SOLUTION AND MELT BEHAVIOUR OF HIGH-DENSITY POLYETHYLENE - Successive Solution Fractionation mechanism - Influence of the molecular structure on the flow In the field of polyethylene characterization, one of the most challenging research topic is certainly an accurate molecular structure determination of industrial products, in terms of molar mass distribution (MMD), corresponding average-molar masses and molecular architecture (branching nature, content and heterogeneity). Solution to this long-term problem necessarily calls for a multi-disciplinary approach. Therefore, respective advantages of molecular structure characterization in solution and in the melt are exploited. In solution, chromatographic and spectroscopic methods allow determination of MMD, average branching content and intermolecular heterogeneity within their detection limits. Rheological testing in the melt could be a very powerful molecular structure investigation tool, due to its extreme sensitivity to high molar mass (MM) tailing or long chain branching (LCB) traces. But when the rheological tests results are in hand, we often still wonder what kind of molecular structure gives rise to such results. Indeed, melt signal depends on MM, MMD and LCB presence. MMD determination and LCB quantification by melt approach is impossible as long as respective effects of these molecular parameters are not clearly quantified. The general purpose of the present work is to contribute to a better molecular structure characterization of high-density polyethylene by developing, in a first time, a preparative fractionation method able to provide narrow-disperse linear and long chain branched samples, essential to separate concomitant effects of MM, MMD and LCB on rheological behaviour. Once such model fractions isolated, influence of MM and LCB on both shear and elongational flow behaviours in the melt is studied. /Dans le domaine du polyéthylène, un des sujets de recherche les plus investigués à l'heure actuelle est la détermination précise de la structure moléculaire de résines industrielles, en termes de distribution des masses molaires (MMD), de masses molaires moyennes correspondantes et d'architecture moléculaire (nature, teneur et hétérogénéité). La résolution de cette problématique nécessite une approche multi-disciplinaire, afin d' exploiter simultanément les avantages d'une caractérisation en solution et à l'état fondu. En solution, certaines méthodes chromatographiques et spectroscopiques permettent de déterminer une MMD, une teneur moyenne en branchement et leur distribution, dans leurs limites de détection. La mesure du comportement rhéologique à l'état fondu pourrait s'avérer un formidable outil de caractérisation de la structure moléculaire en raison de son extrême sensibilité à certains détails moléculaires, tels que la présence de traces de LCB ou de très hautes masses molaires (MM). Malheureusement, le signal rhéologique dépend de manière conjointe de la MM, MMD et de la présence ou non de LCB, de telle sorte que la détermination d'une MMD ou d'une teneur en LCB par cette voie est impossible aussi longtemps que les effets respectifs de ces paramètres moléculaires sur le comportement rhéologique n'ont pas été clairement et distinctement établis. L'objectif global de cette thèse est de contribuer à une meilleure caractérisation de la structure moléculaire du polyéthylène haute densité en développant, dans un premier temps, une méthode préparative de fractionnement capable de produire des échantillons, linéaires ou branchés, à MMD la plus étroite possible, indispensables en vue de séparer les effets concomitants de la MM, MMD et LCB sur le comportement rhéologique à l'état fondu. Une fois de tels objets modèles isolés, l'influence de la MM et du LCB sur le comportement rhéologique, en cisaillement et en élongation, sera étudié.

Wetting and phase transitions play a very important role our daily life. Molecularly thin films of long-chain alkanes at solid/vapour interfaces (e.g. C30H62 on silicon wafers) are very good model systems for studying the relation between wetting behaviour and (bulk) phase transitions. Immediately above the bulk melting temperature the alkanes wet partially the surface (drops). In this temperature range the substrate surface is covered with a molecularly thin ordered, solid-like alkane film ("surface freezing"). Thus, the alkane melt wets its own solid only partially which is a quite rare phenomenon in nature. The thesis treats about how the alkane melt wets its own solid surface above and below the bulk melting temperature and about the corresponding melting and solidification processes.<br> Liquid alkane drops can be undercooled to few degrees below the bulk melting temperature without immediate solidification. This undercooling behaviour is quite frequent and theoretical quite well understood. In some cases, slightly undercooled drops start to build two-dimensional solid terraces without bulk solidification. The terraces grow radially from the liquid drops on the substrate surface. They consist of few molecular layers with the thickness multiple of all-trans length of the molecule. By analyzing the terrace growth process one can find that, both below and above the melting point, the entire substrate surface is covered with a thin film of mobile alkane molecules. The presence of this film explains how the solid terrace growth is feeded: the alkane molecules flow through it from the undercooled drops to the periphery of the terrace.<br> The study shows for the first time the coexistence of a molecularly thin film ("precursor") with partially wetting bulk phase. The formation and growth of the terraces is observed only in a small temperature interval in which the 2D nucleation of terraces is more likely than the bulk solidification. The nucleation mechanisms for 2D solidification are also analyzed in this work. More surprising is the terrace behaviour above bulk the melting temperature. The terraces can be slightly overheated before they melt. The melting does not occur all over the surface as a single event; instead small drops form at the terrace edge. Subsequently these drops move on the surface "eating" the solid terraces on their way. By this they grow in size leaving behind paths from were the material was collected. Both overheating and droplet movement can be explained by the fact that the alkane melt wets only partially its own solid. For the first time, these results explicitly confirm the supposed connection between the absence of overheating in solid and "surface melting": the solids usually start to melt without an energetic barrier from the surface at temperatures below the bulk melting point. Accordingly, the surface freezing of alkanes give rise of an energetic barrier which leads to overheating. / Sowohl Benetzung als auch Phasenübergänge spielen eine sehr wichtige Rolle im täglichen Leben. Molekular dünne Filme langkettiger Alkane an Festkörper/Gas-Grenzflächen (z. B. C30H62 an Silizium-Waferoberflächen) sind sehr gute Modellsysteme um die Wechselbeziehung zwischen Benetzungsverhalten und (Volumen-)Phasenübergängen zu untersuchen. In einem Temperaturbereich knapp oberhalb der Volumenschmelztemperatur benetzt die Alkanschmelze die Substratoberfläche nur partiell (Alkantropfen). In diesem Temperaturbereich ist die Substratoberfläche mit einer molekular dünnen, festkörperartig geordneten Alkanschicht bedeckt ("Oberflächengefrieren" ). Die Alkanschmelze benetzt also die eigene Festkörperoberfläche nur partiell, ein in der Natur ziemlich seltenes Phänomen. Die Dissertation beschäftigt sich damit wie die Alkanschmelze ihre eigene Festkörperoberfläche über und unter dem Volumenschmelzpunkt benetzt und mit den entsprechenden Vorgängen beim Schmelzen bzw. Erstarren. Flüssige Alkantropfen lassen sich einige Grad unter ihren Schmelzpunkt unterkühlen ohne sich sofort zu verfestigen. Dieses "Unterkühlungsverhalten" ist üblich und es ist theoretisch qualitativ gut verstanden. Allerdings beobachtet man bei den Alkanen bei leichter Unterkühlung statt einer eventuellen Volumenverfestigung oft die Ausbildung von zweidimensionalen Terrassen aus erstarrtem Alkanen. Die Terrassen wachsen auf der Substratoberfläche radial aus den flüssigen Tropfen. Sie bestehen aus wenigen Alkanlagen mit jeweils der Dicke einer Moleküllänge. Die Analyse der Terrassen-Wachstumsprozesse zeigt, dass die gesamte Substratoberfläche einschliesslich der Terrassen sowohl oberhalb als auch unterhalb der Volumenschmelztemperatur mit einer dünnen Schicht mobiler Alkanmoleküle bedeckt ist. Durch diese Schicht fliessen bei Unterkühlung die Alkane vom unterkühlten Tropfen zur Terrassenkante und liefern den Nachschub für deren Wachstum. Die Untersuchungen zeigen damit erstmalig die Koexistenz eines molekular dünnen Films ("Precursor") mit einer partiell benetzenden Volumenphase. Die Entstehung und das Wachstum der Terrassen wird nur in einem engen Temperaturfenster beobachtet in dem die Keimbildung zweidimensionaler Terrassen wahrscheinlicher ist als die dreidimensionale Volumenverfestigung. Auch dieses Keimbildungsverhalten wird in der Dissertation genauer analysiert. Noch erstaunlicher als das Terrassenwachstum, d. h. das Verfestigungsverhalten ist das Schmelzverhalten der Terrassen. Sie lassen sich bis zu einer gewissen Temperatur überhitzen bevor sie schmelzen! Weiterhin findet bei genügender Überhitzung das Schmelzen nicht gleichzeitig überall statt sondern es entstehen zuerst kleine Alkantropfen an den Terrassenrändern. Diese bewegen sich dann über die Substratoberfläche und "fressen" sich durch die festen Terrassen. Dabei wachsen sie weil sie das geschmolzene Material aufnehmen und hinterlassen eine alkanfreie Spur. Sowohl die Überhitzung als auch die Tropfenbewegung lassen sich damit erklären dass die flüssige Alkanschmelze ihren eigenen Festkörper nur partiell benetzt. Die Ergebnisse bestätigen erstmals explizit den seit vielen Jahrzehnten vermuteten Zusammenhang zwischen der üblicherweise nicht beobachtbaren Überhitzung von Festkörpern und Oberflächenschmelzen: Festkörper beginnen normalerweise ohne Energiebarriere von der Oberfläche an zu schmelzen. Entsprechend bildet das Oberflächengefrieren der Alkane eine Energiebarriere und erlaubt damit deren Überhitzen.

This thesis presents our recent study of few interesting problems involving activated processes. This chapter gives an overview of the thesis. It is now possible to do single molecule experiments involving enzyme molecules. The kinetics of such reactions exhibits dynamic disorder associated with conformational changes of the enzyme-substrate complex. The static disorder and dynamic disorder of reaction rates, which are essentially indistinguishable in ensemble-averaged experiments, can be determined separately by the real-time single-molecule approach. In our present work we have given a theoretical description of how rate of reactions involving dynamic disorder is studied using path integral approach. It is possible to write the survival probability and the rate of the process as path integrals and then use variational approaches to get bounds for both. Though the method is of general validity, we illustrate it in the case of electronic relaxation in stochastic environment modeled by a particle experiencing diffusive motion in harmonic potential in presence of delta function sink. The exact solution of corresponding Smoluchowski equation was found earlier[1] analytically in Laplace domain with sink having arbitrary strength and position. Exact evaluation of path integral calculation to survival probability is not possible analytically. Wolynes et al.[2] have done an approximate calculation to get bounds to the survival probability in the Laplace domain. A bound in the Laplace domain is not as useful as a bound in the time domain and hence we use the direct approximate variational path integral technique to calculate both lower and upper bound of survival probability in time domain. We mimic the delta function sink by quadratic sink for which the path integral can be solved exactly. The strength of the quadratic sink is treated as variational parameter and using the optimized value for it, one can estimate the optimized lower as well as upper bound of survival probability. We have also calculated a lower bound to the rate. The variational results are compared with the exact ones, and it is found that the results for the two parameter case are better than those of one parameter case. To understand how good our approximation is, we calculate the bounds in survival time and found them to be in good agreement with exact results. Our approach is valid for any arbitrary initial distribution that one may start with. We consider the Kramers problem for a long chain polymer trapped in a biased double well potential. Initially the polymer is in the less stable well and it can escape from this well to the other well by the motion of its N beads across the barrier to attain the configuration having lower free energy. In one dimension we simulate the crossing and show that the results are in agreement with the kink mechanism suggested earlier. In three dimensions, it has not been possible to get analytical “kink solution”for an arbitrary po-tential; however, one can assume the form of the solution of the non-linear equation as a kink solution and then find a double well potential in three dimensions. To verify the kink mechanism, simulations of the dynamics of a discrete Rouse polymer model in a double well in three dimensions were done. We find that the time of crossing is proportional to the chain length which is in agreement with the results of kink mechanism. The shape of the kink solution is also in agreement with the analytical solution in both one and three dimensions. We then consider the dynamics of a short chain polymer crossing over a free energy barrier in space. Adopting the continuum version of the Rouse model, we find exact expressions for the activation energy and the rate of crossing. For this model, the analysis of barrier crossing is analogous to semiclassical treatment of quantum tunneling. Finding the saddle point for the process requires solving a Newton-like equation of motion for a fictitious particle. The analysis shows that short chains would cross the barrier as a globule. The activation free energy for this would increase linearly with the number of units N in the polymer. The saddle point for longer chains is an extended conformation, in which the chain is stretched out. The stretching out lowers the energy and hence the activation free energy is no longer linear in N . The rates in both the cases are calculated using a multidimensional approach and analytical expressions are derived using a new formula for evaluating the infinite products. However, due to the harmonic approximation made in the derivation, the rates are found to diverge at the point where the saddle point changes over from the globule to the stretched out conformation. The reason for this is identified to be the bifurcation of the saddle to give two new saddles. A correction formula is derived for the rate in the vicinity of this point. Numerical results using the formulae are presented. It is possible for the rate to have a minimum as a function of N . This is due to the confinement effects in the initial state. We analyze the dynamics of a star polymer of F arms confined to a double well potential. Initially the molecule is confined to one of the minima and can cross over the barrier to the other side. We use the continuum version of Rouse-Ham model. The rate of crossing is calculated using the multidimensional approach due to Langer[3].Finding the transition state for the process is shown to be equivalent to the solution of Newton’s equations for F independent particles, moving in an inverted potential. For each star polymer, there is a critical total length N Tc below which the polymer crosses over as a globule. The value of NTc depends on the curvature at the top of the barrier as well as the individual arm lengths. So we keep the lengths of (F -1) arms fixed and increase the length of the F th arm to get the minimum total length NTc. Below NTc the activation energy is proportional to the total arm length of the star. Above N Tc the star crosses the barrier in a stretched state. Thus, there is a multifurcation of the transition state at NTc. Above NTc, the activation energy at first increases and then decreases with increasing arm length. This particular variation of activation energy results from the fact that in the stretched state, only one arm of the polymer is stretched across the top of the barrier, while others need not to be. We calculate the rate by expanding the energy around the saddle upto second order in the fluctuations. As we use the continuum model, there are infinite modes for the polymer and consequently, the prefactor has infinite products. We show that these infinite products can be reduced to a simple expression, and evaluated easily. However, the rate diverges near N Tc due to the multifurcation, which results in more than one unstable mode. The cure for this divergence is to keep terms upto fourth order in the expansion of energy for these modes. Performing this, we have calculated the rate as a function of the length of the star. It is found that the rate has a nonmonotonic dependence on the length, suggesting that longer stars may actually cross over faster.

Investigating the biosynthesis of long-chain (C20–24) polyunsaturated fatty acids (LC-PUFA), physiologically important compounds including arachidonic acid (ARA), eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA), in fish is crucial to identify dietary requirements for essential fatty acids (EFA). Moreover, knowledge of the C20–24 LC-PUFA biosynthetic capability of farmed fish species enables us to understand their ability to utilise commonly used raw materials such as vegetable oils, which naturally lack LC-PUFA but include C18 PUFA that are metabolic precursors of LC-PUFA. Studies have shown that the potential of a species for LC-PUFA biosynthesis is associated with the complement and function of fatty acyl desaturase (fads) and elongase of very long chain fatty acid (elovl) genes existing in that species. The present study therefore aimed to investigate these genes in the African catfish (Clarias gariepinus), the most commercially important farmed fish in sub-Saharan Africa. A fads2, a fads6 and four elovl (elovl2, elovl4a, elovl4b, elovl8) cDNAs were cloned and functionally characterised by heterologous expression in yeast. The Fads2 was a bifunctional desaturase enzyme with ∆6∆5 and ∆8 activities, and thus catalysing all the desaturation reactions required for ARA and EPA biosynthesis from C18 precursor fatty acids. Moreover, the C. gariepinus Fads2 enzymes also desaturated 24:5n-3 to 24:6n-3, a ∆6 desaturation required for the biosynthesis of DHA through the so-called “Sprecher pathway”. Functional characterisation of Fads6 by heterologous expression in yeast did not reveal its function. With regards to elongases, the C. gariepinus Elovl2 demonstrated the ability to elongate C20 and C22 PUFA and thus complements the Elovl5 with elongase capability towards C18 and C20 PUFA. The Elovl8 was capable of only limited elongation of C18 and C20 PUFA. Elovl4a and Elovl4b, enable the biosynthesis of very long-chain (>C24) fatty acids, compounds with major roles in vision and fertility of vertebrates. The present study confirmed that C. gariepinus possess all the enzymatic capabilities required for the biosynthesis of ARA, EPA and DHA and, therefore, its physiological EFA requirements could be satisfied with dietary provision of C18 PUFA.

CoordenaÃÃo de AperfeiÃoamento de Pessoal de NÃvel Superior / As ceras naturais, como a carnaÃba, sÃo misturas complexas de Ãsteres compostos de Ãcidos graxos e alcoÃis de cadeia longa. ObtÃm-se a cera de carnaÃba pelo pà cerÃfero depositado na superfÃcie das folhas da palmeira Copernicia sp, popularmente conhecida como carnaubeira. O objetivo deste trabalho foi estudar a produÃÃo de Ãlcoois de cadeia longa a partir da cera de carnaÃba bruta utilizando diferentes mÃtodos de hidrÃlise alcalina. Amostras de cera de carnaÃba filtrada e refinada de cor amarela (tipo I) foram hidrolisadas por trÃs diferentes processos: (1) 5 g de cera de carnaÃba juntamente com 100 mL de soluÃÃo aquosa de hidrÃxido de potÃssio 2, 5, 10, 15 e 20 % (m/v) foram levadas em tempos de 15, 30, 60 e 120 minutos ao condensador de refluxo a 100ÂC; (2) 3 g de cera de carnaÃba juntamente com 50 mL de soluÃÃo aquosa de hidrÃxido de potÃssio 2, 5, 10, 15 e 20% (m/v) foram irradiadas em forno de microondas seguindo uma programaÃÃo de tempo e potÃncia; (3) 10 g de cera de carnaÃba juntamente com 200 mL de soluÃÃo de hidrÃxido de potÃssio a 2, 10 e 20 % (m/v) foram levadas ao reator quÃmico pressurizado. ApÃs o processo de hidrÃlise, as amostras foram filtradas, lavadas a quente, secas em estufa a 80ÂC/6h e transformadas em pÃ, calculando-se o rendimento e o Ãndice de acidez. As amostras hidrolisadas foram extraÃdas com heptano em Soxhlet por 4 horas e o material obtido foi analisado no espectrÃmetro de massas para a determinaÃÃo da composiÃÃo de alcoÃis de cadeia longa. As amostras hidrolisadas em microondas apresentaram os melhores resultados em rendimento e em Ãndice de acidez. Os alcoÃis triacontanol (A30), dotriacontanol (A32) e tetratriacontanol (A34) foram identificados nas amostras de cera de carnaÃba hidrolisadas pelos trÃs diferentes processos, sendo o dotriacontanol o mais abundante entre eles. / The natural waxes like carnauba, are complex mixtures of ester compounds of fatty acids and long chain alcohols. Carnauba wax is obtained from the waxy powder from the leafs of the Copernicia sp palm, known as carnaubeira. The objective of this work was to study the production of long chain alcohols from crude carnauba wax using different methods of alkaline hydrolysis. Samples of yellow carnauba wax (type I) were filtered refined and hydrolyzed by three different processes: (1) 5 g of carnauba wax along with 100 ml aqueous potassium hydroxide 2, 5, 10, 15 and 20% (w/v) were taken at times of 15, 30, 60 and 120 min the reflux condenser at 100 ÂC; (2) 3 g of carnauba wax, along with 50 mL of aqueous solution of potassium 2, 5, 10 , 15, and 20% (w/v) were irradiated in a microwave oven following a time schedule and power; (3) 10 g of carnauba wax along with 200 mL of potassium hydroxide 2, 10 and 20% (w/v) were brought to the pressurized chemical reactor. After the hydrolysis process, the samples were filtered, washed, dried at 80 C/6h and turned into powder. The process yeld and acidity were measured. The hydrolysed samples were extracted with Soxhlet heptane for 4 hours and the material was analyzed by gas-chromatography-mass spectrometry to determine the composition of long chain alcohols. The samples hydrolyzed in a microwave presented the best yield and acidity index. The alcohols triacontanol (A30), dotriacontanol (A32) and tetratriacontanol (A34) were identified in samples of carnauba wax hydrolyzed by the three different processes, and the dotriacontanol was the most abundant among them.

京都大学 / 新制・論文博士 / 博士(医学) / 乙第13429号 / 論医博第2233号 / 新制||医||1053(附属図書館) / 京都大学大学院医学研究科医学専攻 / (主査)教授 長船 健二, 教授 妹尾 浩, 教授 川口 義弥 / 学位規則第4条第2項該当 / Doctor of Medical Science / Kyoto University / DFAM

京都大学 / 新制・課程博士 / 博士(農学) / 甲第23934号 / 農博第2483号 / 新制||農||1089(附属図書館) / 学位論文||R4||N5369(農学部図書室) / 京都大学大学院農学研究科応用生物科学専攻 / (主査)教授 廣岡 博之, 教授 松井 徹, 教授 吉田 天士 / 学位規則第4条第1項該当 / Doctor of Agricultural Science / Kyoto University / DFAM

No description available.

Yes / The shape memory effect of highly oriented long‐chain‐branched poly(lactic acid) (LCB‐PLA) prepared through solid‐phase die drawing technology was studied by comparison with PLA. When the recovery temperature increased from 60°C to 120°C, for PLA, only one‐step recovery at about 80°C can be observed and the recovery ratio was below 21.5%, while, for LCB‐PLA, multiple recovery behavior with high recovery ratio of 78.8% can be achieved. For oriented PLA, the recovery curve of the final sample showed the same trend with that of sample suffering just free drawing; while for oriented LCB‐PLA, the recovery curve of the final sample showed the same trend with that of sample suffering just die drawing. After shape recovery, the mechanical properties of LCB‐PLA showed a linear downward trend with the recovery temperature. Together with amorphous phase, the oriented mesomorphic phase, which formed during solid die drawing, can act as switching domains. And thus, upon heating, the chain segment of amorphous phase relaxed at first and triggered the first macroscopical shape recovery, leading to the decrease of long period (Lac) and the thickness of the amorphous layer (La). Then, with further increasing temperature, the oriented mesomorphic phase gradually relaxed resulting subsequently multi‐shape recovery, and the Lac and the La further decreased. Therefore, by regulating the recovery temperature of oriented LCB‐PLA, the shape recovery ratio and mechanical strength can be controlled effectively, and thus the self‐reinforced and self‐fastening effect can be achieved simultaneously for PLA as bone fixation material.

The regulation of glucagon-like peptide-1 and peptide YY hormone levels are regulated based on different influential factors, but primarily levels are dependent upon ingested food content. As meals today become more fat-enriched, there is greater requirement for evaluation of these hormones that regulate insulin and satiety levels within the body. We have shown that the gene expression transcript production of glucagon-like peptide-1 and peptide YY are modulated by different concentrations, and times of short-chain fatty acids and long-chain fatty acids. Although the peptide hormone levels have the influential physiological role on effector tissue, the regulation of these hormones begins at the transcript levels. Recent research indicates that glucagon-like peptide-1 and peptide YY hormones are altered in response to different free-fatty acids. The present investigation generally demonstrated an overall decrease in both hormones after chronic exposure to fatty acids. Intestinal secretin tumor cell line (STC-1 cells) was used as a representative for intestinal L-cells. Quantitative real-time PCR analysis was used to determine the changes in RNA transcripts. Overall, there was a decrease in the 3-hour timeline, which continued to decrease in the 16-hour and 24-hour timelines for glucagon-like peptide-1. Peptide YY transcript expression in 3-hours increased significantly after exposure to propionate, a significant decrease after exposure to acetate, and no significant increase or decrease after exposure to butyrate. However, there was a significant decrease in peptide YY once reaching 24-hour exposure. It was determined there is a threshold for different concentrations of free-fatty acids to influence glucagon-like peptide-1 and peptide YY production, which was present in the different concentrations of butyrate. Lastly, exposure to both concentrations of linolenic acid caused a significant decrease in glucagon-like peptide-1 and peptide YY.