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<p>In the research presented in this licentiate thesis the surface specific technique Vibrational Sum Frequency Spectroscopy, VSFS, combined with the Langmuir trough has been utilized to investigate Langmuir monolayers and Langmuir-Blodgett (LB) deposited mono- and bilayers of phospholipids. Their molecular structure, stability, and hydration were probed to gain additional understanding of important properties aiming at facilitating the use of such layers as model systems for biological membranes.</p><p>VSFS was applied to <em>in situ</em> studies of the degradation of Langmuir monolayers of 1,2-diacyl-phosphocholines with identical C-18 chains having various degrees of unsaturation. The time-dependent change of the monolayer area at constant surface pressure as well as the sum frequency intensity of the vinyl-CH stretch at the C=C double bonds were measured to monitor the degradation. It was shown that a rapid degradation of the monolayers of unsaturated phospholipids occurred when exposed to the laboratory air compared to the fully saturated lipid, and that the degradation could be inhibited by purging the ambient air with nitrogen. The degradation was attributed to oxidation mediated by reactive species in the air.</p><p>The molecular structure and order of Langmuir monolayers of 1,2-distearoyl-phosphocholine (18:0 PC) and their hydrating water were investigated at different surface pressures using VSFS. The spectroscopic data indicated a well ordered monolayer at all surface pressures with a more intense signal at higher pressures attributed to the subsequent increase of the number density and more ordered lipid molecules due to the tighter packing. Water molecules hydrating the headgroups or being in contact with the hydrophobic parts were observed and distinguished by their vibrational frequencies, and found to have different average orientations.</p><p>Additionally, monolayers of 18:0 PC, its fully deuterated analogue, and 1,2-distearoyl-phosphoserine (18:0 PS) were Langmuir-Blodgett (LB) deposited on CaF₂ substrates and VSFS was used to investigate the structure and order of the films as well as the hydrating water. The CH-region, water region, and lower wavenumber region containing phosphate, ester, carboxylic acid, and amine signals were probed to obtain a complete picture of the molecule. The data indicates that all deposited monolayers formed a well ordered and stable film and the average orientation of the aliphatic chains was determined using the antisymmetric methyl stretch.</p> / <p>I forskningen som presenteras i denna licentiatavhandling har den ytspecifika vibrationssumfrekvensspektroskopin, VSFS, använts tillsammans med Langmuirtråget för att studera Langmuir-monolager och Langmuir-Blod-gett (LB) deponerade monolager och bilager av fosfolipider. För att utvidga förståelsen av egenskaper som är viktiga för att underlätta användandet av dem som modellsystem för biologiska membran undersöktes såväl deras molekylära struktur som stabilitet och hydratisering.</p><p>VSFS användes för att genomföra <em>in situ</em>-studier av nedbrytningen av Langmuir-monolager av 1,2-diacyl-fosfokoliner med identiska 18 kolatomer långa sidokedjor med varierande antal omättade kol-kol-bindningar. För att övervaka nedbrytningen mättes såväl den tidsberoende förändringen av monolagernas area vid konstant yttryck som sumfrekevensintensiteten från dubbelbindningarnas CH-vibration. När monolagerna bestående av omättade fosfolipider utsattes för laboratorieluften bröts de ner hastigt jämfört med det helt mättade monolagret. Denna nedbrytning som sannolikt orsakades av reaktiva ämnen i luften kunde inhiberas fullständigt genom att ersätta den omgivande luften med kvävgas.</p><p>Den molekylära strukturen och ordningen hos Langmuir-monolager av 1,2-distearoyl-fosfokolin (18:0 PC) och deras hydratiseringsvatten undersöktes vid olika yttryck med VSFS. Den spektroskopiska datan visar att monolagerna är välordnade vid alla yttryck samt att sumfrekvenssignalens styrka ökar med ökande yttryck på grund av såväl det större antalet molekyler per ytenhet som den högre ordningen då molekylerna packas tätare. Vattenmolekyler som hydratiserar huvudgrupperna eller är i kontakt med hydrofoba delar och har olika medelorientering observerades och kunde identifieras genom sina vibrationsfrekvenser.</p><p>Vidare deponerades monolager av 18:0 PC, dess fullt deuterade analog och 1,2-distearoyl-fofsfoserin (18:0 PS) på substrat av CaF₂ och VSFS användes för att undersöka filmernas struktur och ordning såväl som hydratiseringsvattnet. CH- och vattenregionerna samt lågvågtalsområdet som innehåller fosfat-, ester-, karboxylsyra- och aminsignaler undersöktes för att få en fullständig bild av den molekylära strukturen. Data visar att alla deponerade monolager bildade en välordnad och stabil film och kolvätekedjornas medelorientering bestämdes med hjälp av signalen från den antisymmetriska metylvibrationen.</p> / QC 20100924

Ce travail porte sur l’élaboration et la caractérisation physico-chimique de nanoparticules hybrides à base d’apatites phosphocalciques biomimétiques proches du minéral osseux, en vue d’applications dans le domaine du diagnostic de cancers voire de thérapeutique. Dans cette étude, une formulation colloïdale a été développée en milieu aqueux à partir de sels aisément manipulables et en présence d’un dérivé phospholipidique (2-aminoéthylphosphate, AEP) jouant le rôle d’agent dispersant et permettant de contrôler la taille moyenne des nanoparticules (dans la gamme 30-100 nm). L’effet de paramètres expérimentaux majeurs (pH, concentrations, température) a été déterminé. La complémentarité des données analytiques (analyses chimiques, spectroscopie FTIR, diffraction des rayons X, diffusion de la lumière, MET, mesures de potentiel zêta) nous a permis de proposer un modèle descriptif des nanoparticules colloïdales mettant en jeu la présence de complexes entre Ca2+ et AEP- en surface de nanocristaux d’apatite. La possibilité de conférer des propriétés de luminescence a été démontrée, par substitution d’ions Ca2+ par des ions europium Eu3+, et une durée de vie de luminescence de l’ordre de la milliseconde permet d’envisager l’étude de matériel biologique. Plus ponctuellement, l’adsorption additionnelle d’acide folique a été étudiée, avec pour objectif final le ciblage de cellules cancéreuses. Divers aspects liés à une potentielle utilisation dans le domaine biomédical ont également été abordés, tels que la purification de telles suspensions par dialyse, la possibilité d’une remise en suspension après lyophilisation, l’évaluation de leur cytotoxicité, l’étude de leur potentiel proinflammatoire par interaction avec des macrophages humains, et une étude préliminaire de l’internalisation de ces nanoparticules par des cellules cancéreuses. Ce travail a permis de développer une « preuve de concept » permettant d’envisager l’utilisation future de tels nano-systèmes colloïdaux dans le domaine biomédical, et en particulier en oncologie. / This work deals with the synthesis and physico-chemical characterization of hybrid nanoparticles based on biomimetic calcium phosphate apatites close to bone mineral, in view of applications in the field of cancer diagnosis, or therapeutics. In this study, a colloidal formulation has been developed in aqueous medium, from easily-handled salts and in the presence of a phospholipid moiety (2-aminoethylphosphate, AEP) acting as dispersing agent and allowing the control of the mean nanoparticle size (in the range 30-100 nm). The effect of major experimental parameters (pH, concentrations, temperature) has been determined. Complementary analytical data (chemical analyses, FTIR spectroscopy, XRD, dynamic light scattering, TEM, zeta potential measurements) enabled us to propose a descriptive model for the colloidal nanoparticles, involving the presence of complexes between Ca2+ and AEP- on the surface of apatite nanocrystals. The possibility to confer luminescence properties was demonstrated by way of ionic substitutions of some Ca2+ ions by europium Eu3+ ions, allowed us to envision the study of biological material. The additional adsorption of folic acid was also addressed, with the final aim to target cancer cell. Other aspects linked to a potential future use of these nano-systems in the biomedical field were also examined, such as the purification of these suspensions by dialysis, the possibility to resuspend the nanoparticles after freeze-drying, the evaluation of their cytotoxicity, the study of the pro-inflammatory potential by following interactions with human macrophages, and a preliminary study of their internalization by cancer cells. This work enabled us to develop a « proof of concept » allowing one to envision the future use of such colloidal nano-systems in the biomedical field, and in particular in oncology.

Bentonite clay is intended to form one of the barriers in most repositories of spent nuclear fuel located in granite. One important function of the bentonite barrier is to retard transport of radionuclides in the event of waste canister failure. Bentonite has a high sorption capacity of cations and its main constituent is montmorillonite. In contact with groundwater of low ionic strength, montmorillonite colloids can be released from bentonite and thereby control transport of radionuclides sorbed onto the colloids. In colloid transport in bedrock fractures, size separation of clay colloids may occur due to physical and chemical interactions with the bedrock fracture surface. This may enhance or retard the overall transport of radionuclides, depending on the sorption capacities and stability of the differently sized clay colloids. The bentonite barrier will be exposed to γ-radiation from the spent nuclear fuel. Irradiation affects surface-related properties of bentonite. If an average sorption capacity value cannot be used for all colloid sizes or if sorption is affected by exposure to γ-irradiation, corrected sorption capacity values would give higher resolution in current reactive transport models. In order to study the size separation process, a protocol was developed and successfully applied to fractionate montmorillonite into different-sized colloid suspensions by means of sequential or direct centrifugation. The stability and sorption capacity were studied using these fractions. Both stability and sorption capacity were found to be similar for all colloid sizes. Bentonite exposed to γ-radiation sorbed less divalent cations with increasing radiation dose. The effect was not large enough to have any impact on diffusion. The presence of bentonite enhanced irradiation-induced corrosion of copper under anaerobic atmosphere. An average sorption capacity value for montmorillonite can be used for all colloid sizes in reactive transport models. The effect of γ-irradiation on sorption capacity is sufficiently large to require consideration in transport modelling. / Bentonite är planerad som en av barriärerna i de flesta slutförvar av använt kärnbränsle. Bentonite har en hög sorptionskapacitet för katjoner. Den huvudsakliga beståndsdelen av bentonit är montmorillonit. Montmorillonitkolloider kommer att frigöras från bentonitbufferten i kontakt med grundvatten av låg jonstyrka och på så vis styra transporten av sorberade radionuklider. Under den kolloidala transporten i bergsprickorna kan en separation med avseende på storlek uppstå genom interaktioner mellan kolloiderna och bergytan. Detta kan få till följd att den genomsnittliga transporten av radionuklider bromsas eller tilltar beroende på sorptionskapaciteten och stabiliteten av de olika kolloidstorlekarna. Bentonitbarriären kommer även att utsättas för γ-bestrålning från det använda kärnbränslet, vilket påverkar dess ytrelaterade egenskaper. Om inte ett medeltal för sorptionskapaciteten är giltigt för alla kolloidstorlekar eller om sorptionen påverkas av γ-bestrålning, behövs nya sorptionskapaciteter bestämmas och impliceras för noggrannare transportmodeller. En metod för att separera montmorillonitkolloider med avseende på storlek via direkt och stegvis centrifugering har utvecklats. Stabiliteten och sorptionskapaciteten för dessa fraktioner har studerats. Både stabilitet och sorptionskapacitet visade sig vara lika för alla kolloidstorlekar. Bestrålad bentonit sorberar mindre andel divalenta katjoner med ökad dos bestrålning. Effekten är dock inte stor nog för att slå igenom i diffusionsexperimenten. Förekomst av bentonit ökar även den strålningsinducerade korrosionen av koppar under anaeroba förhållanden. Ett medelvärde för sorptionskapaciteten kan användas för alla kolloidstorlekar i transportmodeller. Effekten av γ-bestrålning är dock stor nog för att implementeras i modellerna. / <p>QC 20150213</p>

A hemostasia é um evento biológico passível de ser avaliado e estudado, assim como seus distúrbios. Há situações durante a anestesia que podem cursar com alterações hemostáticas culminando com aumento do sangramento ou até mesmo hemorragias graves. Os tempos de coagulação têm recebido especial atenção tendo-se em vista os diferentes contratempos hemostáticos que pode ocorrer durante o procedimento anestésico-cirúrgico. Sendo assim, nesse estudo buscou-se estabelecer os valores padrões para tempo de protrombina (TP) e de tromboplastina parcial ativada (TTPA) para cães submetidos a diferentes procedimentos cirúrgicos. Foram estudados 50 cães hígidos para padronização dos valores de TTPA e TP utilizando aparelho automático. Os valores de TTPA estavam dentro dos valores de normalidade da literatura (6,9 a 17,6 segundos) e valores de TP discretamente maiores (de 6,65 a 12,8 segundos). Foram estudadas 20 cadelas classificadas como ASA I e 18 cães ASA II e III. Nestes animais observaram-se aumentos significativos de valores de TTPA (de 12,04 para 14,29 segundos em ASA I, com P<0,0378; e de 13,4 para 15,11 segundos nos cães ASA II e III, P<0,0067) e de TP (de 8,36 para 9,7 segundos em ASA I, P<0,0323; e de 8,32 para 9,34 segundos nos caes ASA II e III, P< 0,0084) entre os momentos pré e pós-anestésicos Estes aumentos acompanham quedas da pressão coloidosmótica, indicando que o processo de anestesia, cirurgia e fluidoterapia causam hemodiluição, e conseqüente aumento nos tempo de coagulação. / Hemostasis is a biological event that could be evaluated and studied, just like yours disturbs. There are situations in to anesthetic procedures that could curse with hemostatics disturbs causing bleeding increase or even critical blood loss. The blood clotting times have been received special attention because different hemostatic setbacks that could occur during the anesthetic and surgical procedures. This way, this study look for establish the values for reference to protrombine time (PT) and to activated partial tromboplastin time (APTT) for dogs. Were studied 50 healthy dogs to standardize the values of PT and APTT utilizing an automatic instrument. The APTT values was in agreement with the literature values (6,9 to 17, 6 seconds), and the PT values was discret increased when compared with literature (from 6,65 to 12,8 seconds). Was studied 20 bitches classifieds as ASA I and 18 dogs classifieds as ASA II and III. In this animals observed significant increase values of APTT (from 12,04 to 14,29 seconds in the ASA I, P<0,0378; and from 13,4 to 15,11 seconds in the dogs ASA II and III, P<0,0067) and of PT (from 8,36 to 9,7 seconds in ASA I, P<0,0323; and from 8,32 to 9,34 seconds in the ASA II and III dogs) between the pre and post anesthetic moments. These increases attendance decease in the colloid osmotic pressure, indicating that the anesthetic, surgical and fluid therapy procedures can cause hemodilution, and consequent increase in the blood clotting times.

Colloid thrusters are under consideration for NASA missions such as the Laser Interferometer Space Antenna (LISA), which requires the continuous cancellation of external disturbances (approximately 25 microNewtons over a 3-10 year mission). Emissive probes are one diagnostic for the measurement of plasma potential, which can provide valuable information on the level of space-charge neutralization in a thruster plume. Understanding how to achieve effective space-charge neutralization of the positive-droplet thruster plume is important for efficient operation and to minimize the risk of contamination. In this Thesis we describe a laboratory electrospray (colloid) source and accompanying power processing electronics developed for testing of diagnostics in colloid thruster plumes. We present results of an initial series of emissive probe measurements using floating probe and swept bias probe techniques. These measurements were carried out using a single needle emitter operating on a mixture of EMI-IM (an ionic liquid) and tributyl phosphate. For a spray operating at a discharge voltage and current of 2.0kV and 200nA respectively, a potential of 5.0V was measured using the floating probe technique with the probe located at a distance of 2.7cm from the electrospray source. The interpretation of this floating potential as the plasma potential is discussed. In a separate set of tests, we used the swept bias emissive probe technique at the same distance and measured a plasma potential of 2.0V at a discharge voltage of 2.0kV. The discharge current in this latter test was somewhat unstable and varied from approximately 250 nA to over 1000nA. Numerical integration of the Poisson equation was performed to better understand space charge limitations of a probe emitting into a low density plasma. These results are presented and some implications for the measurements discussed. While the electrospray droplet number density was not measured, calculations to estimate this number density are also presented. Based on these estimates and our numerical calculations, the“knee" in the current voltage characteristic measured using the swept probe technique is estimated to be within 1.3 V of the actual plasma potential.

Wax anti-settling additives (WASA) are used to mitigate against the problems caused by the settling of n-alkane wax crystals, which crystallise from petroleum diesel. This can result in the blocking of fuel filters and hence vehicle failure. However, the mode of action for such additives is not currently known and two mechanisms have been proposed: they reduce the wax crystal size to such an extent that they settle very slowly; or they induce gelation in the wax suspension. This project aims to elucidate the mechanism of WASA within the diesel system. A room temperature crystallising model diesel (10 wt% n-alkanes in dodecane) has been developed. This model system has given a good response to the additives, with the wax crystals reduced in size, and is hence suitable for mechanistic studies. Differential scanning calorimetry and infra-red spectroscopy both suggest that the WASA is incorporated in or onto the wax crystal. DSC shows that small amounts of WASA suppress the wax crystallisation temperature and change the shape of the heat flow curve. FT-IR shows the WASA amide stretch present within filtered and dried wax crystals. Intriguingly, electrophoresis experiments show that the WASA imparts a positive charge to the wax crystals, suggesting an electrostatic role in the WASA action. Rheological experiments show the presence of a weak gel in the WASA doped model diesel. However, the gel strength is not altered by the presence of an organic salt and thus cannot be purely electrostatic in origin. Small angle neutron scattering has been conducted to help locate the WASA in the system. It has shown that in solution WASA shows a collapsed polymer coil structure with a single molecule occupying a 28 Å diameter sphere and multiple WASA molecules forming a 2400 Å diameter sphere. In the presence of the wax the WASA scatter does not significantly change suggesting that the WASA is on the surface of the wax crystal. By combining these results, a mechanism of WASA action is proposed as WASA cations interactions bridging between the wax crystals causing a weak bridging flocculation gel with electrostatic and steric effects contributing to stabilisation. The WASA charges are partially dissociated thus giving the electrophoretic effect and the long chains on the cations can contribute to stability via steric stabilisation.

Gold nanoparticles, are one of the most widely investigated nanoparticles (NP) and are normally synthesized by the reduction of metal salts in citrate solution. The reason for studying this nanostructured material from a technological standpoint is mainly the anticipated application in different areas based on optical properties explained with plasmon resonance. The main work of this study was to develop different sensing systems using gold nanoparticles. Three techniques have been utilized, being lateral flow immunoassay (LFIA), surface plasmon resonance (SPR), and surface-enhanced Raman scattering (SERS). A one-step semi-quantitative LFIA strip test was developed using colloidal gold coated by a partially-purified polyclonal antibody (pAb) raised in sheep as a signal generator, and bovine serum albumin-Estriol-16-glucuronide (BSA-E3-16G) conjugates as the capture agent spotted onto a nitrocellulose membrane as the test line. In this system, gold nanoparticles were applied for visualising the response. The application of the strip sensor to urinary samples from pregnant woman proved successful. A quantitative evaluation of low levels of E3-16G in liquid media was developed based on SPR, which used the same pAb-nanogold conjugates employed for the LFIA analysis. The assay can be carried out directly on any urine samples without sample pretreatment. In this system, gold nanoparticles were utilized as high mass label to improve the sensitivity of the assay. A SERS probe was developed which comprised of Raman reporter molecules (RRM) and gold NPs. Results showed that the conducting polymer materials of 3’-[(E)-2-(4-R-phenyl)ethenyl]-2’2’:5’,2”-terthiophene (R-pe3T, where R is NO2 or NH2) showed significant enhancement. Moreover, high bio-activity groups included in the compounds make them potential candidates for the development of a SERS based sensing system.

This dissertation investigates the influence of surface heterogeneities on colloid deposition. First, deposition of colloidal particles on a nanofiltration membrane during cross flow membrane filtration was studied under different operating pressures and solution chemistries. An atomic force microscope (AFM) was then used to observe the deposit morphology formed on the membrane. At the initial stages of fouling, more particles preferentially accumulate near the peaks than in the valleys of the rough nanofiltration membrane surface. This study demonstrates that it is difficult to isolate, correlate and assess the effects that physical (roughness) heterogeneity and chemical heterogeneity has on colloid deposition based on experiments involving surfaces where the physical and chemical heterogeneities are uncorrelated or randomly distributed. In the second phase of the study, the deposition of model colloidal particles onto patterned charge-heterogeneous surfaces was studied both experimentally and theoretically. Controlled charge heterogeneity was created experimentally employing self assembled monolayers of alkanethiols patterned onto gold substrates using a soft lithographic technique. Model colloidal particles and fluorescent nanoparticles were sequentially deposited onto the patterned substrate under no flow (quiescent) conditions, and the deposited structures and the micro-patterns were imaged in situ using a combination of phase contrast and fluorescence microscopy. This study indicates that particles tend to preferentially deposit at the edges of the chemically favourable stripes. The theoretical investigation involved the formulation of a mathematical model based on Random Sequential Adsorption (RSA). This study showed that a simple binary probability distribution assumed in the model is able to predict the experimental deposit morphology adequately, particularly the periodicity of the underlying patterns on the substrate. Furthermore, the effect of charge heterogeneity on the electrostatic double layer interaction between a particle and a charge heterogeneous planar surface was studied numerically employing a 3D finite element model. In this system, significant lateral forces at close separation distances were observed, and found to be appreciably higher when the particle is near the edge of a heterogeneous region of the substrate. From the above studies, it can be concluded that by altering/controlling the chemical heterogeneity of the substrate, it is possible to achieve significant control on the resulting deposit morphology.

Coating colors are applied to the base paper in order to maximize the performance of the end product. Coating colors are complex colloidal systems, mainly consisting of water, binders, and pigments. To understand the behavior of colloidal suspensions, an understanding of the interactions between its components is essential.