Partially hydrogenated oil (PHO) has no longer GRAS status. However, PHO is one of the important ingredients in bakery and confectionary industry and therefore the food industry is seeking for an alternative fat to replace PHO. Waxes have shown promise to fulfill that demand because of its easy availability and cheap in price. Waxes with high melting points (> 40 °C) help in the crystallization process when mixed with low melting point oils. A crystalline network is formed in this wax/oil crystallization process where liquid oil is entrapped in wax crystal network. A new material is formed which is neither completely solid nor completely liquid; it’s called semisolid material. This wax/oil semisolid material is formed physically; there are no chemical processes or treatments involved. This material has a potential use in the lipid industry due to its resemblance to the properties of commercial margarine or similar lipids. BW has shown softer crystalline network formation compared to SFW and RBW. It is understood that presence of higher wax ester in SFW and RBW leads to stronger crystalline material formation. Blending waxes of different chemical composition (e.g. BW: wax ester, hydrocarbon, fatty acids, di-esters, hydroxyl esters. RBW: 100% wax ester) shows differences in physical characteristics at different blending proportions. HIU technology helps in delaying phase separation of crystals in low concentration (0.5 and 1% wt. basis) of wax/oil system. Our overall wax crystallization study has shown that there are different physical characteristics of wax/oil semi-solid system based on different parameters and processing conditions such as wax concentration, wax and oil type, cooling rate, storage temperature, high intensity ultrasound. The hypothesis of this dissertation is that chemical composition of waxes and vegetable oils and also processing conditions affect wax crystallization and physical properties of wax/oil materials.

The objective of this research was to systematically study the effect of processing conditions on crystallization behavior and destabilization mechanisms of oil-in-water (o/w) emulsions. The effects of oil content (20 and 40 wt %); crystallization temperature (Tc = 10, 5, 0, -5, -10 °C); homogenization conditions, such as high shear (HS), very low pressure homogenization (VLPH), and high pressure homogenization (HPH); and cooling rate (0.2 and 30 °C/min) on both thermal behavior and destabilization mechanisms were analyzed. Docosahexaenoic acid (DHA) was added to VLPH emulsions and its effect on the physicochemical and oxidative stabilities and flavor was studied. Emulsions with 20% oil were less stable than those with 40% oil with a fast-cooling rate; however, stability increased when the emulsions were cooled slowly. Stability was also affected by oil and droplet size; the smaller the droplet the more stable the system. Smaller droplets (i.e., VLPH, HPH) had an effect on crystallization by delaying the onset of the crystal formation, which was promoted in emulsions with larger droplets (i.e., HS); 20% o/w emulsion crystallization was delayed more than 40%; and in emulsions crystallized using a slow-cooling rate, the crystal formation was less inhibited (i.e., crystals formed at a higher onset temperature [Ton], but at lower Tc) than when using a fast-cooling rate. The formation of lipid crystals either helped stabilize (small droplets) the emulsion and melted in a less fractionated manner or destabilized (big droplets) the emulsion. In addition, fast-cooling rates have greater fractionation than slow-cooling rates. Due to the greater stability of VLPH emulsions after thawing from being at -10 °C for 3 h, DHA was added to evaluate its effect on flavor (besides the effect on stability) of the emulsion. A descriptive panel was used to evaluate four attributes: oxidized, rancid, fishy, and buttery. The panelists were given samples after 72 h, because contrary to the TBA analysis which showed no significant differences between samples with and without DHA, the fishy smell was evident. The sensory evaluation results showed that there was a significant (p < 0.05) difference in fishiness between the VLPH emulsions with and without DHA, and that the odor was repulsive. No significance was seen for rancid and buttery flavors, and only a marginal significance was seen for oxidized.

There is a constant need of new synthetic emulsifiers in the food industry. Sugar esters are widely used as food grade synthetic emulsifiers, amongst which sucrose esters are the most common. Although sucrose esters are used very frequently, little is known about the use of lactose esters in food. There is a need for characterization of lactose esters before they can be used in foods. The objective of this study was to characterize a lactose ester, lactose monolaurate (LML) as an antimicrobial agent on food pathogens, evaluate its effect on 20 % oil-in-water emulsions as an emulsifier, and to explore its effect on crystallization behavior of anhydrous milk fat. In the first study (Chapter 3), the effect of LML was evaluated on survival of some Gram-positive and Gram-negative bacteria. For Listeria monocytogenes, a concentration of 1 mg/ml showed some inhibition in growth media whereas the cells were completely killed at 5 mg/ml. For Mycobacteria, an LML concentration between 0.1-1mg/ml was lethal. Scanning electron microscopy was also conducted to examine any changes in the morphology of cells. Listeria exhibited a change in morphology and a wrinkling effect was shown in Mycobacteria. In the second study (Chapter 4), the effect of LML as an emulsifier was evaluated in 20 % oil-in-water emulsions. The use level of LML was comparable to commercially available emulsifier polysorbate 20, and produced comparable stabilization in the emulsions upon use. In this study, an attempt was also made to optimize the synthesis of LML with respect to the immobilized enzyme and solvent combination. It was concluded that for 20 % oil-in-water emulsions, LML is a promising emulsifier at 0.5%. In the third study (Chapter 5), the effect of LML was evaluated at two concentrations on the crystallization behavior of anhydrous milk fat at two temperatures with high and low supercooling. On application of high intensity ultrasound (HIU) to anhydrous milk fat (AMF) at 31°C and 0.05 % LML the effect on viscosity of sample and crystallization behavior was evaluated. It was concluded that the viscosity of AMF decreased with the addition of 0.05% LML. The lower viscosity of anhydrous milk fat on addition of LML could be restored with the application of HIU.

The effects of high intensity ultrasound (HIU) on the crystallization behavior and functional properties of shortenings were evaluated. HIU was applied to different shortenings such as interesterified soybean oil (IESBO), multi-purpose commercial shortening, palm oil, and palm stearin. The functional properties measured include crystal morphology, solid fat content, melting profile, viscoelastic properties, hardness, and polymorphism. Different experimental set-ups were evaluated including a static batch system, a temperature cycling design, and flow cell system. Results showed that HIU generated harder material on IESBO, commercial shortening, and palm oil with more uniform and smaller crystal size, sharper melting profile, and higher elasticity. No chemical changes on triacylglycerol (TAG) and fatty acids were observed on IESBO under the sonication conditions used in this dissertation. Application of HIU maintained the texture of the commercial shortening that was subjected to temperature fluctuations, especially when HIU was applied before changes in temperature occurred. When sonication was applied in a flow-cell system lower power levels applied in a continuous manner was proved to be the most effective at inducing crystallization of palm oil. Research also showed that pulse irradiation of sonication and higher flow rates could be used to decrease the thermal effects generated by higher power levels of HIU. In addition, HIU was used in a highly saturated fat (palm stearin) at low power levels with long durations to delay lipid crystallization and generate a softer material. All the research findings suggest the great potential use of HIU in shortening production and food processing to improve the texture and its stability, as well as other functional properties.

The structure, functionality, isolation methods and applications of whey components, particularly the proteins and lactose, have been extensively studied. These studies have had a great impact on the food industry where whey components are increasingly being used as food ingredients. Two generations of whey protein product, namely Lactalbumin, produced by heat-induced precipitation, and Whey Protein Concentration/ Isloate, produced by ultrafiltration/ ion exchange chromatography, have been commercialised. Crystalline lactose in the food and pharmaceutical grades is also being produced. Recently, research activities in whey fractionation have shifted to the isolation of the minor components. This thesis is aimed at developing a Total Whey Utilization strategy by which the several components of the whey stream would be completely recovered by fractionation, resulting in little or no residue to be disposed of in the wastewater stream. Therefore, this study was initially dedicated to the development of novel separation methods which would be suitable for the Total Whey Utilization process. The development of those techniques revealed some previously unknown feature of whey components. The mechanisms of the separation methods have been also investigated. Although crystallization is an efficient method for fractionation or purification, its disadvantage is that the mother liquor is a wastewater containing high salt and BOD (Biological Oxygen Demand). The chromatographic method has been investigated in this work to separate the mother liquor or permeate into lactose and mineral fractions such that a goal of this thesis, namely a 'clean' water stream after processing whey, can be finally achieved. These studies have focused on the effect of resin type, salt form of the resin and the operating conditions on the separation of the lactose and mineral fraction. / Doctor of Philosophy (PhD)

Spectroscopy is increasingly used to investigate and monitor the solid state forms of pharmaceutical materials and products. Spectroscopy�s speed, nondestructive sampling, compatibility with fibre optics and safety also make it attractive for in-line monitoring. In this thesis, the spectroscopic techniques Fourier transform Raman spectroscopy, terahertz pulsed spectroscopy and second harmonic generation were used to characterise and quantify polymorphism and crystallinity of pharmaceutical compounds. Where possible, the multivariate analysis technique partial least squares was used for quantitative analysis. Fourier transform Raman spectroscopy detects polarisability changes mainly associated with molecular vibrations. Terahertz pulsed spectroscopy is a new spectroscopic technique that operates between the infrared and microwave regions of the electromagnetic spectrum and detects dipole moment changes mainly associated with crystalline phonon vibrations in the solid state. Second harmonic generation is a nonlinear optical phenomenon that depends on the dipole moment in crystals and crystal symmetry. Several materials capable of existing in different solid state forms were used. FT-Raman spectroscopy was able to differentiate carbamazepine forms I and III, enalapril maleate forms I and II and γ-crystalline and amorphous indomethacin. Combined with partial least squares the technique could quantify binary mixtures of CBZ forms I and III with a limit of detection as low as 1%, and mixtures of enalapril maleate with a limit of detection of as low as 2%. Terahertz pulsed spectroscopy obtained very different spectra for carbamazepine forms I and III, enalapril maleate forms I and II, γ-crystalline and amorphous indomethacin, crystalline and supercooled thermotropic liquid crystalline fenoprofen calcium, three forms of lactose, and five forms of sulphathiazole. At present the modes in the spectra cannot be attributed to specific phonon modes. Quantitation of binary mixtures of different forms of a compound using partial least squares analysis usually resulted in a limit of detection of about 1%. Second harmonic generation was used to quantify binary mixtures of different forms of enalapril maleate and lactose, as well as binary mixtures of enalapril maleate form II and polyvinylpyrrolidone. A quantitative relationship was present for each of the mixtures, however the limits of detection were usually above 10%. The high value is probably due to the machine being a prototype and univariate analysis associated with a single output variable. Future improvements to the apparatus and measurement parameters are likely to reduce the limits of detection. Ranitidine hydrochloride polymorphs could also be differentiated using second harmonic generation, however γ-crystalline and amorphous indomethacin and forms I and III of carbamazepine could not. The methods used in this thesis were successfully used for qualitative and quantitative analysis of polymorphism and crystallinity of pharmaceutical compounds. TPS and SHG are useful additions to the range of experimental techniques that can be used to investigate and monitor properties of pharmaceutical solids.

Notre recherche se base sur la structuration des polymères conjugués qui présentent des propriétés optiques et électroniques intéressantes en raison de leur structure moléculaire intrinsèque. En effet, la structure des polymères conjugués se compose d’une alternance de simples et de doubles liaisons donnant lieu à une délocalisation des électrons le long des chaînes. Cette conjugaison est à l’origine de leurs propriétés de luminescence et de leur caractère semi-conducteur. Ces polymères sont couramment utilisés dans des dispositifs électroniques où ils jouent le rôle de composant actif. Le fonctionnement de ces dispositifs repose sur la capacité des charges à se déplacer le long des chaînes (processus intramoléculaire) et d'une chaîne à l'autre (processus intermoléculaire) et par conséquent, ces propriétés de transport dépendent de l’arrangement des chaînes polymères dans le solide, qui lui-même découle des interactions supramoléculaires. Il est donc impératif de maîtriser ces interactions et d’étudier l’influence qu’elles ont sur les performances de tels dispositifs électroniques. C’est précisément sur ce point que porte notre travail : étudier et contrôler la formation de nanostructures en termes de dimensions, de forme et de localisation, en appliquant une contrainte physique extérieure à un film de polymère conjugué. Le polymère conjugué sur lequel notre étude se base principalement est le poly(3-hexylthiophène), P3HT. Ce polymère est semi-cristallin et possède une mobilité de charge élevée (0.18 cm2/V.s), ce qui en fait un très bon candidat en tant que composant actif dans les transistors à effet de champ. Nous avons, dans le cadre de notre recherche, étudié la structuration de films minces de P3HT, réalisée par l’application de contraintes physiques extérieures. L’utilisation d’une pointe de microscope à force atomique travaillant en mode contact permet de déformer plastiquement la surface polymère en créant des structures périodiques en surface des films mais elle permet, en outre, d’orienter les chaînes polymères dans la direction de passage de la pointe. Différents paramètres expérimentaux ont été étudiées comme par exemple, la résolution choisie pendant l’expérience, le nombre de passage effectués par la pointe ou encore l’angle avec lequel la pointe structure le film polymère. Nous avons également démontré que cette technique, appliquée au canal polymère d’un transistor à effet de champ, permet d’améliorer les propriétés électriques du P3HT et par conséquent, d’augmenter les performances du dispositif électronique. Nous avons utilisé une autre méthode, dite de « lithographie douce », afin de structurer le P3HT. Cette technique présente l’avantage de « façonner » le polymère lorsqu’il se trouve en solution et ne nécessite donc pas la formation préalable d’un film. Elle consiste à déposer une goutte de solution polymère sur un substrat, à l’entrée de canaux micrométriques de PDMS; l’écoulement de la solution polymère, qui se fait par capillarité dans les canaux, est donc confiné. Le solvant va ensuite s’évaporer et il reste alors, sur le substrat, un dépôt polymère qui est la réplique négative des canaux de PDMS. L’analyse du dépôt polymère formé grâce à cette méthode révèle, comme c’était le cas pour la technique précédente, une orientation des chaînes polymères au sein des canaux. Dans la dernière partie de ce travail, nous avons étudié le dopage de films fibrillaires de P3HT. L'étude de la morphologie des films dopés montre que la structure fibrillaire est conservée, avec une légère augmentation de la largeur des fibrilles. Cette augmentation résulte d'un déplacement des chaînes polymères les unes par rapport aux autres dans l'axe du squelette conjugué afin de laisser des espaces vacants pour accueillir les contre-ions dans le réseau polymère. Les mesures électriques des films dopés montrent un accroissement très important de la conductivité du polymère. On observe une augmentation de six ordres de grandeur entre les conductivités d'un film neutre et dopé.

populärwissenschaftlicher Abstract:<br /> Kristallisation, Biomimetik und halbleitende Polymere in räumlich begrenzten Systemen:<br /> Öl und Wasser mischen sich nicht, man kann aber aus beiden Flüssigkeiten Emulsionen herstellen, bei denen Tröpfchen der einen Flüssigkeit in der anderen Flüssigkeit vorliegen. Das heißt, es können entweder Öltröpfchen in Wasser oder Wassertröpfchen in Öl erzeugt werden. Aus täglichen Erfahrungen, z.B. beim Kochen weiß man jedoch, dass sich eine Emulsion durch Schütteln oder Rühren herstellen lässt, diese jedoch nicht besonders stabil ist. Mit Hilfe von hohen Scherenergien kann man nun sehr kleine, in ihrer Größe sehr einheitliche und außerdem sehr stabile Tröpfchen von 1/10000 mm erhalten. Eine solche Emulsion wird Miniemulsion genannt. <br /> In der Dissertation wurden nun z.B. Miniemulsionen untersucht, die aus kleinen Wassertröpfchen in einem Öl bestehen. Es konnte gezeigt werden, dass das Wasser in diesen Tröpfchen, also in den räumlich begrenzten Systemen, nicht bei 0 &#176;C, sondern bei -22 &#176;C kristallisierte. Wie lässt sich das erklären? Wenn man einen Eimer Wasser hat, dann bildet sich normalerweise bei 0 &#176;C Eis, da nämlich in dem Wasser einige (manchmal ganz wenige) Keime (z.B. Schutzteilchen, ein Fussel etc.) vorhanden sind, an denen sich die ersten Kristalle bilden. Wenn sich dann einmal ein Kristall gebildet hat, kann das Wasser im gesamten Eimer schnell zu Eis werden. Ultrareines Wasser würde bei -22 &#176;C kristallisieren. Wenn man jetzt die Menge Wasser aus dem Eimer in kleine Tröpfchen bringt, dann hat man eine sehr, sehr große Zahl, nämlich 1017 Tröpfchen, in einem Liter Emulsion vorliegen. Die wenigen Schmutzpartikel verteilen auf sehr wenige Tröpfchen, die anderen Tröpfchen sind ultrarein. Daher kristallisieren sie erst bei -22 &#176;C.<br /> <br /> Im Rahmen der Arbeit konnte auch gezeigt werden, dass die Miniemulsionen genutzt werden können, um kleine Gelatine-Partikel, also Nanogummibärchen, herzustellen. Diese Nanogummibärchen quellen bei Erhöhung der Temperatur auf ca. 38 &#176;C an. Das kann ausgenutzt werden, um zum Beispiel Medikamente zunächst in den Partikeln im menschlichen Körper zu transportieren, die Medikamente werden dann an einer gewünschten Stelle freigelassen. In der Arbeit wurde auch gezeigt, dass die Gelatine-Partikel genutzt werden können, um die Natur nachzuahnen (Biomimetik). Innerhalb der Partikel kann nämlich gezielt Knochenmaterial aufgebaut werden kann. Die Gelatine-Knochen-Partikel können dazu genutzt werden, um schwer heilende oder komplizierte Knochenbrüche zu beheben. Gelatine wird nämlich nach einigen Tagen abgebaut, das Knochenmaterial kann in den Knochen eingebaut werden.<br /> <br /> LEDs werden heute bereits vielfältig verwendet. LEDs bestehen aus Halbleitern, wie z.B. Silizium. Neuerdings werden dazu auch halbleitende Polymere eingesetzt. Das große Problem bei diesen Materialien ist, dass sie aus Lösungsmitteln aufgebracht werden. Im Rahmen der Doktorarbeit wurde gezeigt, dass der Prozess der Miniemulsionen genutzt werden kann, um umweltfreundlich diese LEDs herzustellen. Man stellt dazu nun wässrige Dispersionen mit den Polymerpartikeln her. Damit hat man nicht nur das Lösungsmittel vermieden, das hat nun noch einen weiteren Vorteil: man kann nämlich diese Dispersion auf sehr einfache Art verdrucken, im einfachsten Fall verwendet man einfach einen handelsüblichen Tintenstrahldrucker. / The colloidal systems are present everywhere in many varieties such as emulsions (liquid droplets dispersed in liquid), aerosols (liquid dispersed in gas), foam (gas in liquid), etc. Among several new methods for the preparation of colloids, the so-called miniemulsion technique has been shown to be one of the most promising. Miniemulsions are defined as stable emulsions consisting of droplets with a size of 50-500 nm by shearing a system containing oil, water, a surfactant, and a highly water insoluble compound, the so-called hydrophobe<br /> <br /> 1. In the first part of this work, dynamic crystallization and melting experiments are described which were performed in small, stable and narrowly distributed nanodroplets (confined systems) of miniemulsions. Both regular and inverse systems were examined, characterizing, first, the crystallization of hexadecane, secondly, the crystallization of ice. It was shown for both cases that the temperature of crystallization in such droplets is significantly decreased (or the required undercooling is increased) as compared to the bulk material. This was attributed to a very effective suppression of heterogeneous nucleation. It was also found that the required undercooling depends on the nanodroplet size: with decreasing droplet size the undercooling increases.<br /> <br /> 2. It is shown that the temperature of crystallization of other n-alkanes in nanodroplets is also significantly decreased as compared to the bulk material due to a very effective suppression of heterogeneous nucleation. A very different behavior was detected between odd and even alkanes. In even alkanes, the confinement in small droplets changes the crystal structure from a triclinic (as seen in bulk) to an orthorhombic structure, which is attributed to finite size effects inside the droplets. An intermediate metastable rotator phase is of less relevance for the miniemulsion droplets than in the bulk. For odd alkanes, only a strong temperature shift compared to the bulk system is observed, but no structure change. A triclinic structure is formed both in bulk and in miniemulsion droplets.<br /> <br /> 3. In the next part of the thesis it is shown how miniemulsions could be successfully applied in the development of materials with potential application in pharmaceutical and medical fields. The production of cross-linked gelatin nanoparticles is feasible. Starting from an inverse miniemulsion, the softness of the particles can be controlled by varying the initial concentration, amount of cross-link agent, time of cross-linking, among other parameters. Such particles show a thermo-reversible effect, e.g. the particles swell in water above 37 &#176;C and shrink below this temperature. Above 37 &#176;C the chains loose the physical cross-linking, however the particles do not loose their integrity, because of the chemical cross-linking. Those particles have potential use as drug carriers, since gelatin is a natural polymer derived from collagen.<br /> <br /> 4. The cross-linked gelatin nanoparticles have been used for the biomineralization of hydroxyapatite (HAP), a biomineral, which is the major constituent of our bones. The biomineralization of HAP crystals within the gelatin nanoparticles results in a hybrid material, which has potential use as a bone repair material.<br /> <br /> 5. In the last part of this work we have shown that layers of conjugated semiconducting polymers can be deposited from aqueous dispersion prepared by the miniemulsion process. Dispersions of particles of different conjugated semiconducting polymers such as a ladder-type poly(para-phenylene) and several soluble derivatives of polyfluorene could be prepared with well-controlled particle sizes ranging between 70 - 250 nm. Layers of polymer blends were prepared with controlled lateral dimensions of phase separation on sub-micrometer scales, utilizing either a mixture of single component nanoparticles or nanoparticles containing two polymers. From the results of energy transfer it is demonstrated that blending two polymers in the same particle leads to a higher efficiency due to the better contact between the polymers. Such an effect is of great interest for the fabrication of opto-electronic devices such as light emitting diodes with nanometer size emitting points and solar cells comprising of blends of electron donating and electron accepting polymers.

The main objective of this thesis is to understand molecular crystallization as a multistep process with or without polymeric additives, including transient liquid-liquid phase separation, nanocrystal nucleation within the dense phase, and subsequent nanocrystal self-assembly or self-organization in sequence. The thesis starts with a quaternary model system, containing DL-Glutamic acid (Glu), polyethyleneimine (PEI), water, and EtOH, for the understanding of multistep precipitation of Glu with PEI as an additive. The experiments were performed by mixing Glu-PEI aqueous solution with a non-solvent EtOH. First, the phase diagram of the quaternary system is determined, obtaining precipitate, coacervates, or homogeneous mixtures by varying Glu/PEI w/w and water/EtOH v/v. Coacervation is observed to occur over a wide range of Glu/PEI with various volumes. The composition of coacervates is conveniently characterized by nuclear magnetic resonance spectroscopy. The observed coacervates are thermodynamically stable phases rich in solute, which is different from metastable polymer-induced liquid precursors. The combination of atomic force microscopy, small angle scattering, and ξ-potential measurements confirms the coexistence of monomers and Glu/PEI complexes and the aggregation of complexes in Glu-PEI-water systems. This suggests that there might be a direct structural transformation between the Glu-PEI complexes in aqueous solution and the metastable liquid precursors in a water-EtOH mixture. The multistep mechanism of Glu precipitation with PEI as an additive is investigated thereafter. The combination of stopped flow and small angle scattering demonstrates that the initially formed liquid precursors pass through an alteration of growth and coalescence. Combined with results from optical microscopy and scanning electron microscopy, the nucleation of nanoplatelets happens within each liquid precursor droplet, and nanoplatelets reorient themselves and self-organize into a radial orientation in the crystalline microspheres. The recipe was then extended to the precipitation of organics in other oppositely charged amino acid-polyelectrolyte systems. After the success in preparing hierarchical microspheres in solution, the similar recipe can be extended to the preparation of patterned thin films on substrate. By dipping a quaternary DL-Lys·HCl (Lys)–polyacrylic acid (PAA)–water–EtOH dispersion on a hydrophilic slide, the fast evaporation process of the volatile solvent EtOH is responsible for the homogeneous nucleation of NPs. Then, the following complete evaporation causes the mesocrystallization of a continuous spherulitic thin film along the receding line of the liquid, which again transforms into a mesocrystalline thin film. Furthermore, annealing is used to optimize the property of mesocrystalline thin films. As evaporation is a non-equilibrium process, it can be used to tune the kinetics of crystallization. Therefore, hierarchical or periodical thin films are obtainable by starting the evaporation from microspheres recrystallization, obtaining mesocrystalline thin films with 4 hierarchy levels. The results reveal that evaporation provides an easy but effective way for the formation of patterned structures via the positioning of NPs after their fast nucleation, resulting in different kinds of patterns by controlling the concentration of NPs, solvent evaporation rate, and other physical forces. Non-classical crystallization is not limited to crystallizations with polymeric additives. We also observed the nucleation and growth of a new molecular layer on the growing DL-Glu·H2O crystals from a supersaturated mother liquor by using an in-situ atomic force microscopy (AFM), where the nucleation and growth of a molecular layer proceed via amorphous nanoparticle (NP) attachment and relaxation process before the observation of the growth of a newly formed molecular layer. NP attachment to the crystal surface is too fast to observe by using in-situ AFM. The height shrinkage of NPs, combined to the structural transformation from 3D amorphous NPs to 2D crystalline layer, is observed during the relaxation process. The nucleation and growth of a newly formed molecular layer from NP relaxation is contradictory to the classical nucleation theory, which hypothesizes that nuclei show the same crystallographic properties as a bulk crystal. The formation of a molecular layer by NP attachment and relaxation rather than attachment of single molecules provides a different picture from the currently held classical nucleation and growth theory regarding the growth of single crystals from solution. / Das Hauptziel dieser Arbeit ist das Verständnis der molekularen Kristallisation, sowohl mit als auch ohne polymere Additive, als einen mehrstufigen Prozess. Dieser beinhaltet eine transiente flüssig-flüssig Phasentrennung, die Nukleation von Nanokristallen in der dichten flüssigen Precursor-Phase so wie eine anschließende nanokristalline Selbstorganisation. Die Arbeit beginnt mit Untersuchungen an einem quaternären Modelsystem bestehend aus DL-Glutamat (Glu), Polyethylenimin (PEI), Wasser und Ethanol. Das Phasendiagramm dieses quaternären Systems wird durch Variation der Glu/PEI w/w und Wasser/EtOH v/v Verhältnisse bestimmt, wobei Präzpitat aus polymerinduzierten flüssigen Precursor, Koazervate oder homogene Mischungen erhalten werden Das thermodynamisch stabile Koazervat kann als Referenz für das Verständnis von flüssigen Precursorn angesehen werden, welche in der Natur metastabil und transient sind. Der mehrstufige Mechanismus der Glu-Präzipitation mit PEI als Additiv wird dann mittels Neutronen Kleinwinkelstreuung untersucht. Dies zeigt, dass die ursprünglich gebildeten flüssigen Precursor noch vor der Nukleation von Nanokristallen einen Wechsel von Wachstum und Koaleszenz durchlaufen. Die Ergebnisse aus optischer- und Eletronenmikroskopie zeigen, dass sowohl die flüssigen Precursor Superstrukturen ausbilden als auch, dass die Nukleation von Nanoplättchen in jedem einzelnen Precursor Tropfen von statten geht. Dies geschieht noch bevor sich die Nanoplättchen selbst in einer radialen Orientierung ausrichten. Diese Studie liefert die Kinetik der Präzipitation von organischen Stoffen in Gegenwart von polymeren Additiven. Eine ähnliche Vorgehensweise wie für die Herstellung von Mikrokügelchen kann für die Darstellung von gemusterten Filmen angewandt werden. Die homogene Nukleation von Nanopartikeln (NPs) findet während der Verdampfung einer quarternären DL-Lys·HCl-Polyacrylsäure-Wasser-Ethanol Dispersion auf einer hydrophilen Oberfläche statt. Die darauffolgende vollständige Verdampfung löst die Mesokristallisation eines kontinuierlichen sphärolithischen dünnen Films aus, welcher sich wiederum in einen mesokristallinen dünnen Film umwandelt. Mesokristalline Filme mit 4 Hierarchiestufen bzw. auch periodische Filme werden durch die Verdampfung der Mikrokügelchen-Dispersion erhalten. Die Ergebnisse zeigen, dass die Verdampfung eine einfache aber effektive Methode zur Herstellung von verschieden gemusterten hierarchischen Filmen darstellt. Nicht-klassische Kristallisation wird auch in der Abwesenheit von polymeren Additiven beobachtet. Wir verfolgen mittels Rasterkraftmikroskop (AFM) die Nukleation und das Wachstum einer neuen molekularen Schicht auf wachsenden DL-Glu·H2O Kristallen aus übersättigter Mutterlauge. Die Bildung einer neuen molekularen Schicht verläuft durch die Anlagerung von amorphen Nanopartikeln. Das Schrumpfen der NPs zusammen mit der strukturellen Änderung von dreidimensionalen NPs zu 2D Schichten wird während dieses Relaxationsprozesses beobachtet. Schließlich kommt es zu der Ausbildung einer neuen molekularen Schicht. Die Bildung einer molekularen Schicht durch die Anlagerung von Nanopartikeln aus der Lösung und die darauffolgende Relaxation liefert ein abweichendes Bild zu der bisher gängigen klassischen Theorie des Kristallwachstums.

There is a constant need of new synthetic emulsifiers in the food industry. Sugar esters are widely used as food grade synthetic emulsifiers, amongst which sucrose esters are the most common. Although sucrose esters are used very frequently, little is known about the use of lactose esters in food. There is a need for characterization of lactose esters before they can be used in foods. The objective of this study was to characterize a lactose ester, lactose monolaurate (LML) as an antimicrobial agent on food pathogens, evaluate its effect on 20 % oil-in-water emulsions as an emulsifier, and to explore its effect on crystallization behavior of anhydrous milk fat. In the first study (Chapter 3), the effect of LML was evaluated on survival of some Gram-positive and Gram-negative bacteria. For Listeria monocytogenes, a concentration of 1 mg/ml showed some inhibition in growth media whereas the cells were completely killed at 5 mg/ml. For Mycobacteria, an LML concentration between 0.1-1mg/ml was lethal. Scanning electron microscopy was also conducted to examine any changes in the morphology of cells. Listeria exhibited a change in morphology and a wrinkling effect was shown in Mycobacteria. In the second study (Chapter 4), the effect of LML as an emulsifier was evaluated in 20 % oil-in-water emulsions. The use level of LML was comparable to commercially available emulsifier polysorbate 20, and produced comparable stabilization in the emulsions upon use. In this study, an attempt was also made to optimize the synthesis of LML with respect to the immobilized enzyme and solvent combination. It was concluded that for 20 % oil-in-water emulsions, LML is a promising emulsifier at 0.5%. In the third study (Chapter 5), the effect of LML was evaluated at two concentrations on the crystallization behavior of anhydrous milk fat at two temperatures with high and low supercooling. On application of high intensity ultrasound (HIU) to anhydrous milk fat (AMF) at 31°C and 0.05 % LML the effect on viscosity of sample and crystallization behavior was evaluated. It was concluded that the viscosity of AMF decreased with the addition of 0.05% LML. The lower viscosity of anhydrous milk fat on addition of LML could be restored with the application of HIU.