Dissertations / Theses on the topic 'W/o emulsion'

In this thesis, the impact of the interactions between the hydrophilic emulsifiers and aroma compounds as well as emulsion microstructure including droplet size, droplet size distribution, emulsion stability and creaming on aroma release over water-in-oil-in-water (w/o/w) emulsions was investigated. Polyglycerol polyricinoleate (PGPR) was used as the only hydrophobic emulsifier to stabilise the internal water droplets in the primary water-in-oil (w/o) emulsion of the w/o/w emulsions throughout this research. Three hydrophilic emulsifiers investigated to stabilise the w/o droplets in w/o/w emulsions included a low molecular weight non-ionic surfactant, polyoxyethylene 20 sorbitan monolaurate (Tween 20), a chemically modified starch, octenyl succinic anhydride (OSA) starch and a protein, pea protein isolate (PPI), as the large molecular weight emulsifiers. The two emulsification methods of high shear mixing and stirred cell membrane emulsification were used. Controls of water and oil-in-water (o/w) emulsions were prepared with the formulation and process conditions as for the w/o/w emulsions. Emulsion microstructure was characterised in terms of droplet appearance, droplet size, droplet size distribution as well as emulsion stability over time. Both static and dynamic headspace analyses were carried out to investigate the aroma release behaviour over w/o/w emulsions. The results showed that w/o/w emulsions were a suitable vehicle for short time aroma entrapment, which was most successful for the hydrophilic aroma acetoin compared to the hydrophobic aromas acetyl pyridine and hexanal. This entrapment of the hydrophilic aroma resulted from the barrier of the oil phase in the w/o droplets to delay its diffusion or the PGPR micelles in the oil phase to entrap it in the polar inner core. The complex food emulsifiers OSA starch and PPI were for the first time successfully used in stirred cell membrane emulsification to produce similarly sized o/w and w/o/w emulsions. These were produced to eliminate the effect of droplet size in the study of aroma release. The release of aromas (i.e. diacetyl and 3-pentanone) was affected by the combination of the type of the hydrophilic emulsifier (Tween 20, OSA starch and PPI) and the type of the emulsion system (i.e. o/w and w/o/w emulsions) as well as the emulsion microstructure including droplet size, emulsion stability, interface thickness, creaming and diffusion of the internal water phase into the external water phase of w/o/w emulsions. The thinner interface laden by Tween 20 might lead to a quicker diffusion of the hydrophobic aroma 3-pentanone from the w/o droplets into w2. OSA starch interacted with the hydrophilic aroma diacetyl and 3-pentanone, and PPI interacted with 3-pentanone. These findings help to better understand the effect of the hydrophilic emulsifier and emulsion microstructure on aroma release and present a novel study to produce similarly sized emulsion droplets with complex food emulsifiers.

Dwindling conventional oil resources has caused exploration efforts to focus elsewhere. Bitumen from oil sands has emerged as one of the primary unconventional oil resources in use today. Quadrise Canada Corporation has harnessed this unconventional oil by developing their bitumen-in-water emulsion known as MSAR (Multi-Phase Superfine Atomized Residue). Fuel-in-water emulsions are linked to a combustion phenomenon known as micro-explosion, which are associated with an increase in combustion efficiency and decrease in harmful emissions. A study has been conducted of the MSAR fuel to help advance the optimization and modeling of its use in spray combustors so as to best harness the potential. Quantitative and qualitative data has been obtained during combustion experiments of the fuel that will attribute to this end. Additionally, a simplified statistical model is presented based on the governing equations to describe the atomization that occur as a result of micro-explosions of the MSAR fuel as well as a simple model to represent internal force needed for a micro-explosion to occur. The results of this study continue to reinforce the understanding that micro-explosions cannot be attributed to one overriding physical principal, but rather are th result from variations in turbulent, dynamic, and thermal forces.

Cette étude s'inscrit dans le cadre du projet Européen VEGEPHY (VEGEtale-PHYtosanitaire) dont le but est de développer un produit support destiné à être pulvérisé pour protéger les plantes des viroses. Le produit étudié est une émulsion de type eau-dans-huile (E/H) à base d’une solution aqueuse de polysaccharide et d’esterméthylique de colza comme phase continue. Le polysaccharide est utilisé sous forme d'adjuvant afin de modifier les propriétés rhéologiques de la préparation phytosanitaire (bouillie) et ainsi de limiter la dérive des gouttelettes lors de la pulvérisation. Le but est également d’améliorer le contact des gouttes sur le végétal traité. L'objectif de ce travail est de formuler une émulsion (E/H) avec une concentration maximale de polysaccharide, qui soit stable sur le long terme (environ 2 ans) et d'étudier, lors de la mise en œuvre du produit, les mécanismes de relargage dans un laps de temps efficace devant rester inférieur à 600 s. Les émulsions (E/H) concentrées ont été réalisées à l'aide d'un système rotor stator à température ambiante. La phase aqueuse contenant le polysaccharide et du glycérol a été dispersée dans une phase huileuse agitée dans laquelle un surfactant (lécithine ou PolyRicinoléate de PolyGlycérol, PGPR) a préalablement été dissous. Des tests de stabilité ont été menés immédiatement après les phases de préparation ou par un vieillissement accéléré. Différents paramètres qui ont une influence sur cette stabilité ont été étudiés par DSC, observations microscopiques, diffraction laser et mesure des propriétés rhéologiques. Les analyses DSC ont été utilisées poursuivre l'évolution de la taille des gouttes en fonction du temps. En effet, le comportement thermique des émulsions pendant les phases de congélation et de fusion permet de calculer la fraction d’eau congelée dans les gouttelettes et sa mise en relation avec l’évolution de la stabilité des émulsions. Le relargage du polysaccharide (CarboxyMethylCellulose, CMC) est obtenu en deux étapes : déstabilisation de l'émulsion primaire E/H par un produit chimique puis dilution dans l'eau pour obtenir une émulsion (H/E) avec la concentration désirée de polysaccharide dans la phase aqueuse. La déstabilisation a été étudiée en observant l'évolution des gouttelettes par DSC. Le procédé de dilution a été étudié par une mesure de la conductivité de la solution aqueuse couplée à un modèle cinétique de relargage du CMC.La formulation et la stabilité de l'émulsion (E/H) ont montré que la DSC, complétée par d'autres techniques, est une méthode appropriée pour déterminer les caractéristiques des émulsions. L'étude du comportement lors de la congélation montre que la proportion de glace formée dans les gouttelettes durant les tests DSC est en bonne adéquation avec les mesures DSC et les calculs thermodynamiques. L'utilisation du PGPR comme tensioactif et l'ajout du glycérol dans la formulation permettent d'augmenter la stabilité de l'émulsion à long terme. La formulation optimum obtenue contient 3.5 % (m/m) de CMC, 10 % (m/m) de glycérol dans 75 % (v/v) de phase dispersée et 14 % (m/m) de PRPG dans la phase continue. Un modèle empirique peut être utilisé pour décrire la cinétique de relargage. Pour déstabiliser l'émulsion (E/H), la quantité optimum de tensioactif anionique Cynthiorex PMH1125 est de 10 % (m/m) dans première émulsion avec NRe ≥ 4200 et T ≥ 20°C. Dans les conditions réelles d’utilisation de la préparation au champ, le temps minimum de relargage est d'environ 200 secondes<br>This study is a part of the European project VEGEPHY (VEGEtale-PHYtosanitaire) to develop a product for the crop protection purposes. The product is a concentrated W/O emulsion trapping of a polysaccharide in the aqueous phase and rapeseed methyl ester oil as a continuous phase. Polysaccharide is used as a thickening adjuvant to modify the rheology properties of the water-based spray solution in order to reduce the drift of thespray. The objective of this study is to formulate concentrated W/O emulsions incorporation with the maximum amount of polysaccharide which show long stability (for over 2 years) and to study the release mechanism of polysaccharide in suitable conditions with a goal of an efficiency time less than 600 seconds.Concentrated W/O emulsions were realized by using a rotor stator system at room temperature. Aqueous phase containing polysaccharide and glycerol was dispersed into the stirred oil continuous phase where in a surfactant (lecithin and/or polyglycerol polyricinoleate, PGPR) has been previously dissolved. Stability tests were performed immediately after preparation and after ageing tests. Various parameters having an influence on thestability have been interpreted from DSC thermogram parallel with microscopic observation, laser diffraction granulometry and rheology measurement. DSC technique was used to study the emulsions by following the evolution of the droplet size versus time. Thermal behaviour of emulsions may be evaluated when they under gofreezing and melting in which the proportion of ice formed in the droplets may be calculated and their link with the evolution of the emulsion versus time. The release of the polysaccharide (CarboxyMethyl Cellulose, CMC)from the emulsion system is obtained by a two steps process : destabilization of the primary W/O emulsion by achemical product and dilution in water that gives an O/W emulsion containing the required concentration of polysaccharide. Destabilization was observed by following the evolution of dispersed droplets using DSC. Dilution process was assessed by measuring electrical conductivity of the water solution and a mathematical model to represent the kinetic release of CMC in water was proposed.The formulation and the stability of concentrated W/O emulsion has shown that DSC completed with granulometry and rheometry is an appropriate technique to study the emulsion characteristics. The study offreezing behaviour of emulsions show that the proportion of ice formed in the dispersed droplets during DSC test indicates good agreement between DSC measurements and thermodynamics calculation. The use of PGPRas surfactant and the introduction of glycerol in the formulation are beneficial to improve the long‐term stabilityof the emulsion. The optimum formulation of concentrated W/O emulsion was obtained containing : 3.5% w/wof CMC, 10% w/w of glycerol in 75% v/v of dispersed phase and 14% w/w of PGPR in the continuous phase. From the release study, an empirical model may be used to describe the released kinetic. The optimum amount of nonionic surfactant Cynthiorex PMH 1125 to break primary W/O emulsion was found at 10% w/w in the primary emulsion with NRe ≥ 4200 and T ≥ 20°C. Under practical field conditions, the minimum release time isthen around 200 seconds

Dissertation submitted in fulfilment of the requirements for the Masters Degree in Technology: Chemical Engineering in the Department of Chemical Engineering of Cape Peninsula University ofTechnology, 2005<br>The emulsion used for this study is a new thermodynamically unstable multi-component waterin- oil (w/o) explosive type with an internal phase ratio of approximately 94%, i.e. far beyond the close packing limit of spherical droplets of 74%. Economic considerations and the ongoing need for continuous drilling, loading and blasting in the mining industry, has made long-distance pipeline transportation of these emulsion explosive systems a viable economic option. Presently, rheological characterization of emulsion explosives is well documented (Bampfield & Cooper, 1988, Utracki, 1980). However, very little or none has been done for this system, pertaining to the use of rheometry for prediction of pumping characteristics of these systems in long-distance pipeline transport. This Master's dissertation is devoted to develop rheological methods of testing, characterization and correlation in order to develop a basis for predicting the pumping characteristics of highly concentrated w/o emulsion explosives from rheometry. The literature and theory pertinent to the pipeline flow of high internal phase ratio emulsion explosives are presented, as well as the fundamentals of both concentric cylinder rheometry and pipe viscometry. The most relevant is the work of Bampfield and Cooper (1988), Utracki (1980) and Pal (1990). Two experimental test facilities were used for data collection. Pipeline experiments were done using an experimental test facility at African Explosives Limited (AEL), and rheometry was conducted at the Rheology Laboratory of the Cape Peninsula University of Technology Flow Process Research Centre. The AEL experimental test facility consisted of a four-stage Orbit progressive cavity pump, two fluid reservoirs, (a mixing tank and a discharge reservoir), five 45m HOPE (high density polyethylene) pipes of internal diameters of 35.9 mm, 48.1 mm, 55.9 mm, 65.9 mm and 77.6 mm pipes. The test work was done over a wide range of laminar flow rates ranging from 3 kg.min-I to 53 kg.min-I . Rheometry was done using a PaarPhysica MCR300 rheometer, and only standard rotational tests (i.e. flow curve) at 30 °c in controlled rate mode were done. Rheological characterisation was done using three rheological models, i.e. the Herschel-Bulkley, the Power Law and the Simplified Cross models. The coefficients obtained from these models were then used to predict pumping characteristics. The performances of these models were then evaluated by comparing the pipeline flow prediction to the actual pipeline data obtained from pipeline test experiments. It was found that the flow behaviour depicted by this explosive emulsion system was strongly non-Newtonian, and was characterized by two distinct regions of deformation behaviour, a lower Newtonian region of deformation behaviour in the shear rate region lower than 0.001 S-I and a strong shear thinning region in the shear rate range greater than 0.001 S-l. For all the models used for this study, it was evident that rheometry predicts the pumping characteristics of this high internal phase ratio emulsion reasonably well, irrespective of the choice of the model used for the predictions. It was also seen that the major difference between these models was in the lower shear rate domain. However, the Simplified Cross model was preferred over the other two models, since its parameter (the zero shear viscosity denoted by 110) can in general be correlated to the structure of the emulsion systems (i.e. mean droplet size, bulk modulus, etc.). Thus, structural changes induced by shearing (either inside the pump or when flowing inside a pipe) can be detected from changes in the value of the 110. The above statement implies that Tlo can be used as a quality control measure. Different pumping speeds were found to cause different degrees of shear-induced structural changes which were manifested by two opposing processes. These two opposing processes were the simultaneous coalescence and flocculation of droplets encountered at low rates of shear, and the simultaneous refinement and deflocculation of droplets encountered at high rates of shear. These two droplet phenomena were associated with a decrease or an increase in viscous effects, leading to both lower and higher viscous stresses and pumping pressures during pump start-up respectively.

Kyoto University (京都大学)<br>0048<br>新制・課程博士<br>博士(農学)<br>甲第18313号<br>農博第2038号<br>新制||農||1020(附属図書館)<br>学位論文||H26||N4820(農学部図書室)<br>31171<br>京都大学大学院農学研究科食品生物科学専攻<br>(主査)教授 安達 修二, 教授 河田 照雄, 教授 保川 清<br>学位規則第4条第1項該当

Emulsijos yra patrauklios išvaizdos, universalūs produktai, jų naudojimas yra paprastas bei priimtinas, dėl to jos yra ypač dažnai sutinkamos dermatologijoje, gydant įvairias odos ligas. Stabilus puskietis emulsinis pagrindas iš natūralių medžiagų yra aktualus, nes turi dideles pritaikymo galimybes kosmetinių ir gydomųjų kremų gamyboje. Tyrimo objektas – puskietė emulsinė sistema vanduo aliejuje iš natūralių medžiagų su bičių vašku, kaip vaistinių medžiagų nešiklis dermatologiniams preparatams. Darbo tikslas – puskietės emulsinės sistemos vanduo aliejuje (v/a) su bičių vašku sumodeliavimas ir modelinės medžiagos – askorbo rūgšties atpalaidavimo iš sumodeliuotos sistemos įvertinimas biofarmaciniu in vitro tyrimu. Tyrimo uždaviniai: parinkti puskietės emulsinės sistemos sudėtį, remiantis ortogonaliu statistiniu planu, ir atrinkti stabilius pavyzdžius pagal pasirinktus vertinimo kriterijus (tinkamas pH, klampa, mikrostruktūra bei juslinės savybės); nustatyti puskiečių emulsinių sistemų fizikocheminius rodiklius (pH, klampą, mikrostruktūrą) bei įvertinti jų stabilumą po 1 ir 3 mėn.; įvertinti bičių vaško įtaką puskiečių emulsinių sistemų klampai, stabilumui, juslinėms savybėms bei askorbo rūgšties atpalaidavimui iš puskietės emulsinės sistemos; įvertinti modelinės medžiagos – askorbo rūgšties atpalaidavimą iš tiriamų puskiečių emulsinių sistemų, atliekant biofarmacinį tyrimą in vitro per pusiau pralaidžią membraną; atlikti emulsinės sistemos juslinių savybių ir kokybės... [toliau žr. visą tekstą]<br>Emulsion has an attractive conformation and is an universal product. It‘s usage is simple and acceptable. For this reason, it is often used in dermatology for curing different skin disease. Stable semisolid emulsion base from natural materials is relevant because it has a big variety of use in cosmetic and remedial cream production. The object of research – the system of semisolid emulsion water in oil from natural materials and beeswax as a carrier of medical materials in dermatological preparations. The aim of the work – modeling the system of semisolid emulsion water in oil with the beeswax and modeling materials as liberation ascorbic acid from simulated system and it‘s biopharmacy evaluation by in vitro research. The task of research: to choose the composition of semisolid emulsion system on the ground of orthogonal statistic plan and select stable samples according to evaluation criterion (the proper pH, viscosity, microstructure and organoleptic properties); to rate physicochemical rates of the system of semisolid emulsion (pH, viscosity, microstructure) and evaluate their stability after 1 and 3 months; to evaluate the influence of beeswax on the viscosity, stability, sensual properties and the liberation of ascorbic acid from the system of semisolid emulsion; to evaluate modeling materials – the liberation of ascorbic acid from investigative system of semisolid emulsion carrying out biopharmacy research in vitro through semi-permeable membrane; to evaluate sensual... [to full text]

This thesis describes work on the development of several novel stimuli-responsive porous hydrogels prepared from oil-in-water (o/w) high internal phase emulsion (HIPE) as injectable scaffolds for soft tissue engineering. Firstly, by copolymerising glycidyl methacrylate (GMA) derivatised dextran and N-isopropylacrylamide (NIPAAm) in the aqueous phase of a toluene-in-water HIPE, thermo-responsive polyHIPE hydrogels were obtained. The temperature depended modulus of these porous hydrogels, as revealed by oscillatory mechanical measurements, indicated improvements of the mechanical properties of these hydrogels when heated from room temperature to human body temperature, as the polyNIPAAm copolymer segments starts to phase separate from the aqueous phase and causes the hydrogel to form a more compact structure within the aqueous phase of the polyHIPE. Secondly ion responsive methacrylate modified alginate polyHIPE hydrogels were prepared. The physical dimensions, pore and pore throat sizes as well as water uptakes of these ion responsive hydrogels can be controllably decreased in the presence of Ca2+ ions and are fully recovered after disruption of the ionic crosslinking using a chelating agent (sodium citrate). These ion-responsive polyHIPE hydrogels also possess good mechanical properties (modulus up to 20 kPa). Both of these polyHIPE hydrogels could be easily extruded through a hypodermic needle while breaking into small fragments (about 0.5 to 3.0 mm in diameter), but the interconnected porous morphology was maintained after injection as revealed by SEM characterisation. Furthermore, the hydrogel fragments produced during injection can be crosslinked into a coherent scaffold under very mild condition using Ca2+ salts and alginate aqueous solution as the ionically crosslinkable adhesive. In order to increase the pore size of these covalently crosslinked polyHIPE hydrogels and also find a biocompatible nontoxic emulsifier as substitution to traditional surfactants, methyl myristate-in-water and soybean oil-in-water HIPEs solely stabilised by hydroxyapatite (HAp) nanoparticle were prepared. These Pickering- HIPEs were used as template to prepare polyHIPE hydrogels. Dextran-GMA, a water soluble monomer, was polymerised in the continuous phase of the HAp Pickering HIPEs leading to porous hydrogels with a tunable pore size varying from 1.5 μm to 41.0 μm. HAp is a nontoxic biocompatible emulsifier, which potentially provides extra functions, such as promoting hard tissue cell proliferation. HIPE-templated materials whose porous structure is maintained solely by the reversible physical aggregation between thermo-responsive dextran-b-polyNIPAAm block polymer chains in an aqueous environment (for this type of HIPE templated material we coined the name thermo-HIPEs) were prepared. No chemical reaction is required for the solidification of this porous material. This particular feature should provide a safer route to injectable scaffolds as issues of polymerisation/crosslinking chemistry or residual initiator fragments or monomers potentially being cytotoxic do not arise in our case, as all components are purified polymers prior to HIPE formation. Thermo-HIPEs with soybean oil or squalene as dispersed oil phase were prepared. Also in this HIPE system it was possible to replace the original surfactant Triton X405 with colloidal HAp nanoparticles or pH/thermo-responsive polyNIPAAm-co- AA microgel particles. The pore sizes and the mechanical properties of colloidal particles stabilised thermo-HIPEs showed improvement compared with thermo-HIPEs stabilised by Triton X405. In summary new injectable polyHIPEs have been prepared which retain their pore morphology during injection and can be solidified by either a thermal or ion (Ca2+) or chelating ion (Ca2+) stimulus. The materials used are intrinsically biocompatible and thus makes these porous injectable scaffolds excellent candidates for soft tissue engineering.

Oily wastewater produced from petroleum and petrochemical refining processes is one of the gravest environmental threats. Oil waste ending up in sewers and dumps each year is equal to 25 times the amount of crude oil spilled in the Exxon Valdez accident (1989). Oil/Water separation covers a broad spectrum of industrial process operations. There are many techniques employed depending on each situation. The byproduct of water recovery from oily wastewater is a sludge rich in oil, surfactants and particles (oily sludge). The oily sludge still contains significant amounts of waters, which need to be recovered prior to its disposal. The use of polyelectrolytes for the flocculation of the emulsified oil and its separation from the aqueous phase is usually one of the steps of the wastewater as well as oily sludge treatment process. The efficiency of polyelectrolytes as floculants is quite often evaluated via trial and error and the appropriate polymer is selected according to the case. Even in scientific investigations it is rather common to use industrial oily sludge samples. The industrial oily sludge is characterized and treated by polyelectrolytes. Nevertheless industrial oily sludge is quite complicated and variable to be approximated by a model. For the systematic study of polyelectrolytes efficiency a stable, realistic and well-defined oily sludge model is necessary. In the present work an oily sludge model was successfully developed and characterized. The model consists on water, oil (kerosene), surfactant (sodium dodecyl sulphate, SDS) and clay particles (Blauton). The emulsifying efficiency of the surfactant and the clay were studied independently. The interactions between the surfactant and the clay including adsorption of the former on the later and cation exchange reactions were investigated. The four components were finally combined to form a series of emulsions varying the relative amounts of the emulsifiers for the highest stability to be encountered. Having concluded on the composition of the oily sludge model the efficiency of various polyelectrolytes was evaluated. Commercial natural (chitosans), synthetic (PolyDADMACs) polyelectrolytes and oilbreaks as well as lab-scale semi-synthetic polymers (modified chitosans) were tested. The flocculation efficiency was determined based on the amount and quality of water that was recovered as well as on the floc stability, size and sedimentation speed. The recovered water was characterized according to the environmental protection agency (EPA). The analysis included measurements on: total organic carbon (TOC), chemical oxygen demand (COD), biochemical oxygen demand (BOD5), total suspended solids (TSS) and pH. Selection of the appropriate flocculant also depends on the type of flocs formed in combination to the treatment following the flocculation. When filtration or centrifugation is used as a post-flocculation process the appropriate polymers are those that form large and porous flocs, as the case of the modified chitosans AG95 and AG97. Clarification devices on the other hand require dense flocs as these produced by the use of PolyDADMACs, commercial chitosans, oilbreaks and modified chitosans GA35, GA41 and AG79. Regarding the water quality, some of the polymers used that have low values of COD, TOC and BOD5, may not need the secondary treatment (biological) prior to discharge, such as P187K (PolyDADMAC) and GA41 (modified chitosan). The others require a biological treatment for the regulation limits to be reached. The pH values of modified chitosans (except of AG97), lab-scale PolyDADMACs and an oilbreak (OCAA) are all in range of the regulation limits. The applicability of biopolymers as flocculants for oil sludge dewatering is a relatively new field of investigation. As a consequence of the growing demand for environmentally friendly technologies as well as renewable resources the interest on natural flocculants has increased. The aminopolysaccharide chitosan and its modified derivatives have outstanding properties such as biocompability, biodegradability, hydrophilicity, adsorption, flocculating ability and antibacterial properties. These natural polymers derived from the sea-food industry waste products would be very useful as residue oil adsorbents in any oily wastewater and can be among the most promising candidates as a replacement of the synthetic flocculants<br>Ölhaltiges Abwasser, das bei Erdöl- und petrolchemischen Raffinierungsprozessen entsteht, ist eine der größten Umweltgefahren. Dieses Altöl landet jedes Jahr in der Kanalisation und in Deponien. Es handelt sich dabei um die 25-fache Menge an Rohöl, die beim Unfall der Exxon Valdez (1989) ausgeflossen ist. Die Öl/Wasser-Trennung überspannt ein breites Spektrum industrieller Prozesse. Es gibt viele Techniken, die abhängig von jeder Situation eingesetzt werden. Das Nebenprodukt bei der Abtrennung von Wasser aus ölhaltigen Abwässern ist ein Schlamm (Ölschlamm), der reich an Öl, Tensiden und Partikeln ist. Der Ölschlamm enthält noch bedeutende Mengen an Wasser, die vor ihrer Entsorgung verwertet werden müssen. Die Verwendung von Polyelektrolyten zur Ausflockung des emulgierten Öls und seine Trennung von der wässrigen Phase ist in der Regel einer der Schritte zur Behandlung von Abwässern sowie ölhaltigen Schlämmen. Die Effizienz von Polyelektrolyten als Flockungsmittel wird ganz häufig über Versuch und Fehler bewertet, und das passende Polymer wird entsprechend dem jeweiligen Fall ausgewählt. Sogar in wissenschaftlichen Untersuchungen ist es eher üblich, industrielle Ölschlamm-Proben zu verwenden. Der industrielle Ölschlamm wird charakterisiert und mit Polyelektrolyten behandelt. Dennoch ist der industrielle Ölschlamm ziemlich kompliziert und variabel und muss durch ein Modell angenähert werden. Für die systematische Untersuchung der Effizienz von Polyelektrolyten als Flockungsmittel ist ein stabiles, realistisches und klar definiertes Ölschlamm-Modell notwendig. In der vorliegenden Arbeit wurde ein Ölschlamm-Modell erfolgreich entwickelt und charakterisiert. Das Modell besteht aus Wasser, Öl (Kerosin), Tensid (Natriumdodecylsulfat, SDS) und Tonteilchen (Blauton). Die Emulgiereffizienz des Tensids und des Tons wurden unabhängig voneinander untersucht. Die Wechselwirkungen zwischen dem Tensid und dem Ton, die sowohl die Adsorption des Ersteren auf dem Letzteren einschließen als auch einen Kationenaustausch, wurden untersucht. Die vier Komponenten des Ölschlamm-Modells wurden schließlich kombiniert und es wurde eine Reihe von Emulsionen hergestellt, bei denen die relativen Mengen der Emulsionsmittel verändert wurden, um eine möglichst hohe Stabilität zu erreichen. Nachdem ein geeignetes Ölschlamm-Modell zur Verfügung stand, wurde die Effizienz der verschiedenen Polyelektrolyte als Flockungsmittel bewertet. Kommerzielle natürliche (Chitosane), synthetische (PolyDADMACs) Polyelektrolyte und Oilbreaks sowie Labor-semi-synthetische Polymere (modifizierte Chitosane) wurden getestet. Die Flockungseffizienz wurde sowohl basierend auf der Menge und Qualität des Wassers, das zurückgewonnen wurde, als auch bezogen auf die Flockenstabilität, die Flockengröße und die Sedimentationsgeschwindigkeit bestimmt. Das zurückgewonnene Wasser wurde entsprechend der Vorschriften der Behörde für Umweltschutz (EPA) charakterisiert. Die Analysen enthielten die Bestimmung des gesamten organischen Kohlenstoffs (TOC), des chemischen Sauerstoffbedarf (CSB), des biochemischen Sauerstoffbedarfs (BSB5), des Gesamtgehalts an suspendierten Partikeln (TSS) und die Bestimmung des pH. Die Auswahl geeigneter Flockungsmittel hängt auch von der Art der gebildeten Flocken, in Kombination mit der Behandlung, die den Flockungsprozess folgt, ab. Wenn als Postflockungsprozess Filtration oder Zentrifugation folgen, sollten Polymere verwendet werden, die große und poröse Flöckchen bilden, wie im Fall der modifizierten Chitosane AG95 und AG97. Andererseits verlangen Geräte zur Klärung von Abwässern dichte Flocken, wie solche, die beim Einsatz von PolyDADMACs, kommerziellen Chitosanen, Oilbreaks und den modifizierten Chitosanen GA35, GA41 und AG79 entstehen. In Bezug auf die Wasserqualität erhält man mit einigen der verwendeten Polymere so niedrige Werte von CSB, TOC und BSB5, dass wie im Falle von P187K (PolyDADMAC) und GA41 (modifiziertes Chitosan) keine biologische Sekundärbehandlung notwendig ist. Im Falle der anderen Polymere ist eine biologische Behandlung nötig, um die vorgeschriebenen Grenzen zu erreichen. Die pH-Werte der modifizierten Chitosane (außer der AG97), der im Labor hergestellten PolyDADMACs und des Oilbreak OCAA sind alle in Bereich der vorgeschriebenen Grenzen. Die Anwendbarkeit von Biopolymeren als Flockungsmittel für die Ölschlammentwässerung ist ein relativ neuer Forschungsbereich. Als Folge der wachsenden Nachfrage nach umweltfreundlichen Technologien sowie erneuerbarer Ressourcen hat das Interesse an natürlichen Flockungsmitteln zugenommen. Das Aminopolysaccharidchitosan und dessen modifizierte Produkte haben hervorragende Eigenschaften wie Biokompatibilität, Biodegradierbarkeit, Hydrophilie, Adsorption, die Fähigkeit zur Flockung und antibakterielle Eigenschaften. Diese natürlichen Polymere, die aus Meeresfrüchte-Industrieabfallprodukten gewonnen werden, sollten als Restöl-Adsorbentien bei der Aufarbeitung jedes ölhaltigen Abwassers sehr nützlich sein und können zu den vielversprechendsten Kandidaten als Ersatz der synthetischen Flockungsmittel werden

Magister Pharmaceuticae - MPharm<br>Background: Tenofovir disoproxil fumarate (TDF) and Zidovudine (AZT) are both nucleotide and nucleoside analogue reverse transcriptase inhibitors (NtRTIs and NRTIs), respectively. They are used for the management and prevention of the Human Immunodeficiency Virus (HIV) infection. These drugs are faced with oral delivery challenges such as low intestinal permeability and extensive first pass liver metabolism for TDF and AZT, respectively. Their use may also be limited by dose-dependent adverse effects, which may result in treatment failure when patients become non-compliant and non-adherent to their prescribed antiretroviral (ARV) regimen. Non-compliance and non-adherence to ARV regimen may lead to drug resistance and a need for change in regimen, which can be very expensive, not only financially but in terms of morbidity and mortality. To solve such issues, a new drug can be formulated, or an existing drug can be modified. The development and formulation of a new drug is time consuming and expensive, especially with no available data and a high probability of failure. Modifying existing drugs is a cheaper, less time-consuming option with lower probability of failure. Such modification can be achieved via non-covalent interactions using various methods such as preparation of nano-particulates with polymeric micelles (a non-covalent interaction). Polymeric micelles offer a variety of polymers to choose from for drug modification purposes. Purpose: The aim of this study was to formulate polymeric nanoparticles of TDF and AZT using different ratios of poly-lactic-co-glycolic acid (PLGA), characterize the formulated nanoparticles (using the following analyses: particle size, zeta potential, encapsulation efficiency, hot stage microscopy, thermogravimetric analysis, differential scanning calorimetry, Fourier transform infrared spectroscopy and scanning electron microscopy), analyze for stability during storage (2-8˚C) and determine the release rate of the active pharmaceutical ingredients in the formulated nanoparticles. Methods: Nanoparticles were prepared using a modified version of the double emulsion (water-in-oil-in-water) solvent evaporation and diffusion method. Two ratios of PLGA (50:50 and 85:15) were used to prepare four formulations (two each of TDF and AZT). Thereafter, the physicochemical and pharmaceutical properties of the formulations were assessed by characterizing the nanoparticles for particle size, zeta potential, polydispersity index, percentage yield, release profile and particle morphology, using the suggested analytical techniques. Results: For TDF-PLGA 85:15, TDF-PLGA 50:50, AZT-PLGA 85:15 and AZT-PLGA 50:50, nanoparticles of 160.4±1.7 nm,154.3±3.1 nm,127.0±2.32 nm and 153.2±4.3 nm, respectively, were recovered after washing. The polydispersity index (PDI) values were ≤0.418±0.004 after washing, indicating that the formulations were monodispersed. The zeta potential of the particles was -5.72±1 mV, -19.1 mV, -12.2±0.6 mV and -15.3±0.5 mV for TDF-PLGA 85:15, TDF-PLGA 50:50, AZT-PLGA 85:15 and AZT-PLGA 50:50 respectively after washing. The highest percentage yield was calculated to be 79.14% and the highest encapsulation efficiency obtained was 73.82% for AZT-PLGA 50:50, while the particle morphology showed spherical nanoparticles with signs of coalescence and aggregation for all formulated nanoparticles. The release profiles were biphasic; that is, an initial burst which indicated the presence of surface API followed by sustained release. Comparing the release profiles of AZT and TDF at pH 1.2 and 7.4, it was indicative that more AZT was released at pH 1.2 while more TDF was released at pH 7.4. On computing the release data further into various mathematical models, the Weibull model was found to be the best fit. The loaded nanoparticles showed an increase in stability after washing; however, they showed signs of gradual decrease in stability after 10 days of storage at 2-8°C. Conclusions: Relatively small, spherical and smooth nanoparticles were formulated. The nanoparticle release profile was indicative of sustained release; however, there was no conclusive indication that 48 hours duration was sufficient to release all encapsulated drug. Further studies with an increased API or polymer ratio in the formulation needs to be performed to determine if the encapsulation efficiency can be improved and in-vivo studies are required for a better understanding of the API release from formulations as well as its absorption in the body.

A bovinocultura brasileira possui grande ênfase no mercado nacional. Doenças que acometem rebanhos comprometem o mercado além de gerarem grandes prejuízos econômicos. O Clostridium novyi tipo B provoca necrose hepática em bovinos através da produção da alfa toxina, uma potente exotoxina que reduz a produtividade através de alterações como hemoglobinúria, redução do apetite, febre, letargia, diminuição da produção de leite e sangue nas fezes. Conter o microrganismo causador torna-se uma busca necessária tanto do ponto de vista econômico quanto social. Entretanto, o controle da doença ainda é realizado por vacinas formuladas com múltiplos antígenos. A emulsão pode ser uma alternativa promissora para a melhoria da adsorção de antígenos nas formulações vacinais. Camundongos da linhagem Swiss foram utilizados a fim de se avaliar aspectos clínicos e validar resultados referentes a composição de uma nova formulação vacinal contendo adjuvante Montanide ISA 61 VG e antígeno inativado de C. novyi. Os testes de caracterização e antigenicidade indicaram a presença da proteína alfa toxina na composição avaliada. A imunogenicidade do antígeno inativado em emulsão W/O (água/óleo) foi verificada e a proporção empregada (40/60) mostrou ser ideal no uso de múltiplos antígenos, apresentando inocuidade, estabilidade do produto, liberação controlada e estímulo da resposta imune. A determinação da concentração de antígeno foi averiguada pela relação antígeno ativo e inativado com soros de animais doentes, visto a eficácia vacinal de 40%. A adequação da concentração de alfa toxina inativada na emulsão mostrou ser necessária para atingir melhores valores de proteção animal. Análises de hemograma, bioquímicas e morfologia de fígado, baço e coxa contribuíram para elucidar os efeitos da emulsão e comprovar necrose hepática nos grupos não imunizados, além de sugerir avanços na adsorção de vacinas. Os resultados possibilitaram o estabelecimento de um modelo murino de infecção de C. novyi com futuras aplicações relacionadas à produção vacinal com múltiplos antígenos emulsificados para controle das clostridioses.<br>Brazilian cattle breeding has great emphasis on the national market. Diseases that affect herds compromise the market as well as generate great economic losses. Clostridium novyi type B causes hepatic necrosis in cattle through the production of alpha toxin, a potent exotoxin that reduces productivity through changes such as hemoglobinuria, reduced appetite, fever, lethargy, decreased milk and stool production. Containing the causative micro-organism becomes a necessary quest both economically and socially. However, control of the disease is still performed by vaccines formulated with multiple antigens. The emulsion may be a promising alternative for the improvement of antigen adsorption in vaccine formulations. Swiss strain mice were used to evaluate clinical aspects and validate results regarding the composition of a new vaccine formulation containing Montanide ISA 61 VG adjuvant and C. novyi inactivated antigen. Characterization and antigenicity tests indicated the presence of the alpha toxin protein in the evaluated composition. The immunogenicity of antigen inactivated in W / O emulsion (water / oil) was verified and the ratio employed (40/60) showed to be ideal in the use of multiple antigens, presenting innocuousness, product stability, controlled release and stimulation of the immune response. The determination of the antigen concentration was investigated by the active antigen ratio and inactivated with sera from sick animals, since the vaccine efficacy was 40%. The suitability of the inactivated alpha toxin concentration in the emulsion was shown to be necessary to achieve better animal protection values. Hemogram, biochemical and liver, spleen and thigh morphology contributed to elucidate the effects of the emulsion and to verify hepatic necrosis in the nonimmunized groups, in addition to suggesting advances in the adsorption of vaccines. The results allowed the establishment of a murine model of C. novyi infection with future applications related to the vaccine production with multiple emulsified antigens to control clostridia.

Emulsions containing three different types of milk fat fractions (MF13, MF27 and MF42) and anhydrous milk fat (AMF) were prepared at oil to water (O/W) ratios of 1:9, 3:7, 5:5 and 7:3 using rhamnolipids as emulsifiers. The prepared emulsions were analyzed for their storage stability and properties (colour, particle size, zeta potential and rheology). The effects of various factors (freezing/thawing, heating, pH, salts and ionic strength) on the stability of emulsions were also investigated. All emulsions prepared with an O/W ratio of 7:3, regardless of the type of milk fat, rendered a highly condensed, semi solid and cream-like substance whereas other emulsions containing less oil were in a liquid form. Among the four different O/W ratios tested, the highest emulsion stability during the storage of 12 weeks was observed from the emulsions containing 1:9 O/W ratios, due to a combine effect of smaller emulsion particle size and lower collision frequency between droplets. Interestingly, the emulsions with 7:3 O/W ratios were found to be more stable than the ones with 5:5 O/W ratios. This might be due to the limited movements of closely-packed emulsion droplets induced by the high oil concentration of 7:3 O/W ratios. The emulsion stability was significantly affected by low pH, especially at lower than pH 4, due to the loss of electrostatic repulsions between droplets leading to droplet coalescence and also possibly due to hydrolysis of rhamnolipid molecules. The presence of salts (NaCl, KCl and CaCl2) also rendered the emulsion unstable. The degree of instability was gradually increased with increasing salt concentrations. CaCl2 had the most significant effect even at a very low concentration. The viscosity of emulsions increased with increasing oil concentration but was not affected by the types of milk fats. Emulsions with 3:7, 5:5 and 7:3 O/W ratios exhibited non-Newtonian and shear thinning flow behaviour. At 7:3 O/W ratios, MF13 exhibited gel-like properties whereas both MF42 and AMF emulsions became more solid-like at higher frequency.

PONTIFÍCIA UNIVERSIDADE CATÓLICA DO RIO DE JANEIRO<br>COORDENAÇÃO DE APERFEIÇOAMENTO DO PESSOAL DE ENSINO SUPERIOR<br>PROGRAMA DE EXCELENCIA ACADEMICA<br>A eficiência do processo de injeção de água, o método de recuperação secundária mais comum na indústria do petróleo, é limitada por seu padrão de varredura não uniforme, originado da formação de caminhos preferenciais devido à alta razão de mobilidade entre água e óleo, e a elevada saturação de óleo residual, associada aos efeitos capilares. A fim de melhorar a recuperação de petróleo, diferentes abordagens têm sido sugeridas na literatura, com algumas delas baseadas no bloqueio de poros e consequente desvio de água, varrendo assim uma área maior do reservatório e deslocando mais do óleo aprisionado por capilaridade. O bloqueio de poros pode ser realizado com diferentes métodos, sendo um deles a injeção de emulsão, com a fase dispersa, composta por gotas de óleo, atuando como o agente responsável pela diminuição da mobilidade da fase aquosa. Neste trabalho, os mecanismos fundamentais do processo de injeção de emulsão foram estudados experimentalmente, visualizando-se o escoamento em escala de poros em um dispositivo micro-fluídico de vidro composto por uma rede de canais constritos, que modela as principais características de um meio poroso. Os resultados mostram o efeito do tamanho da gota e do número de capilaridade no padrão do escoamento, no tamanho dos gânglios do óleo aprisionado e na recuperação de óleo residual.<br>The efficiency of water flooding, the most common secondary recovery method in the oil industry, is limited by its non-uniform sweep pattern, originating from the formation of preferential paths because of the high mobility ratio between water and oil, and the high residual oil saturation, associated with capillary oil trapping. In order to improve oil recovery, different approaches have been suggested in the literature, with some of them based on pore blocking and consequent water diversion, thus sweeping a bigger area of the reservoir and displacing more of the trapped oil. Pore blockage can be performed with different methods, one of which is emulsion flooding, with the disperse phase, composed by oil drops, acting as the agent responsible for the decreased water phase mobility. In this work, the fundamental mechanisms of emulsion flooding process was studied experimentally, by visualizing the pore-scale flow in a glass microfluidic device composed of a network of constricted channels, that models the main features of a porous media. The results show the effect of drop size and capillary number on the flow pattern, trapped oil ganglia size and residual oil recovery.

Las emulsiones son dispersiones de dos líquidos inmiscibles que, generalmente están estabilizadas por moléculas tensioactivas. Cuando la fracción en volumen de fase dispersa es superior o igual a 0,74 (valor que corresponde al máximo empaquetamiento de gotas esféricas indeformables y monodispersas) se denominan altamente concentradas. Dichas emulsiones tienen una elevada relación superficie/volumen, además de regiones hidrófilas y lipófilas bien definidas que permiten la incorporación de moléculas de diferente naturaleza. Por todo ello, tienen aplicaciones en el campo farmacéutico, cosmético, alimentario, en síntesis de materiales, etc. En la mayoría de aplicaciones, los procesos de difusión desempeñan un papel importante y por este motivo, se han estudiado los mecanismos de difusión para determinar la influencia de las propiedades de las emulsiones en dichos mecanismos. Sin embargo, no se ha estudiado de forma simultánea la influencia que los factores de composición y formación podrían ejercer sobre los procesos de liberación. Por este motivo, el objetivo principal de esta tesis, ha sido el de modelizar la formulación de emulsiones altamente concentradas de tipo W/O estudiando la relación entre el tamaño de gota, sus propiedades reológicas y la liberación de moléculas activas, incorporadas en la fase dispersa, a soluciones receptoras. Para alcanzar dicho objetivo, se seleccionaron componentes biocompatibles y biodegradables para formar emulsiones altamente concentradas de tipo W/O. De este modo, se seleccionaron tensioactivos derivados de ésteres como el poligliceril-2 diisoestearato (IS-202P), el monoleato de sorbitán (Span80) y un polioxietileno de sorbitano (Tween80), de alcoholes etoxilados (Brij52), del aceite de ricino (CremophorWO7), y dos tensioactivos poliméricos de bloque o copolímeros (SynperonicL2 y PluronicL121). Como componentes oleosos, se seleccionaron hidrocarburos alifáticos (aceite de parafina y escualano), un éster derivado del ácido oleico (decil oleato) y un triglicérido derivado de los ácidos grasos caprílico/cáprico (triglicéridos de cadena media). Se realizaron estudios de formación de emulsiones altamente concentradas, caracterizando las emulsiones formadas, que permitieron seleccionar un sistema modelo (solución acuosa/Span80/aceite de parafina), además del método de adición del componente acuoso a la mezcla del componente oleoso y tensioactivo, como el más apropiado para formar las emulsiones. Asimismo, se seleccionaron tres moléculas activas modelo el metilparabeno, etilparabeno y propilparabeno, ya que se podían incorporar en la fase dispersa de emulsiones altamente concentradas seleccionadas, sin modificar las propiedades de dichas emulsiones. Una vez seleccionados el sistema y las moléculas activas modelo, se aplicaron dos diseños de experimentos. El primero, un diseño central compuesto, permitió relacionar el tamaño de gota y las propiedades reológicas con variables de composición y formación de las emulsiones en ausencia de parabenos. El segundo, un diseño factorial fraccionado permitió la obtención de un modelo empírico para modelizar la formulación de emulsiones altamente concentradas, optimizando su tamaño de gota, sus propiedades reológicas, así como la liberación de las moléculas activas incorporadas. Se realizó un estudio comparativo de la formulación optimizada variando el aceite y el componente tensioactivo, determinando que influía más la estructura del tensioactivo que la polaridad del componente oleoso. También se realizó un estudio preliminar de escalado de la formulación óptima poniendo de manifiesto que, a pesar de la complejidad de los procesos de difusión que tienen lugar en las emulsiones altamente concentradas, en el escalado se obtuvieron resultados de liberación razonablemente similares. Mediante la utilización de diseños de experimentos y seleccionado un sistema modelo de tipo componente acuoso/tensioactivo no iónico/componente oleoso, se ha optimizado la formulación de emulsiones altamente concentradas de tipo W/O, obteniendo un modelo empírico que ha permitido optimizar el tamaño de gota, propiedades reológicas y modular el perfil de liberación de moléculas activas incorporadas en el componente acuoso de dichas emulsiones.<br>Emulsions are dispersions of two immiscible liquids, generally stabilized with surfactants. When the volume fraction of the disperse phase exceeds 0.74 (the maximum packing of spherical, undistorted and monodisperse droplets), emulsions are classified as highly concentrated emulsions. In most applications of highly concentrated emulsions, diffusion processes have an important role, and as a consequence, diffusion of active molecules incorporated in the disperse phase of emulsions has been studied to find out their relationship with emulsion properties. However, there is still a lack of knowledge on the relationship among composition and formation factors with diffusion processes. The main objective of this thesis has been to model the formulation of highly concentrated W/O emulsions, studying the relationship between droplet size, rheological properties and the release of active molecules, incorporated in the dispersed phase, to receptor solutions. To achieve this objective, the selected surfactants were: sorbitane monooleate (Span80) and polyglyceryl-2 diisostearate (IS-202P). The oil components were aliphatic hydrocarbons (paraffin oil and squalene). Methylparaben, ethylparaben and propylparaben were chosen as model active molecules. Their incorporation in the aqueous phase of emulsions did not modify emulsion properties. An experimental design was performed to optimize the formulation of emulsions in the model aqueous solution/Span80/paraffin oil system. The optimized formulation was compared with other systems by varying oil and surfactant components, concluding that the influence of surfactant structure was more important than the oil polarity. Furthermore, a preliminary scale up study was carried out with the optimized formulation and the results for the two scales considered were reasonably similar. Using design of experiments and selecting a model aqueous/nonionic surfactant/oil system, an empirical model has been obtained that has allowed to optimize emulsion droplet size, their rheological properties and the release of active molecules incorporated in the aqueous phase of these highly concentrated W/O emulsions.

Memoria para optar al Título de Químico<br>Autorizada por el autor, pero con restricción para ser publicada a texto completo hasta diciembre de 2014, en el Portal de Tesis Electrónicas<br>Las emulsiones son un tipo de sistemas de fases dispersas, se encuentran en forma abundante en nuestro alrededor y comúnmente son utilizados para el confort del hombre en la vida diaria, en la industria de los alimentos, en la industria farmacéutica, en la industria cosmética y en la industria química. Según el tipo de dispersión las emulsiones se clasifican como aquellas del tipo agua en aceite (w/o) o aceite en agua (o/w). Es posible obtener dispersiones más complejas con fines más específicos, tales como las emulsiones múltiples del tipo w/o/w u o/w/o, que requieren, en primer lugar, de la formación de una emulsión primaria estable y luego su dispersión en la fase externa. Estas emulsiones dobles generan una membrana líquida activa, capaz de transferir ciertos elementos entre dos fases extremas, miscibles entre sí pero separadas por la fase intermedia inmiscible. Al dispersar dos fases líquidas inmiscibles, que poseen una elevada fuerza de atracción entre sus propias moléculas, se genera una gran área de interfase produciendo un sistema termodinámicamente inestable, lo que conlleva la ruptura de la emulsión en un determinado tiempo. El grado de inestabilidad del sistema depende de la magnitud de la energía libre interfacial por unidad de área, o la mínima cantidad de trabajo requerido para crear una unidad de área de interfase, denominada tensión interfacial. Para estabilizar los sistemas dispersos o emulsiones se debe agregar un agente que posea actividad interfacial, que permita disminuir la tensión interfacial y las interacciones atractivas entre las gotitas que se encuentran dispersas. Estos agentes que son denominados tensoactivos o surfactantes son especies químicas anfipáticas, que por diversos mecanismos impiden el colapso de las gotitas, evitando su coalescencia o floculación. Se ha propuesto como metodología alternativa económica y efectiva la utilización de doble emulsiones para la extracción y separación de especies químicas que presenten interés. En una emulsión del tipo w/o/w dos fases acuosas están separadas por la fase orgánica inmiscible (fase membrana). Si se agrega un extractante de metales a la fase membrana es posible transferir iones metálicos entre ambas fases acuosas y utilizar el sistema de doble emulsión para la transferencia controlada de especies metálicas. La aplicación de la metodología de doble emulsiones para la separación de iones metálicos requiere de la obtención de un sistema estable, donde no se produzca ruptura o hinchamiento de la emulsión primaria. Es decir, se requiere que el volumen de la emulsión primaria al inicio y al final permanezca invariable, en términos prácticos. En esta memoria de título, se estudió el comportamiento de estabilidad de las emulsiones dobles del tipo w/o/w utilizando el tensoactivo SPAN 80 como agente estabilizador, con la finalidad de aplicarlas como método para separar y concentrar iones metálicos lantánidos, específicamente los iones trivalentes de La, Ce, Pr y Nd. En este estudio se evaluó la influencia de las siguientes variables en la estabilidad de la emulsión doble: las concentraciones de diferentes especies complejantes en la fase acuosa de alimentación, del Cyanex 272 y de los co-extractantes TOPO y TBP en la fase membrana y de ácido clorhídrico en la fase acuosa interna. En todos los casos se trató de determinar la concentración precisa de SPAN 80 capaz de generar una emulsión estable. Debido a que todos los experimentos realizados en esta memoria de título fueron realizados en las mismas condiciones hidrodinámicas de velocidad y tiempo de agitación, manteniendo constante la temperatura, fue posible suponer que siempre se debió obtener el mismo tamaño de glóbulo y una misma área interfacial. Por lo tanto, se pudo considerar un modelo que representa la estabilidad del sistema en términos de la energía libre de Gibbs, considerando dos etapas: la formación de la emulsión propiamente tal y la reacción química interfacial. Teniendo en cuenta estos efectos, referidos a que no es deseable una ruptura parcial o total o un hinchamiento de la emulsión primaria, debe considerarse la adición de una cantidad muy precisa del agente tensoactivo estabilizador, dado que se requiere un mínimo basal para la estabilidad propia del sistema emulsionado y un adicional para compensar el efecto de la reacción química interfacial. Como resultado de este estudio, se lograron obtener las correlaciones matemáticas que permiten determinar la cantidad necesaria de agente tensoactivo SPAN 80 que debe ser adicionada, en función de las concentraciones utilizadas de las otras especies químicas intervinientes en el proceso de extracción y transferencia de los iones lantánidos<br>The emulsions are a kind of dispersed phase systems that can be found in abundant way in people's daily life and are commonly employed in the food, pharmaceutical, cosmetic and chemical industries. According to the kind of dispersion, they are classified as water in oil (w/o) or oil in water (o/w) emulsions. It is possible to obtain more complex dispersions with more specific purposes, such as water in oil in water (w/o/w) or oil in water in oil (o/w/o) multiple emulsions that require in first place, the formation of an stable basic emulsion and then, its dispersion in the external phase. These double emulsions generate an active liquid membrane capable of transferring some elements between two miscible phases separated by one inmiscible phase. At dispersing two inmiscible liquid phases that have high attraction forces between their own molecules, a great interfacial area is created which produces an instable thermodynamic system, causing the breakdown of the emulsion in a determinate time. The grade of instability of the system depend on the value of interfacial free energy per area unit, or on the minimum work amount required to create an interfacial area unit, known as interfacial tension. To stabilize the dispersion systems or emulsions is necessary to add an agent with interfacial activity, that allows to reduce the interfacial tension and the attractive interactions between the disperse droplets. These agents, known as tensoactives or surfactants, are amphipatic chemical species that prevent, by different mechanisms, the flocculation or coalescence of the droplets. The use of double emulsions has been purposed as an economic and effective alternative methodology to the extraction and separation of chemical species of interest. In the case of water in oil in water double emulsion, two aqueous phases are separated by an inmiscible organic phase, known as membrane phase. If a metal organic extractant is added to the membrane phase, it is possible to transfer metal ions between both aqueous phases and, moreover to use the double emulsion for the controlled metallic species transfer. The application of double emulsion methodology to the separation of metallic ions requires the obtainment of a stable system where break or swelling of primary emulsion does not happen. In other words, it is required that the volume of emulsion practically be invariable to throughout and the term of the extraction process. In this title thesis, it was studied the stability of double emulsions (w/o/w) using the surfactant compound SPAN 80 as a stabilizer agent, with the purpose of apply the emulsion system as a method to separate and concentrate lanthanide ions, specifically the trivalent ions La, Ce, Pr and Nd. In this study was evaluated the influence of the following variables in the stability of double emulsions: the concentration of different complexant agents in the feed aqueous phase, of the Cyanex 272 and the co-extractan TOPO and TBP in the membrane phase and the hydrochloric acid in the internal aqueous phase. In every cases, it was tried of determine the precise concentration of SPAN 80 capable of generate a stable emulsion. On account of that all the experiments of this degree thesis, it were realized in the same hydrodynamics conditions of velocity and stirring time, keeping constant temperature, it was possible to suppose that always the same globule size may be attained as well as the same interfacial area. Therefore, it can be considered a model that represents the system stability in terms of the Gibbs free energy, considering two stages: the emulsion's formation and the interfacial chemical reaction. Considering these effects, assuming that is not desire a partial or total break or swelling of the primary emulsion, it should be consider add a very precise amount of the stabilizer surfactant agent, because it is required a basal minimum to the own-stability of the emulsified system and an additional quantity to compensate the effect of the interfacial chemical reaction. As result of this study, it was reached to obtain the mathematic correlations that permit to determine the necessary amount of the surfactant agent SPAN 80 that should be added, in function of the used concentration of the other participant chemical species in the extraction and transfer process of the lanthanide ions<br>Fondecyt

Los procesos de conservación de los alimentos son diversos, sin embargo la aplicación de recubrimientos comestibles para retardar la degradación de frutas y verduras cada día toma más importancia, debido a que el desarrollo de estos recubrimientos podría reducir la contaminación por la sobreutilización de materiales de empaque.<br>El objetivo de este trabajo fue aplicar una emulsión a jitomate (Lycopersicum esculentum mil), donde la emulsión funcionara como recubrimiento, para la preservación de este alimento. Para ello se evaluaron los siguientes parámetros: pérdida de peso, tamaño, pH, acidez, grados Brix, firmeza y cantidad de CO2 desprendido del jitomate; éstos se realizaron en jitomate de dos procedencias distintas: comercial y orgánico a 3 diferentes temperaturas de almacenamiento: 5, 15 y 25°C, manteniendo siempre un jitomate testigo (control) en ambos casos. La mezcla de hidrocoloides usados para preparar la emulsión consistió de: carboximetilcelulosa (CMC- 5%), cera de carnauba (CW-1.5%), glicerol (Gli-1.5%), Gringsted® Acetem (Ester de ácido acético) (Gri-2.0%). También se realizaron análisis de textura y color para evaluar su calidad. Los resultados mostraron que el porcentaje de pérdida de peso en los jitomates recubiertos es menor con respecto a los jitomates control, por lo que se considera que el recubrimiento actúa como barrera permitiendo que disminuya la pérdida de agua del mismo, sin que se interrumpa el proceso natural de respiración-transpiración del fruto. El pH del jitomate disminuyó de 4.3 a 3.2. La acidez reportada como porcentaje de ácido cítrico disminuye en menor medida con respecto al tiempo para los jitomates orgánicos (de 0.39 a 0.34%) en comparación con los jitomates comerciales (de 0.42 a 0.30%). Los grados Brix del jitomate recubierto se encontraron entre 4.5-4.9% después de 21 días de almacenamiento. La firmeza de los jitomates con la emulsión fue mayor que la de los jitomates sin tratamiento obteniéndose para el jitomate recubierto una firmeza inicial promedio de 3760.56 N y final promedio de 2255.53 N, mientras que para el jitomate sin tratamiento se obtuvieron valores promedio entre 3578.10 N - 2168.23 N. xv Se evaluó el cambio en el tamaño del fruto, encontrando que el recubrimiento comestible aplicado a los jitomates impide la deshidratación rápida del fruto, por lo que el tamaño de éstos permanece constante con respecto a los que no se encuentran recubiertos. La tasa de respiración en los jitomates evaluada mediante la cantidad de CO2 desprendido del jitomate disminuyó al aplicar el recubrimiento con respecto al tiempo y la temperatura de almacenamiento; además de que el descenso en la respiración del jitomate fue más visible cuando la temperatura de almacenamiento es baja. Los parámetros L*, a* y b* fueron determinados en las diferentes muestras de jitomate, en los cuales no se encuentra diferencia significativa, manteniéndose el color de los mismos constante, obteniéndose valores de 41.14 a 36.74 para L*, de 27.21 a 22.87 para b* y de 18.68 a 23.61 para a*.<br>No aplica

Memoria para optar al título de químico farmacéutico<br>Las emulsiones son sistemas termodinámicamente inestables, debido al exceso de energía libre asociada al aumento de superficie durante la formación de los glóbulos de la fase interna, estos tienden a la coalescencia lo que ocasionará finalmente la separación del sistema. Para prolongar la estabilidad física de las emulsiones se utilizan diferentes sistemas, entre estos se ha estudiado el uso de nanopartículas (NPs). Por otra parte, las NPs pueden actuar como vehículo de flavonoides y otorgar un mejor rendimiento en términos de actividad antioxidante. El objetivo de este trabajo fue estudiar la capacidad de las nanopartículas mesoporosas de sílice con la superficie modificada con grupo amino, para estabilizar físicamente una emulsión. Además de evaluar de manera preliminar su capacidad de otorgar estabilidad química a la emulsión cuando se adsorbe un flavonoide en su superficie. Para realizar lo anterior, se sintetizaron nanopartículas mesoporosas de sílice superficialmente modificadas con grupo amino. Mediante experimentos tipo Batch, se obtuvieron nanopartículas con morina adsorbida, las cuales fueron caracterizadas midiendo el tamaño, distribución y potencial zeta. Para evaluar la capacidad de las nanopartículas para estabilizar emulsiones, se prepararon emulsiones con y sin tensoactivos a diferentes concentraciones, comparando la distribución y el tamaño de glóbulo obtenido respectivamente, y la estabilidad de las fracciones emulsificadas. Para evaluar la capacidad de otorgar mayor estabilidad química a una emulsión con vitamina E, estas se sometieron a una degradación forzada con peróxido de hidrógeno, para posteriormente ser cuantificada mediante HPLC. Los resultados mostraron que no se logra una estabilidad razonable al utilizar únicamente nanopartículas mesoporosas superficialmente modificadas con grupo amino como emulgente. Se logra un efecto sinérgico en la estabilización de un sistema bifásico, al utilizar tensoactivos y nanopartículas, a una concentración apropiada que permite la formación de una monocapa alrededor de la superficie de las nanopartículas. El estudio preliminar para evaluar la capacidad de otorgar estabilidad química a una emulsión reveló resultados promisorios dado que muestran un efecto protector frente a la degradación de la vitamina E contenida en el glóbulo

Las emulsiones del tipo agua en aceite (w/o) y aceite en agua (o/w) están compuestas por una mezcla de aceite, agua, lodo y otros agentes. Se pueden encontrar en el proceso y/o en los vertidos de diferentes tipos de industrias, tales como refinerías de petróleo, plantas procesadoras de aceite de consumo, industrias farmacéuticas, industrias de alimentos, etc. El calentamiento de un material a una frecuencia de microondas depende de la frecuencia de la onda electromagnética y de las propiedades dieléctricas, así como de la acumulación de energía interna que va ligada a la profundidad de penetración del campo dentro del material. De este modo, el conocimiento preciso de las propiedades dieléctricas de los materiales es fundamental para conocer su comportamiento bajo la influencia de un campo electromagnético. El objetivo general de esta tesis es proponer métodos alternativos basados en la tecnología de microondas para monitorizar, caracterizar y/o separar emulsiones. Para ello, se determinaron los protocolos de preparación de emulsiones prototipo en el laboratorio, empleando dos fases distintas (ácido oleico y aceite mineral SAE 40), de composición similar a las encontradas en la industria. Paralelamente se ha seleccionado, montando y calibrando un sistema de medida de propiedades dieléctricas en un rango de frecuencias de 1 a 4 GHz (rango cercano a la frecuencia estándar de calentamiento f =2.45 GHz) y de esta manera se ha obtenido un amplio espectro de información del comportamiento dieléctrico de las emulsiones, que servirán para diseñar en una fase posterior aplicadores de microondas. En base a este estudio preliminar se planteó una experiencia piloto con emulsiones reales presentes en el proceso de extracción de aceite de palma africana, con el fin de determinar el efecto de las microondas en la separación y en la calidad del aceite recuperado.<br>Pérez Páez, R. (2009). Aplicación de microondas en el tratamiento de emulsiones del tipo agua en aceite (w/o) y aceite en agua (o/w) [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/4328<br>Palancia

Atualmente, decorrente da cultura estética onde há o culto aos corpos esbeltos com aparência saudável e pele lisa, macia e viçosa, a hidrolipodistrofia ginóide, conhecida como celulite, tem sido um dos desafios para os dermatologistas e cirurgiões plásticos. Assim, temse testado diferentes formas de tratamentos entre as quais estão aplicações de cremes à base de xantinas visando a atenuação dos sintomas. O conhecimento das propriedades físicoquímicas de tais formulações é essencial para otimizar as condições de produção e liberação do ativo na pele, além de prover elegância cosmética do produto desenvolvido. Os objetivos desse trabalho foram obter e avaliar a estabilidade de emulsões O/A contendo fase líquida cristalina, adicionada de cafeína, para aplicação no tratamento da hidrolipodistrofia ginóide, bem como avaliar o perfil de liberação da substância ativa in vitro com intuito de determinar sua disponibilidade. A emulsão O/A contendo como fase oleosa, óleos vegetais naturais (óleo de urucum, de café e de melaleuca) foi desenvolvida através da utilização do Sistema Equilíbrio Hidrófilo- Lipófilo (EHL). Utilizando os tensoativos não-iônicos Ceteareth 5 e Steareth 2 nas concentrações de 10,0 e 15,0% foi possível obter fases líquidas cristalinas lamelares. A adição de cafeína a 1,0% foi conseguida em emulsão contendo 15,0% da mistura de tensoativos e com auxílio na solubilização através do uso de benzoato de sódio na mesma concentração (1,0%). As emulsões foram consideradas estáveis segundo as condições experimentais e parâmetros analisados. O perfil de liberação da substância ativa apresentou fase inicial de liberação mais rápida seguida de outra mais lenta. A eletroforese capilar mostrou-se ferramenta mais adequada para quantificação do ativo. Os resultados sugerem que os cristais líquidos lamelares estejam atuando provavelmente como veículo de liberação lenta.<br>Nowadays, due to aesthetic culture that there is the cult to slim body with health appearance and smooth, vigorous skin, the gynoid hydrolipodystrophy, known as cellulite, has been one of the challenges for dermatologists and plastic surgeons. Thus, different kinds of treatments have been tested, and among them, the application of xantines-based creams in order to attenuate the symptoms. The knowledge of the physicochemical properties of such formulations is essential to optimize the production conditions and active skin delivery, besides promoting cosmetic elegance of the developed product. The aims of this research were to attain and to evaluate the stability of O/W emulsions containing liquid crystalline phase, with the addition of caffeine, to be used on the gynoid hydrolipodystrophy treatment, as well as evaluate the release profile of the active in vitro in order to determine its availability. The O/W emulsion containing natural vegetable oils (annatto oil, coffee oil and tea tree oil) as oily phase was developed through the utilization of Hydrophilic Lipophilic Balance System (HLB). When using the non-ionic surfactants Ceteareth 5 and Steareth 2 in the 10.0 and 15.0% concentrations it was possible to obtain lamellar liquid crystalline phases. The addition of caffeine 1.0% was attained in emulsion containing 15.0% of the surfactant mixture and its solubility was improved through the sodium benzoate use in the same concentration. The emulsions were considered stable according to the experimental conditions and evaluated parameters. The release profile of the active agent presented a faster initial phase followed by a slower one. The capillary electrophoresis showed a more suitable tool to quantify the active. The results suggest that the lamellar liquid crystals are probably acting as slow delivery vehicle.

L’exploitation de pétrole s’accompagne de la modification des conditions thermodynamiques internes du puits et favorise, entre autres, la formation de dépôts minéraux pouvant obstruer les pores micrométriques de la formation rocheuse, rendant difficile l’extraction d’huile. L’efficacité du traitement anti-dépôts dépend de la concentration minimale d’inhibiteur et de la vitesse de relargage du produit. Dans ce contexte, nous avons étudié deux techniques d’encapsulation permettant d’obtenir un système préventif à libération prolongée contenant un polyélectrolyte anionique comme additif modèle. La première consiste en la formation de nanoparticules de polyélectrolytes complexés. La libération de l’actif encapsulé y a été stimulée par la modulation de la salinité du milieu. À pH basique, la libération de l’actif a lieu via le mécanisme de gonflement /dissociation des particules, à pH acide aucune libération ne parait avoir lieu car les objets précipitent. Le second système est une émulsion inverse (E/H) diluée contenant un actif modèle en phase dispersée. Ces systèmes sont stables et un faible pourcentage d’actif est libéré sous contrainte mécanique<br>Many thermodynamic changes occur in reservoir rock when oil is produced. These changes enable scale formation on micrometric rock pores that can block them and impede/block oil extraction. Antiscale treatment efficiency depends on minimal inhibitor concentration and product release rate in fluids downhole. In this context, we have studied two encapsulation techniques allowing us to have a sustainable release system composed of an anionic polyelectrolyte as a model additive. The first formulation consists in formation of polyelectrolyte complexes nanoparticles. In this system, active ingredient release was stimulated through medium ionic strength modulation. Under basic conditions, release takes place in particles swelling/dissociation process; whereas, under acidic condition, particles precipitate and no release can be expected. The second system we have worked on is a diluted reverse (W/O) emulsion, in which dispersed aqueous droplets contain a model additive. These systems are stable and small additive percentage is released under mechanic strain

碩士<br>國立臺灣科技大學<br>化學工程系<br>106<br>Microencapsulation has widely used in many areas such as pharmaceutical, agricultural, medical and food industries. Many methods have been developed to produce microcapsules for microencapsulation. In this work, we focus on one-step microencapsulation process. The oil-in-water (O/W) emulsion, in which oil droplets are emulsified in continuous phase of water, is conventionally prepared by synthetic surfactants and polymers. In recent years, various nano or microparticles been demonstrated can stabilize O/W emulsion, which known as Pickering emulsion. In this study, Pickering oil emulsion was prepared by cellulose nanocrystals (CNCs). Stable antimicrobial oil-in-water Pickering emulsion was prepared by employing a low concentration (0.1 wt%) of cellulose nanocrystals and olive oil containing hydrophobic antimicrobial agents. NaCl concentration of 20 mM in the water phase was found to greatly enhance stability of the emulsions prepared at O/W volume ratio of 1 to 4. Oil droplets with an average diameter of 3.70 ± 0.85 µm were uniformly dispersed in the emulsion. These microemulsions are stable even if stored for 1 month. Besides, the stable microemulsions can be maintained at temperature lower than 30°C. Curcumin with its fluorescence and oil-soluble properties was employed to observe the microencapsulated oil droplet under fluourescent microscope. Styrene was also used as an oil phase and polymerized in the Pickering emulsion to observe the CNC layer by Scanning Electron Microscope (SEM). Essential oil of Thymus vulgaris and Calocedrus formosana of various concentrations were employed in the olive oil as active antimicrobial agents. Essential oil of Calocedrus formosana was found to be more effective for killing S. aureus than that of Thymus vulgaris. Broader spectrum of antimicrobial activity was achieved by mixing Calocedrus formosana and Thymus vulgaris oil. Olive oil, essential oils and curcumin showed scavenging activity of DPPH● free radicals. Among them, Thymus vulgaris oil has the highest antioxidant activity that remove approximately 92% DPPH● free radicals. Additionally, the water-in-oil emulsion was prepared by using membrane emulsification method. The tannic acid (TA) solution was flew through polymeric membrane filter into the continuous phase which containing FeIII solution and nonionic Span®80 surfactant. Due to ferric ions cross linked with tannic acid, the FeIII-TA microcapsules can be formed. The volume ratio of W/O was fixed at 1 to 10. The smallest size of microcapsules was obtained at 600 rpm agitation speed of continuous phase, which is 0.38 ± 0.01 µm. The morphology of polymeric membrane and microcapsules were investigated by SEM and TEM, respectively. Microcapsules were dispersed in various pH values to check the stability. To confirm the versatility, the FeIII-TA microcapsule was applied to encapsulate magnetic nanoparticles, enzyme, and hydrogel. However, the microcapsules could not be used to encapsulate something due to the interaction between tannic acid and active ingredients in the dispersed phase before emulsification process. Hence, the enzyme encapsulated in FeIII-TA microcapsules go out from capsule. Besides, the irregular shape of hydrogel microcapsules and aggregation of encapsulated magnetic NPs were obtained.

碩士<br>嘉南藥理大學<br>化粧品應用與管理系<br>102<br>Many different types of mask cosmetics such as gel, wax, and emulsion were commercially available. Among these masks products, mask emulsions with clay are the most wildly used thanks to their efficacy. Using mask creams make the skin more texture and much better rubicundity. It is well known that wherever masks is useful for skin beauty or not is determined by their qualities. When the masks contain a great of amounts of clay, the suspension system may lead to the solution of settling problems and many problems such as poor coverage and brush marks,However, there is a little publication on the influence of varying masks on handling and physicochemical properties. This had led to the development of elegant mask creams and established a method measuring handling of the mask creams. The purpose of the study was to evaluate the influence of various kinds of components such as varying emulsifiers, a triglyceride (Aloe oil), kaolin, titanium oxide, humectants, stabilizer and pigment on the storage stability and the usage of the masks. In order to formulate the elegant masks, we selected Span(Sorbitan Monolaurate)/ Tween(Polysorbate) as a emulsifier because it provides the masks body bright and good rheological behavior. Their physicochemical properties including viscosity, rheological behavior, color appearance, and water lose were evaluated. In addition, handling properties such as, coverage, removal, and dryness were also tested and evaluation while a mask cream was rubbed to volunteer’s arms. To do this, a photograph of the measuring test area on volunteer’s arms was taken by the digital camera and illuminating tubes which is placed in a wooden box. In relating to physicochemical properties, the results showed that the mixture of humectants can result in the decreasing lose in water content of the mask creams. When Sunclear T40 AQS(oily form) was replaced by the mixture of Kaolin with powder TiO2, the mask cream with even coverage were obtained and there are acceptable physicochemical properties. A reasonable viscosity is ranging from 3300cps to 4500cps to have a good rubbing. Adding 3% Aloe oil improves the body of the mask creams. Total color difference (ΔE) of obtained masks arrive 0.95 at 0.21% of pigment (commercial mask cream as a control). Obviously, the color change is invisible. Finally, storage stability can be improved by adding stabilizer such as Sigel 305(Polyacrylamide/C13.14 Isoparaffin/Laureth-7) and PemulenTM TR-2(Acrylates / C10-30 Alkyl Acrylate Crosspolymer). Based on these findings, a desired mask cream was obtained. With a good rubbing and, stability at 45℃ testing for 32 days, and esthetic appearance, it is composed of Span 3%, Tween 2%, DM5 2.1%, CM040 2%, Finsolv TN 1%, Stearic acid 0.4%, Cetyl alcohol 0.6%, Mineral oil 2.3%, C.C.T 2.5%, Unimer U-15 0.7%, Aloe oil 3%, Vite E 0.3%, Pemulen TR-2 Polymer 0.2%, Xanthan gum 0.6%, EDTA.2Na 0.05%, Glycerin 1%, Propylene Glycol 2%, Hyaluronic Acid 2%, Prodew 400 2.5%, Kaolin 3%, TiO2 5%, Pigment0.21%, Saligerm G2 0.8%, Triethanolamine Q.S, D.W 62.54%。

碩士<br>國立海洋大學<br>食品科學系<br>87<br>The objectives of the study are to explore the effects of using water-soluble chitosan obtained by microfluidizing treatment in W/O/W multiple emulsion lotions which carry the lactic acid and vitamin E. The study includes 1. To determine the changes of molecular weight and degree of deacetylation of water-soluble chitosan with conditions and cycles of microfluidization treatment, 2. To explore the effect of adding water-soluble chitosan on the yield, stability, and average droplet size of the W/O/W multiple emulsion prepared. 3. To explore the rheological properties, skin moisture content, pH value and safety of W/O/W multiple emulsion lotion containing water-soluble chitosan. The results obtained are: The molecular weight of water-soluble chitosans obtained by microfluidizier treatment for 1, 3 and 7 cycles are 1.75 x 106, 1.35 x 106 and 1.00 x 106 Dalton respectively. Degree of deacetylation are around 75%. The yield of W/O/W multiple emulsion containing water-soluble chitosan is higher than that containing xanthan gum and the yield of preparation increased with increasing molecular weight of water-soluble chitosans used. But the stability of the W/O/W multiple emulsion lotions containing water-soluble chitosans are less than that containing the xanthan gum. The average droplet size were between 2- 4μm. The average droplet of the lotions containing water-soluble chitosan of 1.79 x 106 Dalton are smaller than that prepared from the other two molecular weight water-soluble chitosans. All the lotions prepared in the studies were pseudoplastic fluids. The pseudoplastic characteristic of the lotions such as shear thinning properties were more pronounced for those lotions containing xanthan gum in the external phase than that containing water-soluble chitosan . The apparent viscosity of the multiple emulsion is mainly affected by the changes of viscosity of the external continuous phase, and is less affected by the changes of the viscosity of the internal phase. The viscosity of the lotion containing xanthan gum in the external phase is higher than that containing water-soluble chitosan. The apparent viscosity of the lotion increased with increasing molecular weight of the water-soluble chitosan in the external continuous phase. Skin moisture content were higher for those lotions containing the water-soluble chitosan in the inner and/or external phase than that containing xanthan gum. Lotions containing W/O/W multiple emulsion carry lactic acid and vitamin E are a long last moisturizer. The effect of molecular weight of the water-soluble chitosan on skin moisture content become no significant different as the water-soluble chitosan was added in the inner phase. However skin moisture content increased with increasing molecular weight of the water-soluble chitosan added in the external phase at the first 40 minute after applying the lotion. Skin moisture content were independent to the molecular weight of water-soluble chitosan used after 40 minute. Decreasing of the skin pH value was lower for the W/O/W multiple emulsion lotions containing water-soluble chitosan in the inner and/or the external phase than that containing xanthan gum as control. The effect of molecular weight of the water-soluble chitosan used on skin moisture content was not significant. Decreasing of the skin pH value was the lowest for those W/O/W multiple emulsion lotions containing water-soluble chitosans in the inner and the external phase. It may due to the protonation of water-soluble chitosan in acidic solution which alleviated the decrease in free hydrogen ion resulted in less pH lowering of the lotion therefore less lowering in the skin pH value.

碩士<br>國立嘉義大學<br>食品科學系碩士班<br>91<br>When starch is dispersed in water with emulsifier and heated, the starch and emulsifier would interact to form starch-emulsifier complex. This thesis studied the effects of starch-emulsifier complexion on physical changes and on the stability of O/W emulsion system. Tree different HLB emulsifiers and various kinds of cornstarch were used in this study. The extent of complexion ( ACI % )of straight chain starch with emulsifier was determined by reacting with I2/KI reagent and measuring the absorbance at 600 nm. The ACI% depended on the amount of emulsifier, heating extent, water content, and dispersion of emulsifier. To observe the effects of complex on viscosity in emulsifier F110-polysaccharides complex system, the viscosity was continuously monitored as temperature was raised from 50℃ to 95℃ and lowered back to 50℃. The increase in heat break down and set back viscosity were only observed in cornstarch complex. When excess amount (10%) of emulsifier was added, the viscosity of cornstarch gel decreased. However, for three other gels (xanthan gum; guar gum; sodium alginate ), no obvious viscosity changes were observed. The thermal properties of complex were also studied by DSC. The DSC curve of starch-emulsifier complex showed two endothermic peaks at 45~54℃ and 98~107℃. The first peak involved the melting of starch crystals. While the second is a typical endothermic peak involved the melting of complex. The DSC curve of waxy cornstarch also showed a 90~110℃ peak but with small DH of 0.05J/g. This result indicates small part of branch-chained starch can form complex with emulsifier. For three other gels (xanthan gum; Guar gum; Sodium alginate), only one endothermic peak at 47~53℃ was observed. The DSC peak at 98~107℃ is a good indicator for the formation of starch-emulsifier complex. The emulsion activity (EA) and emulsion stability (ES) were used to indicate the effects of starch-emulsifier complex on O/W emulsion. The EA and ES for the emulsifier were 23.30% and 23.21% respectively; for the mixture of cornstarch and emulsifier 22.11% and 22.49%; for the mixture after complexing 18.23 % and 18.34%; for starch-emulsifier complex itself 3.08% and 7.74%. The experimental results indicated the complexing decreased the emulsion effect. With emulsifier F160, the measured surface tensions of blank solution, complexing mixture, and complex only were 18.08 mN/m, 9.02 mN/m, and 14.21 mN/m respectively. Which were larger compared with that of the mixture of cornstarch and emulsifier before complexing (4.72 mN/m) or the emulsifier (3.67 mN/m). As for oil drop size distribution, 70% were smaller than 5mm for the emulsifier solution or for cornstarch- emulsifier mixture before complexing; 60% were smaller than 10mm for the mixture after complexing; 60% were smaller than 20mm for the complex. Three different HLB emulsifiers showed similar results. Aabove results indicated that the starch-emulsion complex did not increase the emulsion stability.

碩士<br>國立海洋大學<br>食品科學系碩士在職專班<br>90<br>The objectives of the study are to explore the effect of using Monostroma nitidum aqueous extracts (aqueous extracts) on the characteristic, efficacy and safety of lotions containing vitamin C and vitamin E in W/O/W multiple emulsion. The study includes 1. To explore the effect of adding Monostroma nitidum aqueous extracts on the morphorlogy, average droplet size, oil globules distribution, yield and rheological properties of the W/O/W multiple emulsions thus prepared. 2. To explore the efficacy of applying lotions containing W/O/W multiple emulsions on water holding, pH value and sensitivity of the skin. The result shows that the W/O/W emulsions prepared from different formulas by two-stage emulsification method were multiple structure. The particle size of internal droplet decreased with increasing concentrations of aqueous extracts in the internal aqueous phase. For those emulsions formed whithout aqueous extracts in the internal aqueous phase the particles of internal droplets were bigger and they contacted with oil membrane. The distribution of particle size of W/O/W multiple emulsions studied are all in a narrow range. The W/O/W multiple emulsion containing xanthan gum had a diameter ranging between 11 and 14 μm, with a mean value of 10.59 μm. The W/O/W multiple emulsion containing 2.5 ℅ w/w aqueous extracts in external phase and 0.5 ℅ w/w aqueous extracts in inner aqueous phase had a diameter ranging between 3 and 7 μm, with a mean value of 4.56 μm. The W/O/W yield increased with increasing concentrations of aqueous extracts in the internal aqueous phase. All the multiple emulsions containing xanthan gum or aqueous extract were pseudoplastic fluids. The apparent viscosity and storage stability increased with increasing concentrations of aqueous extracts in the internal aqueous phase. The pH value of lotions containing W/O/W multiple emulsions were between 6.82 and 6.85. Skin sensitivity shows no erythema by the Daize score test. The pH value of the skin decreased after applying the W/O/W lotions but regained its normal pH value within 100 mins. The lotions containing aqueous extracts have better water holding than that containing xanthan gum.

碩士<br>國立宜蘭大學<br>食品科學系碩士班<br>99<br>Ultrasound is a modern and effective technology on emulsification. As emulsion stability and storage play an important role in food industry, how to improve the stability of emulsion becomes an important issue. To achieve this goal we must firstly figure out the processing conditions of emulsions. The purpose of this study is to prepare a stable nano/submicron emulsion, in which different processing methods and variant emulsifiers were employed. It showed that the oil concentration and centrifuged oil height were decreased with time for the lower layer of emulsion. Oil concentration was 9.0-10.7 wt% for the emulsion prepared by high speed blend-ultrasound (HSB/US) processing for one day after, while it was 0.8-2.8 wt% for the sample prepared by HSB/HSB processing. There was no nanoparticles initially observed for the emulsion prepared by HSB/HSB processing; however, there was 12% and 76% of nanoparticles in volume and number, respectively, for the emulsion prepared by HSB/US processing. The turbidity of the lower layer of emulsion denoted to decrease with time. Samples prepared by HSB/US got a less turbidity reduction than did the one by HSB/HSB, which the turbidity reduction was higher than 80% one day after. In general, HSB/US processing successfully produced a stable nano/submicron o/w emulsion. Sugar ester of HLB 11 (SE11) enhanced the emulsion stability than did the sugar ester of HLB 15 (SE15) and the complex of SE15/SE3. Addition of Tween 80 and Tween 80/Span 80 showed a worse stability.

碩士<br>嘉南藥理科技大學<br>化妝品科技研究所<br>96<br>At present, the cosmetics only focus on the efficiency but have no stability evaluation to stand on the shelf life. The stability of cosmetic is relation to efficiency and safety, so the study is discussing the stability with different types of cosmetics to build a system of the stability evaluation. The study uses different types of cosmetic products to be the sample, include 4 kinds of W/O emulsion and 8 kinds of solubility, this solubility is dividing to 1) water-soluble 2) oil-soluble 3) gel-soluble. After these samples are exposed to different aging factors (ex. temperature、moisture and centrifugation ), measuring the change of physical and chemical characters(ex. pH、color、viscosity and water content ). After the discussion about the stability of each sample, we can get these results: 1) W/O emulsion cosmetic change form aging shows that (a) The pH has slight change(△pH <0.5);(b)Almost show under level 3 (△E <3) ;(c) When water content change difference between upper and lower layers are more than 5%, we can observe that after aging has liquid suspend in the surface ;(d) Under a shear rate 0.2 sec-1, the viscosity shows decrease phenomenon(about 3~5 folds) ;(e)Between pH with chrominance shows the Pearson Correlation Coefficient ,r=0.680, its mean that when pH changes more bigger and opposites to the chrominance. 2) Solubility cosmetic changes form aging shows that (a) The type of water-soluble and gel-soluble which pH has slight change(△pH <0.5), the oil-soluble product show acidification phenomenon (△pH >1.0) ;(b) The type of water-soluble and oil-soluble which chrominance above level 4 (△E >3), and gel-soluble product has slight change(△E <1.5) ;(c) The water content change of dissolution are slight(<2%);(d) The type of water-soluble and oil-soluble which viscosity have no distinct change, but only the gel-soluble product which lower layer under a shear rate 0.2 sec-1, the viscosity shows increase phenomenon(about 0.3~0.5 folds) ;(e)The water-soluble product which between pH with chrominance、viscosity and water content are both show low relationship(r<0.3); the oil-soluble product which pH with water content(r=0.857) and chrominance with viscosity(r=0.824) show high relationship; the water-soluble product which between chrominance with water content shows high relationship(r=0.864). In this research, it provides 1) Set up a stability evaluation of the emulsion and solubility cosmetics. 2) Build an indicator to correct the formula and product process. 3) A reference of the shelf life.

碩士<br>國立海洋大學<br>食品科學系<br>88<br>The objectives of the study are to explore the effect of using different concentrations and different molecular weights water-soluble chitosan obtained by microfluidizing treatment on the characteristic, efficacy, and safety of O/W/O multiple emulsion lotions containing vitamin C and vitamin E. The study includes 1. To characterize molecular weight, degree of deacetylation, and solubility of water-soluble chitosan obtained by microfluidization treatment. 2. To explore the effect of adding water-soluble chitosans on the emulsion stability, average droplet size and vitamins release rates from the prepared O/W/O multiple emulsion. 3. To explore the rheological properties of the lotion, effective on moisture content, sebum content and pH value of the skin and safety of using O/W/O multiple emulsion lotion containing water-soluble chitosans. The results obtained are: The molecular weight of water-soluble chitosans prepared by cyclic microfluidizier treatment for 0, 1, 3and 7 times were 1.84 ×106、1.47 ×106、1.42 ×106 and 1.35 ×106 Dalton respectively. Degree of deacetylation were around 85%. Solubility of those chitosans were higher than 0.7 g/dl in water. The stability of O/W/O multiple emulsion lotions containing water-soluble chitosan were inferior to than that containing xanthan gum. The lotions containing 0.3% or 0.5% polysaccharides were more stable than that containing 0.1% polysaccharide ones. The average droplet size of O/W/O multiple emulsion lotions containing 0.3% water-soluble chitosan was smaller than those containing higher or lower concentrations of water-solbule chitosan. The average droplet size decreased with decreasing molecular weight of water-soluble chitosans used. The release rate of vitamin E from O/W/O multiple emulsion lotions has no significant difference among lotions containing xanthan or water-soluble chitosans. Vitamin E release rates decreased with increasing molecular weight of water-soluble chitosans or with increasing concentration. The release rate of vitamin C also decreased with increasing concentration of water-soluble chitosan used. However, release rates of vitamin C from lotions containing xanthan gum were higher than those containing water-soluble chitosan. All the lotions prepared in this study were pseudoplastic fluids. The apparent viscosity of the prepared lotions containing xanthan gum were higher than those containing water-soluble chitosans and increased with increasing concentration and/or molecular weight. Using the lotions containing 0.3% water-soluble chitosan resulted in decreasing skin pH value. However, no significant difference was found among lotions containing different molecular weights of water-soluble chitosan. The skin pH recovery rates were slower for lotions containing water-soluble chitosans than that containing xanthan gum. The skin pH value after using O/W/O multiple emulsion lotions were between 5.8～6.4. Skin sensitivity test showed no erythema on the dorsal skin of shaved rabbit based on the Daize score test. After applying lotions containing water-soluble chitosan, skin moisture content and sebum value were lower than that containing xanthan gum. Effect on the skin elasticity did not differ significantly after using the multiple emulsion lotions containing 0.3% xanthan gum or 0.3% water-soluble chitosan for one month. Decrease in skin elasticity was detected after using the multiple emulsion lotions for one week, however further increase in skin elasticity was slowed down.

碩士<br>國立成功大學<br>化學工程學系碩博士班<br>90<br>Abstract This research is about production of silica-shell microcapsules synthesized in O/W emulsion. Pentadecane is encapsulated in the microcapsules. We change the charge of silicates and surfactants, the reaction rate of silicates, etc. by adjusting the pH value, surfactant type, reaction temperature and stirring. The results of encapsulated content, morphologies and sizes of particles can be the base of investigating the mechanism of encapsulation. Stirring provides the emulsion stability and let silicates formed on the oil/water interface. After the thin inorganic shell formed, stopping of stirring can prevent the shell from breaking and let it grows. Then spherical, core-shell form, particle size of 4~8mm and encapsulated content of 30% microcapsules are formed. It might because of the high solubility of silicate at high pH value, there are no particles produced. The property and stability of interfaces are different due to using of different surfactants. This results in different morphologies of products. Therefore, formation of microcapsules should be under the system of a stable emulsion and low solubility of silicates. No matter it is under the charge system, S-M＋I-, S+I- or S-I+, there are no particles formed. Even it is S+X-I+, microcapsules formed only upper then a certain H+ concentration. Also, the encapsulated content increases with H+ concentration. It indicates that the formation mechanism of microcapsules is not due to electrical triple-layer. It means that it’s not charge controlled mechanism but rate controlled mechanism.

In der heutigen chemisch-pharmazeutischen Industrie sind Biokatalysen nicht mehr wegzudenken. Abhängig von der zu realisierenden Biotransformation, wurden signifikante Limitationen vor allem bei der Umwandlung von hydrophoben Substraten identifiziert. Wässrige und organische Einphasenreaktionssysteme treffen hier sehr schnell an ihre Grenzen, sodass nur geringe Ausbeuten realisierbar sind. Eine Alternative stellen mehrphasige Reaktionssysteme dar, wobei hier grundlegend klassische 2-Phasensysteme und Emulsionen unterschieden werden können. Mit Hilfe dieser alternativen Systeme können die bereits genannten Limitationen überwunden werden. Pickering Emulsionen stellen einen Spezialfall der klassischen Tensid stabilisierten Emulsion dar, wobei hier Nano- und Mikropartikel als Stabilisatoren die Tenside an der Tröpfchengrenzfläche ersetzen. Pickering Emulsionen stellen hoch dynamische Systeme dar und trotz kontinuierlicher Forschung auf diesem Gebiet bleiben bisher grundlegende Frage ungeklärt: Welche Parameter für bioaktive w/o Pickering Emulsionen wie Lösungsmittelkomposition, deren Phasenverhältnis, Partikelcharakteristika und -menge, Dispergierverfahren, als auch die Biokatalysatorkonzentration haben auf die Dispersität und Stabilität der Pickering Emulsionen den größten Effekt? Lässt sich eine Vielzahl von Biokatalysatoren in diesem Reaktionssystem einsetzen? Kurzum, eignen sich Wasser in Öl (w/o) Pickering Emulsionen als universelle Reaktionssysteme für effiziente Biokatalysen und stellen somit eine Plattformtechnologie dar? In dieser Studie konnte gezeigt werden, nahezu alle organischen Lösungsmittel, insbesondere leicht wassermischbare Vertreter, können w/o Pickering Emulsionen ausbilden. Ebenso ist eine Stabilisierung sowohl durch Naturstoffpartikel als auch durch hydrophobe und hydrophile Silicon-Compositpartikel realisierbar. In einer umfassenden Charakterisierung der typischen Stellräder für Emulsionen wurden kommerziell erhältliche Lipasen als bioaktive Komponenten zugesetzt, da diese die meistgenutzten Biokatalysatoren in diesem System darstellen. Die Veränderungen der Emulsionsstabilität und Tröpfchengrößen, als Maß der Dispersität, wurden über 24 Stunden erfasst. Hierbei wurde ein maßgebender Einfluss der Proteinkomponente gegenüber allen anderen Parametern wie Partikelmenge, Phasenverhältnis und Dispersionsgeschwindigkeit festgestellt. Proteine mit ihrer amphiphilen Oberflächenbeschaffenheit sind somit nicht nur als Biokatalysatoren, sondern auch als zusätzliche Nanopartikel zu betrachten, die gemeinsam mit hydrophoben Partikeln einen synergetischen und normalisierenden Effekt auf Tröpfchengrößen und Emulsionsstabilität ausüben. Jedoch waren durch Proteinzugabe auch negative Effekte wie Nicht-Etablierung der Emulsion oder eine Phasenumkehr im zeitlichen Verlauf auslösbar, wenn eine Grenzkonzentration überschritten wurde. Hinsichtlich der (bio)chemischen Charakterisierung von enzymbeladenen w/o Pickering Emulsionen konnte deutlich gezeigt werden, kleinere Tröpfchendurchmesser führen zu erhöhten Enzymaktivitäten und besseren Ausbeuten. Im moderat gerührten Batchreaktor wurde die volumetrische Raum-Zeit-Ausbeute um 500% bis 1100% gegenüber dem konventionellen 2 Phasen- und mikroaquatischen Reaktionssystem verbessert. Beim Einsatz von ganzen Zellen im Vergleich zum freien Enzym wurde mit normierter Biokatalysatoraktivität eine Verbesserung auf 130% bis 220% erzielt. Als beste Herstellungsmethodiken konnten das Dispergieren über Schütteln und Zahnkranzdispergierer ermittelt werden. Grenzflächentoxizität, als oft diskutierter Vorgang in Mehrphasensystemen, spielte auch in bioaktiven w/o Pickering Emulsionen eine wichtige Rolle. Es konnte gezeigt werden, hydrophilere Lösungsmittel, wie 2 Methyltetrahydrofuran, sorgten für eine minimierte Grenzflächendenaturierung der Proteine. Hingegen denaturierten hydrophobere Vertreter wie Cyclopentylmethylether und Cyclooctadien einen erheblichen Anteil des gelösten Proteins an der Grenzfläche. Eine eventuelle Kontamination der organischen Produktphase mit gentechnisch veränderten Enzymen durch assimiliertes Protein wurde ebenfalls untersucht. Es konnten geringe gelöste Proteinmengen festgestellt werden, wobei die Spannweite der gelösten Mengen 1 – 4% der Proteingesamtmenge betrug. Hydrophobere Lösungsmittel nahmen generell weniger Protein auf. Für die Evaluation der Verteilung von Substraten und Produkten zwischen beiden flüssigen und der festen Phase der Pickering Emulsion wurden exemplarisch das hydrophilste Substrat und das hydrophobste Produkt getestet. Es wurde keine signifikante Diffusion der gelösten Stoffe in die wässrige bzw. feste Phase ermittelt, insofern konnte eine dauerhaft hohe Bioverfügbarkeit der Substrate in der organischen Phase angenommen werden. Im gerührten Batch konnte eine Übertragung von Ionen zwischen den Dispersionströpfchen nur mit Hilfe von gelstabilisierten Dispersionströpfchen Einhalt geboten werden. Über derartige Modifikationen kann nun auch der Einsatz von mehreren Biokatalysatoren mit verschiedenen pH-Optima und Puffer-Präferenzen verwirklicht werden. Weiterhin konnte die disperse Phase auch gegen stark eutektische Lösungsmittel ausgetauscht werden, sodass Pickering Emulsionen auch als annähernd wasserfreie Reaktionssysteme nutzbar erschienen. In der Risiko- und Anwendungsanalyse über drei Enzymklassen mit drei als „grüner“ klassifizierten Lösungsmitteln in abgestuften Hydrophobizitäten, erwies sich Cyclopentylmethylether als das Lösungsmittel der Wahl für die Etablierung bioaktiver w/o Pickering Emulsionen. Bei der Anwendung verschiedener Biokatalysator-Phänotypen in verschiedenen Reaktionssystemen und Lösungsmitteln, kristallisierten sich bioaktive w/o Pickering Emulsion in Cyclopentylmethylether als produktivstes System heraus. Jedoch wurden bei allen Versuchen inaktivierende Vorgänge auf die verschiedenen Biokatalysatoren beobachtet, wobei Enzyme mit einer augenscheinlichen Gleichverteilung von hydrophoben und hydrophilen Aminosäureresten auf ihrer Oberfläche deutlich bessere Ergebnisse zeigten. In der Anwendung von freiem Enzym und Ganzzell-Biokatalysator, bei normierter Gesamtaktivität, resultierten für den Einsatz in bioaktiven Pickering Emulsionen die ganzen Zellen als beste Biokatalysator-Formulierung. Es wurde signifikant höhere Produktivität sowie auch 300% kleinere Tröpfchen der dispergierten Phase erreicht. Die Modularisierung von Biokatalysen gegenüber One-Pot-Synthesen zeigte ebenfalls deutliche Vorteile in den Kennzahlen der durchgeführten Biotransformation, wobei der jeweilige Prozessschritt an den Biokatalysator angepasst und so ein Optimum an Effizienz erreicht werden kann. Auf diese Weise können biokatalytische Umwandlungen kombiniert werden, die sich im One-Pot-System durch Inhibierungen der angewandten Biokatalysatoren ausschließen würden.:Vorwort/ Danksagung I Zusammenfassung III Abstract VII Liste der Publikationen XIV Abkürzungsverzeichnis und Symbole XIV 1 Einleitung 1 1.1 Biokatalysatoren – Generelle Aspekte und spezielle Vertreter 1 1.2 Angewandte Biokatalyse in Ein-und Mehrphasen-Reaktionssystemen 6 1.3 Pickering Emulsionen - Stand der Technik 14 1.4 Zielstellung der Arbeit: Optimierte bioaktive w/o Pickering Emulsionen 16 2 Material & Methoden 17 2.1 Material 17 2.1.1 Geräte & Zubehör 17 2.1.2 Chemikalien & Kits 19 2.1.3 Puffer 21 2.1.4 Enzyme 22 2.2 Proteinchemische Methoden 22 2.2.1 Bestimmung der Proteinkonzentration - BCA-Test 22 2.2.2 Bestimmung der Proteingröße und -reinheit - SDS-Polyacrylamidgelelektro- phorese (SDS – PAGE) 23 2.2.3 Photometrische Aktivitätsbestimmungen in wässrigem Milieu 24 2.2.4 Zusammenfassung Enzym-Charakteristika 27 2.3 w/o Pickering Emulsion – Essentielle Komponenten und Modifikationen 29 2.3.1 Definition des w/o PE-Standardsystems 29 2.3.2 Partikel zur Stabilisierung von w/o Pickering Emulsionen 29 2.3.3 Siliconbeschichtung von hydrophilen Partikeln und Bakterien 31 2.3.4 Bestimmung der Morphologie und Tröpfchengrößenverteilung 32 2.3.5 Lösungsmittelscreening 33 2.3.6 Phasen-Migration von Proteinen 34 2.3.7 Verteilungskoeffizienten von Substraten und Produkten im triphasischen Reaktionssystem Pickering Emulsion 34 2.4 Biokatalyse in Pickering Emulsionen 35 2.4.1 Bioaktive w/o PE - Definition des Standard-Reaktionssystems 35 2.4.2 Biokompatibilität „grüner“ Lösungsmittel 36 2.4.3 GC – Analytik 38 2.5 Statistische Auswertung der Experimente 40 2.5.1 Gewichteter Mittelwert, interne und externe Konsistenz 40 2.5.2 Lösungsmittelscreening: statistische Auswertung 41 3 Ergebnisse und Diskussion 42 3.1 Modifizierung von Nano-, Mikro- und Naturstoffpartikeln durch Siliconbeschichtung und Anwendungsscreening in w/o PE 42 3.1.1 Hydrophobizität der Silicon-Polymere 42 3.1.2 Morphologie von anorganischen Partikel-Materialien mit und ohne Silicon- Beschichtung 43 3.1.3 Morphologie von Naturstoff-Partikeln mit und ohne Silicon-Beschichtung 47 3.1.4 Partikel-Aggregation und Gegenmaßnahmen 51 3.1.5 Partikel-Screening 53 3.2 Charakterisierung von w/o Pickering Emulsionen im gerührten Batch 59 3.2.1 Pickering Emulsionen in biokatalytisch relevanten organischen Lösungs- mitteln 59 3.2.2 Bioaktive w/o PE - Auswirkung von Enzym – und Proteinmengen 66 3.2.3 Bioaktive w/o PE - Effekte der eingesetzten Partikelkonzentrationen 68 3.2.4 Bioaktive w/o PE - Einfluss der Phasenverhältnisse 70 3.2.5 Bioaktive w/o PE - Einfluss der angewandten Dispergiergeschwindigkeit 71 3.2.6 Bioaktive w/o PE - Herstellungsverfahren und Einfluss auf das Enzym 73 3.2.7 Vergleich 2-Phasensystem und bioaktive w/o Pickering Emulsion im gerührten Batch 75 3.2.8 Tröpfchengröße und Einfluss auf Produktbildung des PE-Systems 77 3.2.9 Phasen-Migration von Proteinen - Evaluation von Enzymwechselwirkungen mit dem Reaktionssystem 79 3.2.10 Verteilungskoeffizienten von Substraten und Produkten in den Standard– Reaktionssystemen 81 3.2.11 Protonen-Transfer zwischen zwei dispergierten Phasen in w/o Pickering Emulsionen 82 3.2.12 Alternative DES/o Pickering Emulsionen für wasserfreie Systeme 83 3.3 Bioaktive w/o Pickering Emulsion: Einschritt-Synthesen 84 3.3.1 Lipasenkatalysierte Umesterung in wässrigem Milieu 84 3.3.2 Carboligation mittels Benzaldehydlyase 86 3.3.3 Reduktionen via Alkoholdehydrogenasen 95 3.3.4 Transaminase 106 3.4 Bioaktive w/o Pickering Emulsionen: Mehrschritt-Synthesen 112 3.4.1 One-Pot-Biokatalyse gegen modularisierte Mehrschritt-Chemo-Biokatalyse 112 4 Bioaktive w/o Pickering Emulsionen als Reaktionssystem für Biokatalysen: Zusammenfassung & Bewertung 117 5 Plattform w/o Pickering Emulsion: Schlussfolgerung und Ausblick 130 6 Literatur 131 Anhang 150 Versicherung 150 Abbildungsverzeichnis 151 Tabellenverzeichnis 158 Download Datensammlung 164 A3.1.5 TMODS-Silicat-NP-Benchmark 165 A3.2.1-1 Lösungsmittel-Screening: physiko-chemische Eigenschaften 167 A3.2.1-2 Regressionsanalyse: Qualität PE gegen alle physiko-chemischen Eigenschaften 171 A3.2.1-3 Optimierte Regressionsanalyse: Qualität PE gegen Molekulargewicht, Dichte und Dampfdruck 173 A3.2.3 Auswirkungen von Protein- und Enzymmengen 175 A3.2.4 Effekte der eingesetzten Partikelmengen 175 A3.2.5 Einfluss der Phasenverhältnisse 176 A3.2.6 Einfluss der angewandten Dispersionsgeschwindigkeit/ -energie 176 A3.3.1 Lipasenkatalysierte Umesterung 177

碩士<br>逢甲大學<br>化學工程研究所<br>82<br>In this research project,a novel microwave demulsification method is applied in the emulsion liquid membrane(ELM) system to study the phenomena of breaking W/O emulsion and recovery of the internal concerntrated solution and the oil membrane phase. By applying the Taguchi's Orthogonal Array Experimental Design, the demulsification rate of different kinds of emulsion under various operating conditions of microwave radiation were studied.Operating conditions are treating power,treating time, surfactant concerntration, carrier type,carrier concerntration, internal solution type, internal solution concerntration, solvent type,O/A,emulsion rpm,emulsion time and emulsion volumn. Two kinds of analysis skill,"Causes and Effects" and "ANOVA Table",were adopted to determine the important factors and their corresponding levels and thus the final optimum conditions of the mcirowave demulsification.Moreover,we also studied the interaction between surfactant(Span 80) molecule and carrier(D2EHPA and M2EHPA) molecule by way of the measurement of the emulsion stability and the IR spectrophotometric analysis.