Theoretical predictions of behaviour of various parameters governing the free flow of a single, very long, denser-than-liquid carrier, cylindrical capsule in a horizontal pipeline are reported in this dissertation. The study was carried out for average flow velocities of approximately 1 to 10 ft/sec in pipes of diameters 4, 6, 12 and 24 in. with diameter ratios varying from 0.9 to 0.99. While two liquid carriers -- water and oil (µ = 10 cP and sp. gr. = 0.85) were used, the eccentricity of the capsule-pipe system was fixed at 0.999. The theoretical solution was found to be in good agreement with the experimental results. / Thesis / Master of Engineering (ME)

No description available.

A terapia fotodinâmica consiste em uma nova e promissora técnica de tratamento de câncer. O tratamento se baseia na administração tópica ou sistêmica de um fotossensibilizador, que se acumula seletivamente em tecido tumoral. Na presença de luz e oxigênio o fotossensibilizador produz espécies tóxicas levando as células à morte. Neste trabalho foi determinada a eficiência fotodinâmica dos corantes fenotiazínicos (Azul de Metileno e Azul de Toluidina O) e xantenos (Rose Bengal, Eritrosina B, Eosina Y e Fluoresceína) através da comparação dos valores de concentração inibitória media (IC50) em células tumorais HEp-2; atividade fotodinâmica utilizando o ácido úrico como dosímetro químico; interação com proteína através da constante de ligação (KA) com BSA e coeficiente de partição em octanol-água (logP). Os resultados foram relacionados com as propriedades moleculares destes corantes afim de se obter uma melhor compreensão de suas estruturas e fornecer subsídios para o planejamento de novos e melhores compostos para serem utilizados como fotossensibilizadores em PDT. Os experimentos mostraram que os fenotiazínicos são mais citotóxicos nesta linhagem celular do que os xantenos, sendo que o Azul de Toluidina O possui o menor valor de IC50. Dentre os xantenos, o Rose Bengal foi o fotossensibilizador mais eficiente em causar fotoxidação do ácido úrico e o Azul de Toluidina O dentre os fenotiazínicos. Estes resultados estão de acordo com os resultados obtidos nos experimentos citotóxicos, em que Rose Bengal e Azul de Toluidina O apresentam os menores valores de IC50, em suas respectivas famílias. Os xantenos possuem maior interação com BSA do que os fenotiazínicos. Os corantes fenotiazínicos são mais hidrofóbicos do que os xantenos (com vii exceção do Rose Bengal), o que corrobora com os valores de IC50, pois também são os mais citotóxicos. Relacionando algumas propriedades moleculares dos corantes obtidos no estudo teórico com os dados experimentais observou-se que; i) quanto menor os valores das energias dos orbitais HOMO e LUMO maior foi os valores obtidos de IC50; ii) os corantes fenotiazínicos são moléculas menores que os corantes xantenos, facilitando sua difusão pela membrana plasmática e a localização nas organelas; iii) nos corantes xantenos a substituição por um átomo de número atômico maior provoca aumento no valor da atividade fotodinâmica e iv) os xantenos apresentam momentos de dipolo maiores do que os fenotiazínicos, explicando assim a maior hidrofilicidade dos xantenos. Os resultados obtidos mostraram que os corantes fenotiazínicos possuem uma eficiência fotodinâmica superior aos dos corantes xantenos, sendo que o Azul de Toluidina O é o mais eficiente e deve ser considerado como agente potencial para aplicação em PDT. / The photodynamic therapy consists in a new technique for cancer treatment. The treatment is based on topic or systemic administration of a photosensitizer, which is selectively retained in tumor tissue. In the presence of light and oxygen, it produces toxic species to cells leading to their death. In this work it was determinated the photodynamic efficiency of phenothiazinium (Methylene Blue and Toluidine Blue O) and xanthene dyes (Rose Bengal, Erythrosin B, Eosin Y and Fluorescein) by comparing the values of medium inibitory concentration (IC50) in HEp-2; photodynamic activity using the uric acid as a chemical dosimeter; interaction with protein through the binding constant (KA) with BSA and the octanolwater partition coefficient (logP). The results were related with the molecular properties of these dyes, in order to obtain a better understanding of their structures and provide insights for the design of new and better compounds to be used as photosensitizers in PDT. The experiments showed that the phenothiazine dyes are more cytotoxic in this cell line than the xanthenes, being Toluidine Blue the one that has the lower IC50. Among the xanthenes, Rose Bengal was the most efficient photosensitizer in causing photoxidation of uric acid and the Toluidine Blue O among the phenothiazines. These results are consistent with the ones obtained in the cytotoxicity experiments, once the Rose Bengal and Toluidine Blue O have the lower IC50 values, when compared with the other dyes studied in the same family. The xathenes have higher interaction with BSA than the phenothiazines. The phenothiazine dyes are more hydrophobic than the xanthenes (with the exception of Rose Bengal), which corroborate with the IC50 values, once they are also the most cytotoxic. Relating some molecular properties of the dyes obtained in the theoretical studies with the experimental data, it could be observed that; i) the lower is the values of HOMO and LUMO energy, the high is the IC50; ii) the phenothiazine dyes are smaller molecules than the xanthenes, which facilitate their diffusion across the plasmatic membrane and the localization in organelles; iii) in xanthenes dyes the substitution for an atom with higher atomic number increases the photodynamic activity, and iv) the xanthenes dyes have the higher dipole moment than the phenothiazines, explaining the higher hydrophilicity of the xanthenes. The obtained results showed that the phenothiazine dyes have higher photodynamic efficiency than the xanthenes dyes, being Toluidine Blue the most efficient of these dyes and it should be considered as a potential agent for photodynamic therapy.

A terapia fotodinâmica consiste em uma nova e promissora técnica de tratamento de câncer. O tratamento se baseia na administração tópica ou sistêmica de um fotossensibilizador, que se acumula seletivamente em tecido tumoral. Na presença de luz e oxigênio o fotossensibilizador produz espécies tóxicas levando as células à morte. Neste trabalho foi determinada a eficiência fotodinâmica dos corantes fenotiazínicos (Azul de Metileno e Azul de Toluidina O) e xantenos (Rose Bengal, Eritrosina B, Eosina Y e Fluoresceína) através da comparação dos valores de concentração inibitória media (IC50) em células tumorais HEp-2; atividade fotodinâmica utilizando o ácido úrico como dosímetro químico; interação com proteína através da constante de ligação (KA) com BSA e coeficiente de partição em octanol-água (logP). Os resultados foram relacionados com as propriedades moleculares destes corantes afim de se obter uma melhor compreensão de suas estruturas e fornecer subsídios para o planejamento de novos e melhores compostos para serem utilizados como fotossensibilizadores em PDT. Os experimentos mostraram que os fenotiazínicos são mais citotóxicos nesta linhagem celular do que os xantenos, sendo que o Azul de Toluidina O possui o menor valor de IC50. Dentre os xantenos, o Rose Bengal foi o fotossensibilizador mais eficiente em causar fotoxidação do ácido úrico e o Azul de Toluidina O dentre os fenotiazínicos. Estes resultados estão de acordo com os resultados obtidos nos experimentos citotóxicos, em que Rose Bengal e Azul de Toluidina O apresentam os menores valores de IC50, em suas respectivas famílias. Os xantenos possuem maior interação com BSA do que os fenotiazínicos. Os corantes fenotiazínicos são mais hidrofóbicos do que os xantenos (com vii exceção do Rose Bengal), o que corrobora com os valores de IC50, pois também são os mais citotóxicos. Relacionando algumas propriedades moleculares dos corantes obtidos no estudo teórico com os dados experimentais observou-se que; i) quanto menor os valores das energias dos orbitais HOMO e LUMO maior foi os valores obtidos de IC50; ii) os corantes fenotiazínicos são moléculas menores que os corantes xantenos, facilitando sua difusão pela membrana plasmática e a localização nas organelas; iii) nos corantes xantenos a substituição por um átomo de número atômico maior provoca aumento no valor da atividade fotodinâmica e iv) os xantenos apresentam momentos de dipolo maiores do que os fenotiazínicos, explicando assim a maior hidrofilicidade dos xantenos. Os resultados obtidos mostraram que os corantes fenotiazínicos possuem uma eficiência fotodinâmica superior aos dos corantes xantenos, sendo que o Azul de Toluidina O é o mais eficiente e deve ser considerado como agente potencial para aplicação em PDT. / The photodynamic therapy consists in a new technique for cancer treatment. The treatment is based on topic or systemic administration of a photosensitizer, which is selectively retained in tumor tissue. In the presence of light and oxygen, it produces toxic species to cells leading to their death. In this work it was determinated the photodynamic efficiency of phenothiazinium (Methylene Blue and Toluidine Blue O) and xanthene dyes (Rose Bengal, Erythrosin B, Eosin Y and Fluorescein) by comparing the values of medium inibitory concentration (IC50) in HEp-2; photodynamic activity using the uric acid as a chemical dosimeter; interaction with protein through the binding constant (KA) with BSA and the octanolwater partition coefficient (logP). The results were related with the molecular properties of these dyes, in order to obtain a better understanding of their structures and provide insights for the design of new and better compounds to be used as photosensitizers in PDT. The experiments showed that the phenothiazine dyes are more cytotoxic in this cell line than the xanthenes, being Toluidine Blue the one that has the lower IC50. Among the xanthenes, Rose Bengal was the most efficient photosensitizer in causing photoxidation of uric acid and the Toluidine Blue O among the phenothiazines. These results are consistent with the ones obtained in the cytotoxicity experiments, once the Rose Bengal and Toluidine Blue O have the lower IC50 values, when compared with the other dyes studied in the same family. The xathenes have higher interaction with BSA than the phenothiazines. The phenothiazine dyes are more hydrophobic than the xanthenes (with the exception of Rose Bengal), which corroborate with the IC50 values, once they are also the most cytotoxic. Relating some molecular properties of the dyes obtained in the theoretical studies with the experimental data, it could be observed that; i) the lower is the values of HOMO and LUMO energy, the high is the IC50; ii) the phenothiazine dyes are smaller molecules than the xanthenes, which facilitate their diffusion across the plasmatic membrane and the localization in organelles; iii) in xanthenes dyes the substitution for an atom with higher atomic number increases the photodynamic activity, and iv) the xanthenes dyes have the higher dipole moment than the phenothiazines, explaining the higher hydrophilicity of the xanthenes. The obtained results showed that the phenothiazine dyes have higher photodynamic efficiency than the xanthenes dyes, being Toluidine Blue the most efficient of these dyes and it should be considered as a potential agent for photodynamic therapy.

We have modeled in one-dimension two-dimensional (2-D) quantum wire structures: the notched electron stub tuner (NEST) and the double-notched electron stub tuner (D-NEST). The models consisted of square barriers representing the notches and square wells representing the stubs. We have calculated the transmission coefficient as a function of electron energy and/or device geometries to study electron transport through these quantum wire models. The transfer matrix method was used to calculate the transmission coefficient by utilizing a program written with Mathematica. The program and technique were verified using one-dimensional systems from the literature.We studied the principle of wave interference in the NEST model in the form of intersection points of several curves of the transmission coefficient versus barrier/well separation plotted with no offset. The creation of standing waves, in certain regions of the NEST model, by the interference of incident and reflected waves, gives rise to these intersection points. We have identified features in the conductance curves of the NEST and the transmission coefficient curves of the NEST model (the intersection points) that are very similar and may be explained by the same principle of wave interference.We have studied double-barrier resonant tunneling (DBRT) to assist in our study of the D-NEST model. The resonances in DBRT are attributed to the creation of standing waves between the two barriers for the tunneling and non-tunneling regimes. We attempted to prove the existence of these standing waves by studying the probability density in the D-NEST model. The well of the D-NEST model was scanned down the length of the double-barrier well region to investigate its effect on the transmission coefficient for this purpose. A small square barrier, used as a probe, was also used to study the probability density in the same way as the well was used. Initial scans of the probe above a simple square barrier gave us insight into the possibility of using it to scan for the probability density in the well region. The "over-the-barrier" resonances (attributed to standing waves) were studied in this case.We have developed knowledge of the transmission properties of these models that may aid in the understanding of the electron transport through the 2-D devices. We believe that to "fine tune" the conductance output of the D-NEST device, the second notch should be placed at a location that permits the creation of standing waves, for a specific electron energy value, between the two notches of the device. The "fine tuning" of the conductance output into a square-wave pattern could improve the devices performance as a potential switching mechanism. / Department of Chemistry

Partant des composés ATiO3 (A=Ba, Pb, Sr) bien connus pour leurs propriétés de type ferroélectriques, il est possible de concevoir des super-réseaux de basse dimensionnalité (multi-couches, phases de type ,…) où ces propriétés peuvent être modulées en fonction de la composition, de l'épaisseur des couches mises en jeu, des contraintes aux interfaces. Nous proposons ici d'étudier par calculs de premiers principes les instabilités structurales et la dynamique de réseau pour des systèmes simples dans cette famille. En définissant clairement les zones interfaciales et de cœur des couches, et en étudiant la convergence de leurs propriétés en fonction de l'épaisseur, ce travail vise à établir des potentiels interatomiques modèles, analytiques et transférables, pour la prédiction des propriétés dynamiques et des instabilités structurales de super-réseaux étendus et/ou complexes. / The aim of the present thesis is to investigate, from first-principles, the ferroelectricproperties and related phase transition behaviors in perovskite type compounds. Wewill not focus only on the bulk perovskite systems, but also on related layered superlatticeswhere the interface may play an important role and induce new phenomena.

La réception plurielle du développement durable interpelle et interroge. Malléable, il fédère les différents acteurs de la société qui l’utilisent à différentes fins, traduisant ainsi la difficulté de la définition de sa nature juridique. Est-il un droit contraignant impliquant des obligations ? Au moyen de quel mécanisme peut-il être respecté ? A partir de ces interrogations, se dessine tout l’intérêt juridique devant être porté au développement durable. Du point de vue académique, il nous permet de concilier la philosophie naturaliste du droit avec sa traduction dans l’ordre juridique. Décloisonnant les branches du droit, il crée des interactions entre les différents foyers normatifs dans un ordre qui apparaît sous la forme d’un réseau. De par cette circulation, le développement durable se présente comme une force créatrice de droits à travers lesquels il tend à devenir un droit objectif. Du point de vue humain, il reconnaît la possibilité de croire à un avenir pour notre postérité. Au-delà, il se présente comme un droit du vivant promis à évoluer de génération en génération, constituant déjà en lui-même l’expression du patrimoine dont nous héritons de nos ancêtres et destiné au futur. / The plural reception of the sustainable development questions us. Malleable it federates the various actors who use in various purposes so translating the difficulty of the definition of its legal nature. Is it a binding law implying obligations ? How can it be respected? From these questions, he appears all the interest of the legal study of the sustainable development. From the academic point of view, he links the naturalistic philosophy of the right with his translation in the legal legal network. Which decompartmentalizes areas of law, he creates interactions wich each other. The sustainable development creating the right and tends to become a blinding law.From the human point of view, he recognizes the possibility of believing in a future for our offspring. Beyond, he appears as a right of alive promised to evolve from generation to generation, already establishing in himself the expression of the heritage of which we inherit from our ancestors and intended for the future.

I den här rapporten har fokus varit att undersöka och identifiera förbättringsområden i användandet av  fjärrvärme inom dagens fjärrvärmesystem. Rapporten är huvudsakligen en teoretisk studie som är kombinerad med egna simuleringar via programvaran NetSim.  Användningen av fjärrvärme utvecklas ständigt och i dagsläget används främst tredje generationens fjärrvärme med en pågående utveckling av fjärde generationens fjärrvärme. Fjärrvärme kan produceras via olika anläggningar  där kraftvärme har  valts att avgränsa och fokusera på. Den producerade fjärrvärmen inom Sverige består av en framledningstemperatur med ett medelvärde av +86 ̊C och +47,2 ̊C i returledningen. Rapporten inriktar sig specifikt på användning av fjärrvärme inom bostads-  och service sektorn där fjärrvärme stod för 31% av uppvärmningsbehovet år 2019. Detta skapar en bra grund för argumentet att effektivisera dess användning vilket kan möjliggöras utanför byggnaden i fjärrvärmenätet men även inuti byggnaden.   Genomförandet har varit att ta fram slutsatser via simuleringar, tidigare forskning samt litteratur. Programvaran NetSim som är utvecklat för fjärrvärmesimuleringar användes för att simulera och undersöka hur fjärrvärmenätet påverkas utifrån tre olika scenarion (i) referensscenario (ii) lägre nättemperatur (iii) lägre nättemperatur vid högre påfrestning i fjärrvärmenätet.  Scenarierna  reflekterar  dagens fjärrvärmenät och vilken potential som finns inom framtida fjärde generationens fjärrvärmenät.   De resultat rapporten visar är att det finns potential för ett antal förbättringar inom fjärrvärmesystemet, första förbättringen är kring ändring av kopplingsprincip i fjärrvärmecentralen. Olika kopplingar har potential att uppnå olika returtemperatur utifrån dess utformning. De principer som studerades var parallell-, tvåstegs-, trestegs- och seriekoppling, där trestegskoppling åstadkom lägst returtemperatur på bekostnad av ökad komplexitet, miljöpåverkan och pris. Andra förbättringen är att frångå användningen av varmvattencirkulation då det estimeras att det stå för omkring 10 – 20% av flödet i fjärrvärmesystemet, det leder till en ökad returledningstemperatur vilket är ej något som eftersträvas. Lösningen är introduktionen av en tredje ledning som återcirkulerar varmt vatten från framledningen tillbaka till framledningen igen fast i ett tidigare skede.   Framtidens fjärde generation för med sig stora förbättringar vilket visades i litteratur, tidigare forskning och egna simuleringar men det är i ett tidigt skede än. Endast tio projekt kring fjärde generationen hade startat eller planerades i Sverige år 2020. Fjärde generationen medför lägre nättemperatur med en framledningstemperaturen kring +50 ̊C till +55 ̊C och en returtemperatur på omkring +20 ̊C. Den lägre nättemperatur ger möjlighet till användning av lägenhetsväxlare i flerbostadshus i stället för en gemensam fjärrvärmecentral på botten-  eller källarplan, det eliminerar användningen av varmvattencirkulation och risk för Legionella. Lägre nättemperatur möjliggör även att större mängd elektricitet i kraftvärmeverk kan produceras vid samma värmebehov samtidigt som högre effekt uppnås med rökgaskondensering ifall kraftvärmeverket använder sig av det.  Det noteras även  att  det bör finnas  större initiativ  för  fjärrvärmekunder  att sänka dess returledningstemperatur antingen via ekonomiska medel eller alternativa lösningar. I dagsläget finns det ej tillräckligt stort incitament för kunden att vilja genomgå en förändring, en förändring som har potential att påverka nätet positivt ur ett ekonomiskt och miljömässigt perspektiv. / The focus of this report has been to investigate and identify areas for improvement in the use of district heat  within  our  current  district heating system. The report is mainly a theoretical study combined with own simulations via the software NetSim.   The use of district heating is constantly evolving and currently mainly third generation district heating is used with ongoing development of fourth generation district heating. District heating can be produced by different plants, where  CHP-plants  has been chosen to be delimited and focused on. The district heat produced within Sweden consists of a supply temperature with an average value of +86 ̊C and +47.2 ̊C in the return line. The report focuses specifically on the use of district heating in the residential and service sector where district heating accounted for 31% of the heating demand in 2019. This creates a good basis for the argument to make its use more efficient which can be made possible outside the building in the district heating network but also inside the building.    The methodology  has been to  develop  conclusions via simulations, previous research, and literature. The NetSim software developed for district heating simulations was used to simulate and investigate the impact on the district heating network based on three different scenarios (i) reference scenario (ii) lower network temperature (iii) lower network temperature at higher demand in the district heating network. The scenarios reflect the current district heating network and the potential of the future fourth generation district heating network.    The results of the report show that there is potential for a number of improvements in the district heating system, the first improvement is around the change of the coupling principle in the district heating plant. Different couplings have the potential to achieve different return temperatures depending on their design. The principles studied were parallel, two-stage, three-stage and series coupling, where three-stage coupling achieved the lowest return temperature at the cost of increased complexity, environmental impact, and price. The second improvement is to abandon the use of hot water circulation as it is estimated to account for around 10 - 20% of the flow in the district heating system, leading to an increased return line temperature which is not desirable. The solution is the introduction of a third pipe that recirculates hot water from the supply line back to the supply line again but at an earlier stage.    The fourth generation of the future brings great improvements  which has been  shown in literature, previous research, and own simulations but it is in an early stage yet. Only ten fourth generation projects had started or were planned in Sweden in 2020. Fourth generation brings lower net temperature with a supply temperature around +50 ̊C to +55 ̊C  and a return temperature of around +20 ̊C. The lower net temperature allows the use of apartment exchangers in apartment buildings instead of a collective  district heating  substation  on the ground or basement level, it eliminates the use of hot water circulation and the risk of Legionella. Lower net temperature also allows a larger amount of electricity to be produced in CHP-plants for the same heating demand, while higher output can be achieved with flue gas condensation if the CHP-plant uses it.   It is also noted that greater initiative should be given to district heating customers to lower their return line temperature either through financial means or alternative solutions. At present, there is not enough incentive for the customer to want to undergo a change, a change that has the potential to positively impact the network from an economic and environmental perspective.

Cette thèse est une étude théorique sur la interface de porphyrine de cobalt avec des surfaces métalliques avec le code VASP DFT. Le cadre DFT nécessaire a été introduit dans le chapitre 1. La structure de la jBardeen, une programme ecrit en Java, pour la simulation de la STM est expliqué dans le chapitre 2 et le code source est jointe en annexe. Une étude de l'adsorption de CoTPP sur les surfaces métalliques a été entrepris dans le chapitre 3. Différents paramètres de calcul ont été évalués: Le site d'adsorption et de la géométrie à la fois la molécule et la surface ont été étudiés par rapport à la xc-fonctionnel et correction de la dispersion utilisée. Une adsorption site le plus stable est identifié. Par conséquent, ce site plus stable a été étudiée pour sa structure électronique. Calculés images STM avec le code jBardeen ont été comparés avec une experimentation de CoTPP Cu sur une surface (111) avec une couverture sous monocouche. Dans le chapitre 4, un adatome Fe a été présenté à la CoTPP sur Ag système (111). Trois sites de liaison symétrique différentes pour l'atome Fe ont été identifiés sur le macrocycle, marqué les , bi-, brd- et bru-positions. Un moment magnétique pouvait être attestée qui a été principalement situé sur l'atome Fe. Voies possibles entre les quatre, symétriquement équivalentes, sites bi- ont été étudiées avec des méthodes différentes. Simples calculs dans le vacuum et calculs de la “Nudged Elastic Band” (NEB) de l'ensemble du système a révélé une hauteur de barrière légèrement au-dessus de 0,2 eV allant de position bi à la posititon brd. Une analyse de vibration a montré que la commutation de l'atome Fe est susceptible, lorsqu'il est perturbé hors d'équilibre dans les positions brd et bru. / This thesis is a theoretical study on the cobalt porphyrin - coinage metal surface interface with the DFT code VASP. The necessary DFT framework has been introduced in chapter 1. The structure of the Java program jBardeen for STM simulation is explained in chapter 2 and the source code is attached as Appendix. A study of the adsorption of CoTPP on coinage metal surfaces has been undertaken in chapter 3. Different parameters of the calculation have been evaluated: the adsorption site and the geometry of both the molecule and surface have been investigated with respect to the xc-functional and dispersion correction used. A most stable adsorption site -bridge down- is identified. Consequently, this most stable site was investigated for its electronic structure. Calculated STM images with the jBardeen code were compared with an experiment of CoTPP on a Cu(111) surface with sub monolayer coverage. In chapter 4 an Fe adatom was introduced to the CoTPP on Ag(111) system. Three symmetrically different binding sites for the Fe atom were identified on the macrocycle, labelled the bi-, brd- and bru-positions for bisector, bridge down and bridge up respectively. A magnetic moment could be evidenced which was mainly located on the Fe atom. Possible pathways between the four symmetrically equivalent bisector sites were investigated with different methods. Single point calculations in vacuum and Nudged Elastic Band (NEB) of the whole system revealed a barrier height of slightly above 0.2 eV going from bi- to the brd-position. A vibrational analysis showed that switching of the Fe atom is likely, when perturbed out of equilibrium in the brd- and bru- positions.