In this doctoral thesis, new methodologies for dendrimer synthesis are based on the concept of click chemistry in combination with traditional chemical reactions for dendrimer synthesis. This thesis discusses an accelerated growth approach, dendrimers with internal functionality, concurrent reactions and their applications. An accelerated growth approach for dendrimers was developed based on AB2- and CD2-monomers. These allow dendritic growth without the use of activation or deprotection of the peripheral end-groups. This was achieved by combining the chemoselective nature of click chemistry and traditional acid chloride reactions. Dendrimers with internal azide/alkyne functionality were prepared by adding AB2C monomers to a multifunctional core. Dendritic growth was obtained by employing carbodiimide mediated chemistry. The monomers carry a pendant C-functionality (alkyne or azide) that remains available in the dendritic interior resulting in dendrimers with internal and peripheral functionalities. The orthogonal nature of click chemistry was utilized for the simultaneous assembly of monomers into dendritic structures. Traditional anhydride chemistry and click chemistry were carried out concurrently to obtain dendritic structures. This procedure allows synthesis of dendritic structures using fewer purification steps. Thermal analyses on selected dendrimers were carried out to verify their use as templates for the formation of honeycomb membranes. Additionally, a light emitting dendrimer was prepared by coupling of azide functional dendrons to an alkyne functional cyclen core. A Europium ion was incorporated into the dendrimer core, and photophysical measurements on the metal containing dendrimer revealed that the formed triazole linkage possesses a sensitizing effect. / QC 20100629

As the environmental concern grows, researchers try to find material which can be environmental friendly and biodegradable to some extent. At present, flax fibre cannot fully replace glass fibre. Some attempts have been made to replace the glass fibre.<p> Studies show the physical and mechanical properties of natural fibres are comparable with glass fibre, so it can replace glass fibre in the process of making biocomposites. <p> The properties of biocomposites depend on the fibre used. Research shows that to get a better biocomposite, the fibre has to be chemically treated to improve adhesion between fibre and polymer matrix. After the chemical treatment, the fibre has to be dried to minimum moisture content so the drying of flax fibre is essential in the process of making biocomposites. <p> In this research, oilseed flax fibre is dried and drying characteristics were investigated. After drying, the physical properties of the fibre were tested and analysed.<p> The fibre was dried using three different drying methods, namely, microwave, microwave-convection, and microwave-vacuum environments. Curve fitting with four empirical methods has been carried out to determine the drying constant, coefficient of determination and standard error values. The results showed that microwave-vacuum drying method is more efficient (in terms of final moisture content) than microwave and microwave-convection drying. Although microwave-vacuum drying took the most time and did not result in promising colour values, the maximum moisture removal is achieved because fibres can be dried for a longer period of time with a comparatively low temperature.<p> The results of physical properties were analysed for untreated and treated and dried flax fibre. The tensile strength and elastic modulus of untreated and treated fibre did not show any significant change. Because the diameter of flax fibre cannot be consistent, a range of values can be obtained. The diameter range of fibre bundle 30-300 µm was examined for these tests. The tensile strength obtained from these fibre bundles ranged between 16 to 667 MPa and elastic modulus values were 2 GPa up to 63 GPa.<p> The scanning electron micrograph (SEM) was also analysed for untreated and treated-dried fibre. The fibre which was dried with high power or longer period of time showed black spots, probably due to local heating. The fibre dried with microwave-vacuum developed some black spots which were clearly seen in the SEM.<p> Differential scanning calorimetric data showed a shift in temperature of degradation. In this research, degradation temperature of cellulose was found 350(+/-10)°C for the treated and dried flax fibre.<p> In conclusion, the flax fibre has a potential to be used in biocomposite production. The microwave-vacuum works best for drying where the fibre can be dried up to a less than 1% of moisture content.

The problem of inaccurate measurement techniques for quantifying isothermal solidification kinetics during transient liquid phase (TLP) bonding in binary and ternary systems; and resulting uncertainty in the accuracy of analytical and numerical models has been addressed by the development of a new technique using differential scanning calorimetry (DSC). This has enabled characterization of the process kinetics in binary and ternary solid/liquid diffusion couples resulting in advancement of the fundamental theoretical understanding of the mechanics of isothermal solidification. The progress of isothermal solidification was determined by measuring the fraction of liquid remaining after an isothermal hold period of varying length. A 'TLP half sample', or a solid/liquid diffusion couple was setup in the sample crucible of a DSC enabling measurement of the heat flow relative to a reference crucible containing a mass of base metal. A comparison of the endotherm from melting of an interlayer with the exotherm from solidification of the residual liquid gives the fraction of liquid remaining. The Ag-Cu and Ag-Au-Cu systems were employed in this study. Metallurgical techniques were used to compliment the DSC results. The effects of sample geometry on the DSC trace have been characterized. The initial interlayer composition, the heating rate, the reference crucible contents, and the base metal coating must be considered in development of the experimental parameters. Furthermore, the effects of heat conduction into the base metal, baseline shift across the initial melting endotherm, and the exclusion of primary solidification upon cooling combine to systematically reduce the measured fraction of liquid remaining. These effects have been quantified using a modified temperature program, and corrected using a universal factor. A comparison of the experimental results with the predictions of various analytical solutions for isothermal solidification reveals that the moving interface solution can accurately predict the interface kinetics given accurate diffusion data. The DSC method has been used to quantify the process kinetics of isothermal solidification in a ternary alloy system, with results compared to a finite difference model for interface motion. The DSC results show a linear relationship between the interface position and the square root of the isothermal hold time. While the numerical simulations do not agree well with the experimental interface kinetics due to a lack of accurate thermodynamic data, the model does help develop an understanding of the isothermal solidification mechanics. Compositional shift at the solid/liquid interface has been measured experimentally and compared with predictions. The results show that the direction of tie-line shift can be predicted using numerical techniques. Furthermore, tie-line shift has been observed in the DSC results. This study has shown that DSC is an accurate and valuable tool in the development of parameters for processes employing isothermal solidification, such as TLP bonding.

The problem of inaccurate measurement techniques for quantifying isothermal solidification kinetics during transient liquid phase (TLP) bonding in binary and ternary systems; and resulting uncertainty in the accuracy of analytical and numerical models has been addressed by the development of a new technique using differential scanning calorimetry (DSC). This has enabled characterization of the process kinetics in binary and ternary solid/liquid diffusion couples resulting in advancement of the fundamental theoretical understanding of the mechanics of isothermal solidification. The progress of isothermal solidification was determined by measuring the fraction of liquid remaining after an isothermal hold period of varying length. A 'TLP half sample', or a solid/liquid diffusion couple was setup in the sample crucible of a DSC enabling measurement of the heat flow relative to a reference crucible containing a mass of base metal. A comparison of the endotherm from melting of an interlayer with the exotherm from solidification of the residual liquid gives the fraction of liquid remaining. The Ag-Cu and Ag-Au-Cu systems were employed in this study. Metallurgical techniques were used to compliment the DSC results. The effects of sample geometry on the DSC trace have been characterized. The initial interlayer composition, the heating rate, the reference crucible contents, and the base metal coating must be considered in development of the experimental parameters. Furthermore, the effects of heat conduction into the base metal, baseline shift across the initial melting endotherm, and the exclusion of primary solidification upon cooling combine to systematically reduce the measured fraction of liquid remaining. These effects have been quantified using a modified temperature program, and corrected using a universal factor. A comparison of the experimental results with the predictions of various analytical solutions for isothermal solidification reveals that the moving interface solution can accurately predict the interface kinetics given accurate diffusion data. The DSC method has been used to quantify the process kinetics of isothermal solidification in a ternary alloy system, with results compared to a finite difference model for interface motion. The DSC results show a linear relationship between the interface position and the square root of the isothermal hold time. While the numerical simulations do not agree well with the experimental interface kinetics due to a lack of accurate thermodynamic data, the model does help develop an understanding of the isothermal solidification mechanics. Compositional shift at the solid/liquid interface has been measured experimentally and compared with predictions. The results show that the direction of tie-line shift can be predicted using numerical techniques. Furthermore, tie-line shift has been observed in the DSC results. This study has shown that DSC is an accurate and valuable tool in the development of parameters for processes employing isothermal solidification, such as TLP bonding.

As the environmental concern grows, researchers try to find material which can be environmental friendly and biodegradable to some extent. At present, flax fibre cannot fully replace glass fibre. Some attempts have been made to replace the glass fibre.<p> Studies show the physical and mechanical properties of natural fibres are comparable with glass fibre, so it can replace glass fibre in the process of making biocomposites. <p> The properties of biocomposites depend on the fibre used. Research shows that to get a better biocomposite, the fibre has to be chemically treated to improve adhesion between fibre and polymer matrix. After the chemical treatment, the fibre has to be dried to minimum moisture content so the drying of flax fibre is essential in the process of making biocomposites. <p> In this research, oilseed flax fibre is dried and drying characteristics were investigated. After drying, the physical properties of the fibre were tested and analysed.<p> The fibre was dried using three different drying methods, namely, microwave, microwave-convection, and microwave-vacuum environments. Curve fitting with four empirical methods has been carried out to determine the drying constant, coefficient of determination and standard error values. The results showed that microwave-vacuum drying method is more efficient (in terms of final moisture content) than microwave and microwave-convection drying. Although microwave-vacuum drying took the most time and did not result in promising colour values, the maximum moisture removal is achieved because fibres can be dried for a longer period of time with a comparatively low temperature.<p> The results of physical properties were analysed for untreated and treated and dried flax fibre. The tensile strength and elastic modulus of untreated and treated fibre did not show any significant change. Because the diameter of flax fibre cannot be consistent, a range of values can be obtained. The diameter range of fibre bundle 30-300 µm was examined for these tests. The tensile strength obtained from these fibre bundles ranged between 16 to 667 MPa and elastic modulus values were 2 GPa up to 63 GPa.<p> The scanning electron micrograph (SEM) was also analysed for untreated and treated-dried fibre. The fibre which was dried with high power or longer period of time showed black spots, probably due to local heating. The fibre dried with microwave-vacuum developed some black spots which were clearly seen in the SEM.<p> Differential scanning calorimetric data showed a shift in temperature of degradation. In this research, degradation temperature of cellulose was found 350(+/-10)°C for the treated and dried flax fibre.<p> In conclusion, the flax fibre has a potential to be used in biocomposite production. The microwave-vacuum works best for drying where the fibre can be dried up to a less than 1% of moisture content.

The epilepsies are a heterogenous group of symptom complexes, whose common features is the recurrence of seizures. There is no certain therapy for epilepsy. In order to promote new advances for the prevention of epilepsy the molecular mechanism of epileptic activities should be clarified. In the present study the goal is to obtain information for molecular mechanism of epilepsy. To achieve this, molecular alterations from pentylenetetrazol (PTZ)-induced epileptic activities on rat brain tissue and cell membranes were investigated by Fourier Transform Infrared (FTIR) spectroscopy, Fourier Transform Infrared Microscopy and Atomic Force Microscopy (AFM). Moreover, the therapeutic role of an antiepileptic agent vigabatrin (VGB) on epileptic rat brain membranes were examined at molecular level. For better understanding of the action mechanism of PTZ and an antiepileptic drug VGB in cell membranes we firstly studied at model level using multilamellar liposomes (MLVs). We investigated PTZ-DPPC MLVs interactions in terms of lipid phase behavior, order and dynamics and nature of hydrogen bonding around its polar part, using Fourier Transform Infrared (FTIR) spectroscopy, Differential Scanning Calorimetry (DSC), Electronspin Resonans Spectroscopy (ESR) and Steady State Fluorescence Spectroscopy. According to our data, PTZ has no ability to interact with membrane lipids. On the other hand, the results of VGB-DPPC interactions showed that VGB strongly interact with the head group and/or the region near the head of membrane phospholipids. The molecular investigation of PTZ-induced epileptic activities revealed that PTZ-induced seizures cause a decrease in the lipid and protein content, membrane fluidity and glycogen level. They stimulate alterations in membrane packing and the secondary structure of proteins as well as lipid peroxidation. In addition, our results show the transcription of early genes following high dose PTZ administration. All these molecular alterations variatins are only resulted from the consequences of epileptic activities not from convulsant agent PTZ itself. The important finding is that, VGB restored some of the alterations by PTZ-induced epileptic activities on brain cell membrane. For instance, it restored membrane fluidity, lipid peroxidation, phospholipid degradation and changes in membrane organization. However, it was found that VGB has no significant effects on the changes in protein secondary structure.

<p>Due to climatic change, increasing thermal loads inbuildings and rising living standards, comfort cooling inbuildings is becoming increasingly important and the demand forcomfort cooling is expanding very quickly around the world. Theincreased cooling demand results in a peak in electrical powerdemand during the hottest summer hours. This peak presents newchallenges and uncertainties to electricity utilities and theircustomers.</p><p>Cool thermal storage systems have not only the potential tobecome one of the primary solutions to the electrical powerimbalance between production and demand, but also shift coolingenergy use to off-peak periods and avoid peak demand charges.It increases the possibilities of utilizing renewable energysources and waste heat for cooling generation. In addition, acool storage can actually increase the efficiency of combinedheat and power (CHP) generation provided that heat drivencooling is coupled to CHP. Then, the cool storage may avoidpeaks in the heat demand for cooling generation, and this meansthat the CHP can operate at design conditions in most oftime.</p><p>Phase Change Materials (PCMs) used for cool storage hasobtained considerable attention, since they can be designed tomelt and freeze at a selected temperature and have shown apromising ability to reduce the size of storage systemscompared with a sensible heat storage system because they usethe latent heat of the storage medium for thermal energystorage.</p><p>The goal of this thesis is to define suitable PCM candidatesfor comfort cooling storage. The thesis work combines differentmethods to determine the thermophysical properties oftetradecane, hexadecane and their binary mixtures, anddemonstrates the potential of using these materials as PCM forcomfort cooling storage. The phase equilibrium of the binarysystem has been studied theoretically as well asexperimentally, resulting in the derivation of the phasediagram. With knowledge of the liquid-solid phase equilibriumcharacteristics and the phase diagram, an improvedunderstanding is provided for the interrelationships involvedin the phase change of the studied materials. It has beenindicated that except for the minimum-melting point mixture,all mixtures melt and freeze within a temperature range and notat a constant temperature, which is so far often assumed in PCMstorage design. In addition, the enthalpy change during thephase transition (heat of fusion) corresponds to the phasechange temperature range; thus, the storage density obtaineddepends on how large a part of the phase change temperaturerange is valid for a given application.</p><p>Differential Scanning Calorimetery (DSC) is one frequentlyused method in the development of PCMs. In this thesis, it hasbeen found that varying results are obtained depending on theDSC settings throughout the measurements. When the DSC runs ata high heating/cooling rate it will lead to erroneousinformation. Also, the correct phase transition temperaturerange cannot be obtained simply from DSC measurement. Combiningphase equilibrium considerations with DSC measurements gives areliable design method that incorporates both the heat offusion and the phase change temperature range.</p><p>The potential of PCM storage for peak shaving in differentcooling systems has been demonstrated. A Computer model hasbeen developed for rapid phase equilibrium calculation. The useof phase equilibrium data in the design of a cool storagesystem is presented as a general methodology.</p><p><b>Keywords:</b>Comfort cooling, peak shaving, PCM, coolthermal storage system, DSC, phase change temperature range,the heat of fusion, phase equilibrium, phase diagram. Language:English</p>

Recientemente, la semilla de chía (Salvia hispanica L.) ha sido redescubierta como una importante fuente de ácidos grasos omega-3, proteínas, fibra dietética y antioxidantes, a partir de la cual puede obtenerse aceite con una elevada proporción de ácidos grasos esenciales. Su incorporación en la dieta permite disminuir la incidencia de enfermedades coronarias, refuerza el sistema nervioso; la fibra dietaria es una valiosa alternativa para regular el tránsito intestinal, lo cual ayuda a prevenir la obesidad, el cáncer de colon, así como los elevados niveles de colesterol y de glucosa en sangre. En nuestro país, la creciente expansión de su cultivo en las provincias del noroeste puede representar un aporte tendiente a la diversificación de la producción agrícola con el consecuente impacto socioeconómico en dicha región. Por otra parte, Argentina es uno de los principales productores y exportadores de aceite de girasol (Helianthus annuus L.) y la industria local se destaca por su avanzada tecnología y alta competitividad. Asimismo, el girasol es el segundo cultivo oleaginoso en importancia a escala nacional luego de la soja. El 92% del girasol producido en la Argentina es procesado, siendo exportado el 70% como aceite crudo a granel y harina proteica y el 30% restante como aceite refinado. Los aceites comestibles constituyen un componente importante en nuestra alimentación, cuya variedad y consumo depende de la disponibilidad de cada país y región. La composición de los aceites varía considerablemente en el aporte de ácidos grasos saturados, monoinsaturados y poliinsaturados y particularmente, en el tenor de ácidos grasos omega-6 y omega-3. La nutrición en el mundo occidental se caracteriza por una elevada ingesta de ácidos grasos omega-6 y un bajo consumo de ácidos grasos omega-3, debido mayoritariamente al origen vegetal de los aceites que se producen y al bajo consumo de pescados grasos. De esta forma, la relación omega-6:omega-3 está alejada de la que recomienda la FAO/OMS. En virtud de ello, es posible preparar aceites con relaciones omega-6:omega-3 muy cercanas a las recomendadas, desarrollando productos que contengan mezclas de aceites con una adecuada composición de ácidos grasos. En nuestro país, debido a la gran producción de aceite de girasol, es interesante la revalorización de los subproductos generados en el proceso de extracción y/o refinación del mismo. Entre ellos se encuentran las gomas, constituidas por una mezcla de fosfolípidos, agua y restos de aceite. La posterior deshidratación de las mismas da lugar al subproducto denominado lecitina. Cada fosfolípido constituyente contribuye a la funcionalidad de la lecitina, por lo que la modificación de su estructura y/o de su concentración posibilita ampliar las propiedades funcionales de las mismas. En el Capítulo I se presenta una introducción sobre la chía y el girasol, describiendo el origen y los antecedentes históricos de estas especies, las principales características botánicas, así como la composición química de las semillas y sus respectivos aceites. Además, se describe el proceso de obtención de los aceites vegetales y de la lecitina, la cual es principalmente utilizada como agente emulsificante en la industria alimentaria. Por último, se describen los mecanismos de formación, estabilidad y desestabilización de las emulsiones. En el Capítulo II se detalla el proceso de fraccionamiento de lecitina nativa de girasol, mediante el empleo de diferentes soluciones etanol-agua y distintos niveles de pH del solvente de extracción. Además, se analizan las propiedades funcionales de las fracciones enriquecidas en fosfatidilcolina PC, como agentes emulsificantes de emulsiones O/W. En el Capítulo III se estudia la obtención, caracterización, estabilidad oxidativa y condiciones de almacenamiento más adecuadas de aceites mezcla girasol-chía, los cuales presentan relaciones omega-6:omega-3 acordes a las recomendadas por la FAO/OMS, evaluando la eficiencia de la adición de antioxidantes (extracto de romero, palmitato de ascorbilo y su mezcla) con respecto al deterioro oxidativo de los mismos. Además, se presentan los resultados del análisis sensorial. En el Capítulo IV se evalúa la estabilidad física de emulsiones O/W formuladas con aceites mezcla girasol-chía, lecitinas modificadas de girasol mediante “deoiling” y fraccionamiento (agente emulsificante) y mucílago de chía (agente estabilizante). Finalmente, se exponen las Conclusiones generales obtenidas a partir de este trabajo de Tesis y en base a ellas, las Perspectivas futuras.

La consommation de puissance des microprocesseurs embarqués ne cesse d'augmenter avec la multiplication des fonctions qu'ils doivent assurer Ainsi, les générations actuelles de microprocesseurs ont une forte consommation en courant sous une très faible tension (autour du volt) avec des transitoires contraignants. Cette thèse est consacrée à la design des systèmes d'alimentation rapprochées des cartes mères des PC où régulateurs de tension (VRMs) qui englobent fort courant et faible tension de sortie ainsi que haute fréquence de découpage. A cet effet, les architectures entrelacées ou multi-phase sont une bonne alternative pour atteindre ces niveaux énergétiques si rigoureux. Traditionnellement, ces types de systèmes d'alimentation sont contrôlés avec une commande analogique. Cependant, les nouvelles générations de microprocesseurs exigent des performances plus élevées en même temps qu'une régulation plus précise. Alors, la commande classique analogique est de plus en plus remplacée par une commande numérique plus flexible et plus performante. Cette thèse s'intègre dans le cadre du projet régional LISPA où le LAAS et Freescale Semiconductor collaborent pour développer de nouveaux systèmes d'alimentations pour microprocesseurs de puissance.

La corrosion des gaines dans les réacteurs nucléaires à eau pressurisée représente le facteur limitant la durée de vie des crayons dans cet environnement. L'alliage communément utilisé pour ces tubes de gainage est le zircaloy-4. Ce dernier sera remplacé à moyen terme par un alliage, dont l'élément principal d'addition est le niobium, noté ZrNbO. Dans ce cadre, les objectifs de ce travail sont de confirmer ou d'infirmer les hypothèses proposées dans la littérature et de proposer, le cas échéant, de nouvelles interprétations sur les régimes cinétiquement limitants.Au cours de ce travail, quatre systèmes réactionnels ont été étudiés : l'oxydation de ces deux alliages sous oxygène et sous vapeur d'eau. L'oxydation a été suivie par thermogravimétrie, dans un domaine de température compris entre 490 et 550°C et pour des pressions partielles inférieures à la pression atmosphérique, que ce soit sous oxygène ou sous vapeur d'eau. En parallèle, une caractérisation morphologique des couches a été réalisée par MEB. Enfin, d'autres techniques ont été mises en œuvre pour décrire la composition chimique de la couche ou du métal (SDL, XPS, ). L'analyse de nos résultats sur Zircaloy-4 nous conduit à valider l'interprétation classique du régime pré-transitoire par une étape limitante de diffusion des lacunes d'oxygène dans la couche d'oxyde. En revanche, les résultats obtenus avec ZrNbO en pré-transition ont été interprétés, quelle que soit l'atmosphère, par un cas pur de diffusion d'ions adsorbés dans la couche poreuse. Enfin, le régime cinétique post-transitoire est toujours différent de celui observé en pré-transition.