Nanopartículas de prata (AgNPs) vêm ganhando grande importância na prevenção contra infecções, principalmente pela sua incorporação em dispositivos médicos, tecidos entre outros produtos relacionados. Estudos prévios indicaram que partículas de menores tamanhos têm ação biocida mais efetiva. Nesse contexto, a separação granulométrica pode ser explorada para se obter partículas com as dimensões desejadas. A centrifugação foi escolhida, entre outros métodos de separação granulométrica, por sua possibilidade de ressuspensão das AgNPs após a separação, pela facilidade do aumento de escala e baixa complexidade. Um modelo do perfil de concentração (em uma cela centrífuga) de AgNPs em função do tempo e intensidade de centrifugação foi proposto a partir da Equação de Lamm, considerando a difusividade Browniana e o coeficiente de Svedberg calculado a partir do balanço de forças. A equação foi resolvida com a solução semi-analítica proposta inicialmente por Fujita (1962) e melhorada pelos alemães Joachim Behlke e Otto Ristau (2001). O desempenho da centrifugação de AgNPs sintetizadas pelo Método Turkevich foi avaliado analisando-se as partículas sobrenadantes por DLS, UV-Vis e microscopia eletrônica e comparando com o modelo proposto. O modelo previu razoavelmente a concentração total de partículas e a sua distribuição de tamanhos em diferentes tempos de centrifugação para forças de campo baixas (força centrífuga relativa até 1480). Para maiores forças de campo, houve uma sedimentação mais acelerada que a prevista pelo modelo. / Silver nanoparticles (AgNPs) have gained great importance in preventing infections, especially by their incorporation into medical devices, tissues and related products. Previous studies indicated that particles of smaller sizes have more effective biocidal action. In this context, granulometric separation may be explored to deliver nanoparticles of desired size. Centrifugation was chosen, among other particle size separation methods, for their ability to resuspend the AgNPs after separation, for the ease of scale-up and low complexity. A profile concentration model (in the centrifuge cell) of AgNPs as a function of time and intensity of centrifugation has been proposed from the Lamm equation, considering the Svedberg and Brownian diffusivity coefficients calculated from a force balance. The equation was solved with the semi-analytical solution proposed initially by Fujita (1962) and improved by the Germans Joachim Behlke and Otto Ristau (2001). The centrifugation performance of AgNPs synthesized by the Turkevich method was evaluated by analyzing the supernatant particles by DLS, UV-Vis and electron microscopy and comparing to the proposed model. The model reasonably predicted the total concentration of particles and their size distribution at different centrifugation times at low field strengths (1480 RCF). For higher field strengths, the sedimentation was faster than expected by the model.

Les travaux de recherche présentés ici avaient pour objectif principal la synthèse de copolymères statistiques à base d’éthylène et d’acide acrylique (AA). Pour cela, la déprotection des groupements esters d’un copolymère statistique précurseur, le poly(éthylène-co-(tert-butyl)acrylate), a été effectuée par hydrolyse à l’aide d’iodure de triméthylsilyle. La synthèse de ce précurseur est réalisée par polymérisation catalytique en présence d’un système à base de Palladium (Pd). Le deuxième objectif a été d’étudier et de caractériser des polymères synthétisés à l’état solide et en suspension colloïdale. Plusieurs copolymères précurseurs comprenant différents pourcentages molaires en tert-butyl acrylate (4 à 12% molaires) ont été synthétisés avec succès, puis déprotégés par hydrolyse pour obtenir des poly(éthylène-coacide acrylique) (pE-co-AA) avec différentes compositions. Seuls les copolymères comprenant 10% molaire ou plus de AA sont solubles dans le Tétrahydrofurane (THF) et uniquement dans ce solvant. De telles solutions peuvent être dialysées dans l’eau, ce qui conduit à un échange lent entre cette dernière et le THF, et l’autoassemblage du copolymère dans l’eau peut ensuite être étudié. C’est ainsi qu’ont pu être observées des nanoparticules stables dans le temps dont le comportement est sensible au pH et à la température. Les polymères synthétisés ont été caractérisés par Résonance Magnétique Nucléaire (RMN) ainsi que par spectroscopie Infra-Rouge (IR), avant et après déprotection. Les pourcentages molaires d’AA ont été déterminés par combinaison des résultats de RMN et ii de titrages conductimètriques. A l’état solide, les échantillons ont été analysés par Calorimétrie différentielle à balayage (DSC) et par Diffraction des rayons X. Les solutions colloïdales des polymères pE-co-AA ont été caractérisées par Diffusion dynamique de la lumière et par la DSC-haute sensibilité. De la microscopie électronique à transmission (TEM) a permis de visualiser la forme et la taille des nanoparticules. / The first objective of this research is to synthesize random linear copolymers of ethylene and acrylic acid (AA). The synthesis relies on the deprotection of the functional groups in the copolymer’s precursor, which is represented by poly(ethylene-co-tertbutyl acrylate). The synthesis of the precursor was realized by the catalytic approach, where Pd-based catalytic systems are frequently utilized nowadays. The deprotection was carried out by hydrolysis of the ester functionality using trimethylsilyl iodide agent. The second objective is to investigate and characterize the synthesized polymers in the bulk and in colloidal solution. A set of different precursor polymers with various degrees of molar incorporation of tertbutyl acrylate (from 4 to 12 mol %) was successfully synthesized and deprotected. The resulting poly(ethylene-co-acrylic acid) copolymers were found to be soluble in tetrahydrofuran THF, when the molar incorporation of AA reaches the value of 12 and more. This aspect gave the possibility to study the self-assembly of this copolymer in aqueous medium by slow THF to water exchange (dialysis). It was found that the copolymers self-assemble into nano-sized structures and these nanoparticles remain stable in colloidal solution for extended periods of time. Moreover, it was shown that the nanoparticles formed by the discussed copolymer possess thermo- and pH-responsive behaviour. The polymers synthesized were characterized by nuclear magnetic resonance (NMR) and infrared spectroscopies (IR) before and after deprotection. The bulk samples were analyzed by conventional differential scanning calorimetry and by X-ray diffraction iv technique. The molar percentages of AA were determined using a combination of NMR and conductimetric titration. Colloidal solutions of pE-co-AA copolymers were analyzed by dynamic light scattering and high-sensitivity differential scanning calorimetry techniques. The nanoparticles formed were visualized and characterized by transmission electron microscopy.

I denna studie undersöktes avkodningsförmåga, läshastighet, motivationsgrad och läsvanor hos 40 vuxna personer, som grupperades utifrån kön, ålder och utbildningsnivå. För att testa avkodningsförmåga användes LäsKedjor-2 (Jacobsson, Läskedjor-2, 2014), för att testa läshastighet användes DLS Läshastighet (Järpsten, DLS läshastighet, 2002) och för att skatta motivationsgrad och läsvanor skapades Självrapport av uppsatsförfattaren själv. Testresultaten omräknades till staninevärden. Ingen signifikant skillnad uppmättes beträffande kön eller ålder på något av testerna. Signifikans beträffande utbildningsnivå uppmättes på alla test utom på det första deltestet i LäsKedjor-2, Bokstavskedjor, samt på läsvanor i Självrapport. Det befanns vara stark korrelation (r=0,62) mellan höga resultat på läshastighet och hög motivationsgrad relaterad till läsning. / In this study decoding skill and reading speed was tested together with level of reading motivation and reading habits in 40 adults, grouped by gender, age and educational level. To test decoding skill LäsKedjor-2 (Jacobsson, Läskedjor-2, 2014) was used, to test reading speed DLS Läshastighet (Järpsten, DLS läshastighet, 2002) was used, and to test level of reading motivation and reading habits the self-assessment questionnaire Självrapport was constructed by the author. The results were transformed into a staninescale. No significant difference was observed regarding gender or age in any of the tests. Significance regarding educational level was observed in all tests except the first part of LäsKedjor-2, Bokstavskedjor, and in reading habits in Självrapport. A strong correlation (r=0,62) was evident in high results in reading speed and high level of reading motivation.

Made available in DSpace on 2014-12-17T15:01:58Z (GMT). No. of bitstreams: 1 DamilsonFS_TESE.pdf: 10674685 bytes, checksum: 7f06df7e27225da9012b623997ac7e3b (MD5) Previous issue date: 2014-09-02 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / The growing utilization of surfactants in several different areas of industry has led to an increase on the studies involving solutions containing this type of molecules. Due to its amphiphilic nature, its molecule presents one polar part and one nonpolar end, which easily interacts with other molecules, being able to modify the media properties. When the concentration in which its monomers are saturated, the airliquid system interface is reached, causing a decrease in interfacial tension. The surfactants from pure fatty acids containing C8, C12 and C16 carbonic chains were synthesized in an alcoholic media using sodium hydroxide. They were characterized via thermal analysis (DTA and DTG) and via infrared spectroscopy, with the intention of observing their purity. Physical and chemical properties such as superficial tension, critical micelle concentration (c.m.c), surfactant excess on surface and Gibbs free energy of micellization were determined in order to understand the behaviour of these molecules with an aqueous media. Pseudo-ternary phase diagrams were obtained aiming to limit the Windsor equilibria conditions so it could be possible to understand how the surfactants carbonic chain size contributes to the microemulsion region. Solutions with known concentrations were prepared to study how the surfactants can influence the dynamic light scattering spectroscopy (DLS) and how the diffusion coefficient is influenced when the media concentration is altered. The results showed the variation on the chain size of the studied surfactant lipophilic part allows the conception of surfactants with similar interfacial properties, but dependent on the size of the lipophilic part of the surfactant. This variation causes the surfactant to have less tendency of microemulsionate oil in water. Another observed result is that the n-alcanes molecule size promoted a decrease on the microemulsion region on the obtained phase diagrams / O crescente uso de tensoativos nas mais diferentes ?reas da ind?stria tem levado a um aumento nos estudos envolvendo solu??es contendo este tipo de mol?cula. Devido a sua natureza anfif?lica, sua mol?cula apresenta uma parte polar e outra apolar, que facilmente interage com outros tipos de mol?culas, podendo modificar as propriedades do meio. Quando a concentra??o, na qual seus mon?meros saturam, a interface do sistema ar-l?quido, ? atingida promovendo a redu??o da tens?o interfacial. Os tensoativos dos ?cidos graxos puros com cadeias carb?nicas C8, C12 e C16 foram sintetizados em meio alco?lico, utilizando hidr?xido de s?dio. Eles foram caracterizados por an?lise t?rmica (DTA e DTG) e espectroscopia de infravermelho com o objetivo de se observar a pureza dos mesmos. Foram determinadas algumas propriedades f?sicoqu?micas como: tens?o superficial, c.m.c. , excesso de tensoativo na interface e energia livre de Gibbs de miceliza??o a fim de se entender o comportamento das intera??es dessas mol?culas com meio aquoso. Foram elaborados diagramas de fase pseudotern?rios com o intuito de realizar as delimita??es do equil?brio de Winsor para compreender como o tamanho da cadeia carb?nica dos tensoativos contribui com a regi?o de microemuls?o. Preparou-se solu??es com concentra??es conhecidas para se estudar como os tensoativos podem influenciar a espectroscopia de espalhamento din?mico de luz (Dynamic Ligth Scattering - DLS) e como o coeficiente de difus?o ? influenciado quando a concentra??o do meio ? alterada. Os resultados mostraram que o aumento ou diminui??o do tamanho da cadeia da parte lipof?lica dos tensoativos estudados permite conceber tensoativos com propriedades interfaciais similares, mas tamb?m dependente do tamanho da parte lipof?lica do tensoativo. Esta varia??o deixa o tensoativo com menor tend?ncia a microemulsionar ?leo em ?gua. Outro resultado observado ? que o tamanho das mol?culas de n-alcanos promoveu uma redu??o da regi?o de microemuls?o dos diagramas de fases obtidos

Nanopartículas de prata (AgNPs) vêm ganhando grande importância na prevenção contra infecções, principalmente pela sua incorporação em dispositivos médicos, tecidos entre outros produtos relacionados. Estudos prévios indicaram que partículas de menores tamanhos têm ação biocida mais efetiva. Nesse contexto, a separação granulométrica pode ser explorada para se obter partículas com as dimensões desejadas. A centrifugação foi escolhida, entre outros métodos de separação granulométrica, por sua possibilidade de ressuspensão das AgNPs após a separação, pela facilidade do aumento de escala e baixa complexidade. Um modelo do perfil de concentração (em uma cela centrífuga) de AgNPs em função do tempo e intensidade de centrifugação foi proposto a partir da Equação de Lamm, considerando a difusividade Browniana e o coeficiente de Svedberg calculado a partir do balanço de forças. A equação foi resolvida com a solução semi-analítica proposta inicialmente por Fujita (1962) e melhorada pelos alemães Joachim Behlke e Otto Ristau (2001). O desempenho da centrifugação de AgNPs sintetizadas pelo Método Turkevich foi avaliado analisando-se as partículas sobrenadantes por DLS, UV-Vis e microscopia eletrônica e comparando com o modelo proposto. O modelo previu razoavelmente a concentração total de partículas e a sua distribuição de tamanhos em diferentes tempos de centrifugação para forças de campo baixas (força centrífuga relativa até 1480). Para maiores forças de campo, houve uma sedimentação mais acelerada que a prevista pelo modelo. / Silver nanoparticles (AgNPs) have gained great importance in preventing infections, especially by their incorporation into medical devices, tissues and related products. Previous studies indicated that particles of smaller sizes have more effective biocidal action. In this context, granulometric separation may be explored to deliver nanoparticles of desired size. Centrifugation was chosen, among other particle size separation methods, for their ability to resuspend the AgNPs after separation, for the ease of scale-up and low complexity. A profile concentration model (in the centrifuge cell) of AgNPs as a function of time and intensity of centrifugation has been proposed from the Lamm equation, considering the Svedberg and Brownian diffusivity coefficients calculated from a force balance. The equation was solved with the semi-analytical solution proposed initially by Fujita (1962) and improved by the Germans Joachim Behlke and Otto Ristau (2001). The centrifugation performance of AgNPs synthesized by the Turkevich method was evaluated by analyzing the supernatant particles by DLS, UV-Vis and electron microscopy and comparing to the proposed model. The model reasonably predicted the total concentration of particles and their size distribution at different centrifugation times at low field strengths (1480 RCF). For higher field strengths, the sedimentation was faster than expected by the model.

Syftet med denna studie har varit att ta reda på hur en interventionsstudie med intensivläsning under en femveckorsperiod, fyra dagar i veckan, med material som är anpassat efter elevernas intressen påverkar elevernas läsförståelse. Metoder som används i studien är enskilda intervjuer med elever, observationer och DLS- test som är ett diagnosinstrument för att mäta elevers läsoch skrivförmåga. De teoretiska utgångspunkter som undersökningen grundar sig på är den sociokulturella lärandeteorin, kognitivism samt embodied learning. Den sociokulturella lärandeteorin valdes för att eleverna i undersökningen lär i samspel med andra, kognitivism för att förstå hur barn tänker. Embodied learning där fokus på den kroppsliga aktiviteten ligger som grund för att förstå hur eleven använder sin kropp vid intensivläsning. Tidigare forskning visar i PISA- undersökningar att svenska elever har en allt sämre läsförmåga. Resultatet i studien visar på kroppens betydelse för att förstå det som läses men även den avsaknad av reflektion i läsundervisningen för att eleverna ska få förståelse för hur processen läsning går till. / The purpose of this study has been to find out how an intervention study with intensive reading during a five-week period, four days a week, with the material specifically adjusted to the pupils’ interests impacts their reading comprehension. The methods used in the study is individual interviews with the pupils, observations and DLS-tests which is a diagnosticinstrument for measuring the pupils reading and writing ability. The theories of this study are based on sociocultural learning theory, cognitivism and embodied learning. The sociocultural learning theory was chosen because the students in this study learn together with other, cognitivism because trying to understand how children think. Embodied learning where focus lies on activity of the body to understand how student use their body when they learn intensive reading. Earlier studies show in PISA studies that the Swedish pupils is getting lesser and lesser reading ability. The results in the study shows the body’s importance in understanding what we read. But it also shows the lack of reflection in the reading instructions for the pupils to understand how the process of reading works.

In this study, four and a half months of ceilometer data from Östergarnsholm are used to analyze cloud related to processes in the boundary layer. Measurements are divided into two categories, which are defined by wind direction: a continental and a marine sector. The results show that there are significant differences in the height of the lowest cloud bases detected for the two sectors, where cloud base heights are lower for the marine wind sector during unstable and neutral conditions. The ceilometer’s ability to detect several cloud base heights simultaneously is utilized to test whether a double layer structure (DLS) can be detected. The results of this particular analysis are inconclusive as to whether a DLS has been observed or not. Detected cloud base heights differ greatly from heights suggested by the lifting condensation level (LCL). A new empirical formula for lowest cloud base height is then derived using the measurements. The Ceilometer’s estimations of sky cover are assessed to be of reasonable quality. This is suggested by computed high correlation with incoming shortwave radiation at noon for three months.  However, histograms of cloud cover measurements suggest that the ceilometer tends to probably either overestimate or underestimate cloud cover.  Large differences in cloud cover were observed for the two wind sectors during unstable conditions. For the months of July and August, a diurnal cycle in cloud cover for the continental wind sector was observed which suggest the presence of Stratocumulus. Measurements performed during upwelling conditions closely resemble those of the marine wind sector performed during stable conditions.

Dans le cadre de l'étude de faisabilité d'un site de stockage de déchets radioactifs, nous nous sommes intéressés au rôle de la matière organique naturelle altérée dans le transport éventuel de radionucléides dans l'environnement. Nous nous sommes plus attachés à la détermination des propriétés électrocinétiques de ces substances humiques dans différentes conditions expérimentales plutôt qu'à la description des réactions de spéciations déjà largement discutées dans la littérature. Pour cela, nous avons choisi de déterminer la taille et la charge de ces substances humiques à l'aide d'une méthode originale : la conductimétrie haute précision. Cette technique associée à une théorie du transport adaptée permet de décrire la mobilité d'espèces chargées en solution en prenant en compte les interactions de paires. Après avoir contribué au développement de cette théorie, nous l'avons utilisée afin de déterminer les propriétés électrocinétiques des substances humiques et d'un polyélectrolyte de référence dans différentes conditions de pH et de force ionique. Tous ces résultats obtenus par conductimétrie ont été corrélés avec d'autres méthodes expérimentales et théoriques : la microscopie à force atomique, la diffusion de lumière dynamique, la zêtamétrie laser et les simulations Monte-Carlo. Les résultats obtenus confirment les hypothèses généralement admises selon lesquelles, les substances humiques sont des petites entités nanométriques ayant des propriétés complexantes vis à vis des cations et sont susceptibles de s'agréger pour former des structures supramoléculaires. L'effet des différents ions présents dans l'environnement (notamment sodium, calcium et magnésium) a été analysé. De plus, la complexation de l'europium – considéré comme un bon analogue de l'américium 241 – a également été étudiée.

La coacervation complexe, une séparation de phase associative principalement induite par des interactions électrostatiques, entre la ß-lactoglobuline (BLG, protéine animale) et la gomme d'Acacia (AG, polysaccharide végétal) a été étudiée dans ce travail. La plus grande difficulté pour comprendre la coacervation complexe au niveau moléculaire entre BLG et AG révèle être la polymolécularité élevée d'AG. A partir de là, la motivation principale de cette thèse était de comprendre et contrôler les interactions entre la BLG et les fractions moléculaires d'AG, FI (~88% d'AG) et FII (~10% d'AG) en utilisant la titration calorimétrique isotherme, la diffusion statique et dynamique de lumière, la mobilité électrophorétique, la Granulo- Polarimétrie et la microscopie optique. Une énergie d'interaction plus forte, une stoechiométrie d'association plus faible et ainsi une complexation favorable ont étés montrées entre la BLG et FII en relation avec l'accessibilité et la densité de charges plus élevées de FII. Les résultats majeurs de cette étude ont ainsi montré des rôles différents des fractions de l'AG dans la coacervation complexe avec la BLG.

Στόχος της παρούσας διπλωματικής εργασίας είναι η μελέτη μέτρησης της διασποράς μεγέθους λιποσωμάτων με την τεχνική της συντονιζόμενης ανίχνευσης παλμών ωμικού ρεύματος, σε σύγκριση με την μέθοδο της δυναμικής σκέδασης φωτός, που χρησιμοποιείται συνήθως. Για τον σκοπό αυτό, μελετήθηκε η διασπορά μεγέθους διαφόρων λιποσωμικών διασπορών, σε διάφορους χρόνους μετά την παρασκευή τους, πριν και μετά από λυοφιλοποίηση, καθώς και όταν επωάστηκαν (για διάφορες χρονικές περιόδους) παρουσία πρωτεϊνών. Όλοι οι τύποι λιποσωμάτων χαρακτηρίστηκαν ως προς το μέγεθος και τον δείκτη πολυδιασποράς και με τις δύο τεχνικές: Δυναμική σκέδαση φωτός (DLS) και την τεχνική συντονισμένης ανίχνευσης παλμών ωμικού ρεύματος (TRPS). Από την μελέτη σταθερότητας μεγέθους των λιποσωμάτων μετά από λυοφιλοποίηση (freeze-drying), φαίνεται ότι η σταθερότητα του μεγέθους, εξαρτάται από το υδατικό μέσο στο οποίο βρίσκονται και από την λιπιδική συγκέντρωση του δείγματος. Ακόμα, έγινε προσπάθεια να διερευνηθεί αν το ποσοστό του φορτίου που φέρουν τα λιποσώματα, επηρεάζει την σταθερότητα του μεγέθους, και παρασκευάστηκαν SUV λιποσώματα με διαφορετικό φορτίο. Σύμφωνα με τα αποτελέσματα, η σταθερότητα μεγέθους των λιποσωμάτων με την πάροδο του χρόνου, δεν εξαρτάται από τη συγκέντρωση της διασποράς (τουλάχιστον στην περιοχή συγκεντρώσεων που μελετήθηκαν), αλλά από το φορτίο που φέρουν. Πιο συγκεκριμένα, στα λιποσώματα με 20% PG, το μέγεθος αυξήθηκε κατά 5-22%, σε αντίθεση με τα λιποσώματα που φέρουν 10% PG, στα οποία το μέγεθος αυξήθηκε κατά 2,5-10%. Τέλος, η επώαση παρουσία πρωτεϊνών, φάνηκε να επηρεάζει σημαντικά το μέγεθος των λιποσωμάτων (με και χωρίς φορτίο) μετά από 48 ώρες. / The aim of this study is to investigate the results of a TRPS technique to measure the size distribution of various types of liposomes in comparison with those obtained by the classically used DLS methodology. For this, the size stability of liposomes was studied (using both techniques) before and after a freeze drying cycle, and also before and after their incubation (for various time periods) in presence of proteins. All types of liposomes were characterized for their size and polydispersity index, by using the two techniques: Dynamic light scattering (DLS) and Tunable Resistive Pulse Sensing (TRPS). The size stability study of liposomes, after freeze-drying, was found to depend on the aqueous medium in which they are dispersed (buffer or glucose) and (more) on the lipid concentration of the dispersions. The effect of adding a charged lipid in the liposome bilayer on their size stability was additionally investigated. For this, charged and non-charged SUV liposomes were prepared. According to the results the size stability of liposomes is affected by their charge. Specifically, liposomes with 20% PG, size increased by 5-22 % and liposomes with 10% PG, size increased by 2,5-10 %. Finally, the size stability of liposomes in the presence of proteins was studied, by using two different liposome types, with or without charge. The results showed that the size distribution remained stable during the first 48 hours of incubation but after that, liposome size was significantly increased.