This work seeks to fabricate, optimize, and characterize nanofibers of cactus Opuntia ficus-indica mucilage and Poly (vinyl alcohol) (PVA) by electrospinning. Mucilage is a neutral mixture of sugars produced by cactus and PVA is a non-toxic, water-soluble, synthetic polymer, which is widely used as a co-spinning agent for polymers. Mucilage was extracted from the cactus pad and prepared for electrospinning by mixing with acetic acid. Two types of PVA were used differentiating in high and low molecular weights. Concentrations of PVA were varied to find an adequate threshold for fiber formation. Changing the ratio of PVA to cactus mucilage produced fibers of different diameter and quality. The optimizations of the parameters used in the electrospinning setup were also a factor in creating quality fibers without deformity. An acceptable PVA to mucilage ratio mixture was reached for the use of the electrospinning process and consistent nanofibers were accomplished with the use of both the low and high molecular weight PVA. The fibers were observed using a Scanning Electron Microscope, Atomic Force Microscopy, and Differential Scanning Calorimetry. In this project we were able to obtain nanofiber meshes made with environmentally friendly materials with fiber diameters raging from 50nm to 7um sized. The produced nanofibers were made in the hope that it can be utilized in the future as an inexpensive, biocompatible, and biodegradable water filtration system.

Dans ce travail, nous nous sommes intéressés au développement d’un nouveau biocapteur enzymatique ultrasensible pour la détection conductimétrique d’une mycotoxine, l’ochratoxine A (OTA). Une peptidase, la thermolysine (TLN), a été choisie comme élément de reconnaissance. Le biocapteur proposé est basé sur l’immobilisation de la TLN dans une matrice d’alcool polyvinylique (PVA)/polyéthylènimine (PEI) contenant des nanoparticules d’or et réticulée à la surface de microélectrodes interdigitées à l’aide de vapeurs de glutaraldéhyde. Dans les conditions optimales (35 min de réticulation, mesure à pH 7 et 25°C), la réponse du biocapteur est linéaire jusqu’à 60 nM et la limite de détection est de 1 nM. Cette valeur est 700 fois plus basse que celle obtenue en utilisant une méthode d’immobilisation basée sur la co-réticulation de la TLN en présence d’albumine de sérum bovin (BSA). La matrice PVA/PEI crée un environnement aqueux favorable à l’enzyme. Par ailleurs, les interactions entre les groupements amines protonés du PEI et les charges négatives des nanoparticules citratées et de la TLN améliore leur dispersion dans la matrice et favorise la stabilisation de l’enzyme et son accessibilité au substrat (OTA). Le biocapteur conductimétrique développé est très reproductible et stable pendant 30 jours lorsqu’il est stocké à 4°C dans du tampon phosphate 20 mM pH7 entre 2 mesures. Le biocapteur a ensuite été évalué sur des échantillons d’huile d’olive commerciale dopée. Aucun prétraitement de l’échantillon n’a été nécessaire et des taux de recouvrement proches de 100% ont été obtenus, démontrant l’absence d’effet de matrice / A new ultrasensitive enzymatic biosensor for the direct conductometric detection of ochratoxin A (OTA) has been developed in this work. Thermolysin (TLN), a peptidase, was chosen as recognition element. The proposed biosensor is based on TLN immobilization into a polyvinyl alcohol (PVA)/polyethylenimine (PEI) matrix containing gold nanoparticles (AuNPs) and cross-linked at the surface of gold interdigitated microelectrodes using glutaraldehyde vapor. Under optimal conditions (35 min cross-linking time, working pH of 7 and temperature of 25◦C), the biosensor response was linear up to 60 nM OTA and the limit of detection was 1 nM. This value was 700 times lower than the detection limit obtained using the more classical method based on enzyme cross-linking in the presence of bovine serum albumin (BSA). PVA/PEI hydrogel creates a very favorable aqueous environment for the enzyme. In addition, interactions between protonated amino groups of PEI and negative charges of both citrated AuNPs and thermolysin improve their dispersion in the polymer blend, favoring enzyme stabilization and accessibility to the substrate (OTA). The developed OTA biosensor was very reproducible and stable over a 30 days period when stored at 4◦C in 20 mM phosphate buffer between two measurements. The method was further evaluated using commercial doped olive oil samples. No pretreatment of the sample was needed for testing and no matrix effect was observed. Recovery values were close to 100%, demonstrating the suitability of the proposed method for OTA screening in olive oil

This diploma thesis investigates the suitability of relaxation tests as a part of complex characterization of hydrogel materials using classical rheology methods. With respect to the current research, creep and three interval thixotropy tests were taken into account. For them, general optimization was done aiming to find an ideal parameter settings. The optimization was performed using physically crosslinked agarose (AG) hydrogel and the tuned tests were also applied to two more samples: hyaluronan (HyA) and polyvinyl alcohol (PVAl) gel. These materials were selected due to their mutually different crosslinking principle. The experiments showed, the AG gel proved to have the best ability to recover after deformation of all studied samples. On the other hand, the HyA gel relaxed the worst. Although the final results of both tests were comparable, the regeneration process itself was different. Hence, the complex relaxation characteristics cannot be described using one of the performed tests alone and both the creep and three interval thixotropy tests have great importance in the scope of complex relaxation behaviour. The obtained results may lead to more precise description of deformation and relaxation, which are frequent phenomena occurring during treatment and application of hydrogel materials.

The subject of the thesis is to improve the moisture resistance of MDF (macro-defect-free) composites prepared on the basis of aluminous cement and polyvinyl alcohol. These materials are characterized by the absence of defects in the structure and high mechanical performance. These features make MDF composites a promising type of material that could be used in the future for construction purposes. The basic deficiency of MDF composites is insufficient resistance to water or moisture, accompanied by a significant decrease in strength. Therefore, this work deals with increasing of moisture resistance using organotitanate agent and modification of the polymer. Two types of polyvinyl alcohols differing in hydrolysis degree and degree of the polymerization has been modified. Based on the results of the measurement the effect of storage conditions on the properties and structure of prepared MDF composites was observed. The characterization of MDF composites were realized by measurement of flexural strength in bending, scanning electron microscopy with EDS analysis, TG-DTA-EGA, water absorption and consequently the porosity of all prepared MDF composites.

This diploma thesis deals with preparation and characterization of aqueous solutions of polyvinyl alcohol suitable for electrospinning. In the theoretical part method of electrospinning is described, including parameters which influence this process. Literary research also includes a chapter about rheology, which deals with the rheological properties of polymers, specifically PVA. The experimental part describes the preparation and rheological study of of aqueous solutions of polyvinyl alcohol, which were then spun. The morphology of prepared nanofibers was studied by using scanning electron microscopy (SEM). The effect of molecular weight, the solvent, concentration of solution, rheological properties, electrical conductivity and surface tension on the spinability, diameter and morphology of nanofibers is discussed.

Im Rahmen des Transferprojektes T01 „Textilbeschichtung mit hochviskosen Massen“ des Sonderforschungsbereiches 532 (SFB 532) wird die Realisierung und Bewertung eines integrierten Beschichtungskonzeptes zur nachhaltigen Verbesserung der Tragfähigkeit von textilbewehrten Betonbauteilen an der RWTH Aachen University untersucht. Dazu wird eine neue Auftragstechnik für hochviskose Beschichtungsmassen entwickelt, die eine vollständige Penetration von Multifilamentgarnen mit großen Garntitern und einer hohen Anzahl an Filamenten in textilen Gelegen erzielt. Des Weiteren werden aktive Beschichtungsmassen auf der Basis von Polyvinylalkohol-Zement-Compositen, die eine homogene Anbindung aller Einzelfilamente an die Zementmatrix ermöglichen, erforscht.

Pelvic floor disorder is an emerging research area and is highlighted in many pelvic floor studies. Assessment methods for this type of injury are lacking and new methods for prevention and diagnosis are needed. Pelvic floor disorders are common among women and can lead to suffering for the patient. Levator ani muscle injuries are the main cause for pelvic floor disorders. This muscle group is an anisotropic skeletal muscle that helps support the pelvic viscera. Assessment of this muscle is difficult due to its complex geometry and location. Therefore, two muscle phantoms were constructed to mimic different properties of the levator ani muscle. The muscle phantoms provided more availability and a more controlled setting. The muscle phantoms were examined using ultrasound-based shear wave elastography which is an elastography method that can help determine the elasticity of tissue. A PVA-graphite phantom and a water-based gelatine-graphite phantom, both with fishing lines network as fibers for anisotropy, were constructed in this project. Shear wave elastography results of the PVA phantom indicated no anisotropy but visually resembled a muscle. Although not achieving anisotropy, the shear modulus of the PVA did match the shear modulus of skeletal muscle tissue. Shear wave elastography results of the gelatine phantom indicated anisotropy but visually did not resemble a muscle due to the low shear modulus of the gelatine. A 3D model of the female bony pelvis, that was provided for this project, was measured, and compared with reference value of previous study for future construction and 3D printing of the model. Results of measurements showed similarities between the 3D model and the female pelvis except for the sagittal outlet which had a deviant value. For future work, the muscle phantom can be developed by applying the complex geometry of the levator ani muscle, assembly of the muscle phantom, and the 3D rendering of the pelvis. The combination of these two parts provides a more complete phantom where shear wave elastography can be applied in the same way as in female patients. / Bäckenbottenbesvär är ett framväxande forskningsområde och lyfts fram i många bäckenbottenstudier. Bedömningsmetoder för denna typ av skador saknas och det behövs nya metoder för förebyggande och diagnostik. Bäckenbottenbesvär är vanliga bland kvinnor och kan leda till lidande för patienten. Levator ani muskelskador är den främsta orsaken till bäckenbottensjukdomar. Denna muskelgrupp är en anisotrop skelettmuskel som hjälper till att stödja inälvorna i bäckenet. Bedömning av denna muskel är svår på grund av dess komplexa geometri och läge. Därför konstruerades två muskelfantomer för att efterlikna olika egenskaper hos levator ani-muskeln. Muskelfantomerna gav mer tillgänglighet och en mer kontrollerad inställning. Muskelfantomerna undersöktes med hjälp av ultraljudsbaserad skjuvvågselastografi som är en metod som kan hjälpa till att bestämma vävnadens elasticitet. En PVA-grafitfantom och en vattenbaserad gelatin-grafitfantom, båda med fiskelinsnätverk som fibrer för anisotropi, konstruerades i detta projekt. Resultat från skjuvvågselastografi på PVA-fantomen indikerade ingen anisotropi, men liknade visuellt en muskel. Även då anisotropi inte uppnåddes, så matchade skjuvmodulen för PVA skjuvmodulen för skelettmuskelvävnad. Resultat från skjuvvågselastografi på gelatinfantomen indikerade anisotropi dock visade resultatet ingen visuell liknelse av en skelettmuskel på grund av gelatinets låga skjuvmodul. En 3D modell av bäckenbenet, som förseddes det här projektet, mättes och jämfördes med referensvärde av tidigare studie för framtid 3D friformsframställning av modellen. Resultat av mätningar visade på liknelser mellan 3D modellen och det kvinnliga bäckenbenet förutom sagittal outlet som hade ett avvikande värde. Inför fortsättning av det här projektet kan en utveckling av muskel fantomen ske genom applicering av den komplexa geometrin hos levator ani muskeln samt sammansättning av muskel fantomen och 3D framställningen av bäckenbenet. Sammansättningen av dessa två delar ger en mer komplett fantom där skjuvvågselastografi kan appliceras på samma sätt som hos kvinnliga patienter. / Ja

In this thesis the possibilities of using capillary electrophoresis as a separation technique for analysis of proteins and microbubbles is presented. A complete analytical process consists of five necessary steps of which one is the actual analysis step. For this step a suitable analytical technique is needed. Capillary electrophoresis (CE) is one of the common analytical separation techniques used for analysis of a diversity of analytes, and can be both used in routine analysis and for research purposes. The reason for using CE, compared to other liquid-based separation techniques, is mainly short analysis time, high resolution, and negligible sample volumes and solvent waste. Depending on the characteristics of the analytes, and the sample matrix, different modes of CE can be used, where capillary zone electrophoresis (CZE) is the most employed one. The basic principle of CZE is separation of the analytes due to differences in total mobility, which is dependent on the charge and size of the analytes, and the electroosmotic flow (EOF). The EOF can be controlled by several parameters e.g. choice of background electrolyte (BGE), and the optimization of the parameters has been discussed throughout the thesis. To improve the properties of the BGE, an ethylammonium nitrate (EAN) water solution was used as BGE for CE analysis in Paper I. The precision of the EOF with this method was determined by adjusting the pH of the BGE, the concentration of EAN in the BGE, and the electric field. Model proteins were thereafter analysed using the optimal parameters yielding a precision sufficient for routine control. One example of the applications of CE is separation of novel contrast agents, which consist of polyvinyl alcohol microbubbles (PVA-MBs). In Paper II, a method for analysis of PVA-MBs in biological samples using CE with UV-detection was developed. It was also established that intact PVA-MBs could be distinguished from ultrasound degraded PVA-MBs in the same set-up. / <p>QC 20171012</p>

Current research within the field of ultrasound contrast agents (UCAs) aims at developing capsules which are not only acoustically active, but also have a chemically modifiable surface. This enables use in new areas, including targeted drug delivery and theranostics. For such purposes, air-filled microbubbles (MBs) with a polyvinyl alcohol (PVA) shell are being studied. Ultrasound imaging velocimetry (UIV) is a technique used to evaluate various types of liquid flows by tracking patterns caused by UCAs across ultrasound images, and has shown great potential for flow measurements in terms of accuracy. The aim of this thesis was to implement a basic UIV program in Matlab to investigate the flow behavior of air-filled PVA MBs being pumped through a phantom, mimicking a blood vessel. The images were acquired using the programmable Verasonics research system by plane wave imaging with coherent compounding, and UIV was implemented as a post-processing technique. Three parameters were varied to study how the UIV performance and flow behavior of the MBs were affected: the concentration of MBs, the flow velocity, and the transducer voltage. The resulting velocity vector fields showed that it is possible to track PVA MBs using the implemented UIV program, and that the concentration 5·106 MBs/ml gave the best results out of the five concentrations tested. The generated velocity vector fields indicated a turbulent and pulsatile flow behavior, which was in line with the predicted flow behavior, although there was a disparity between the measured average flow velocity of the MBs and the predicted flow velocity. It was also observed that the MBs were increasingly pushed in the axial direction with increasing voltage, as according to theory. Even though a more advanced UIV algorithm could improve the accuracy of the velocity measurements, the results show possible use of air-filled PVA MBs in combination with UIV. / Nuvarande forskning inom ultraljudskontrastmedel syftar till att utveckla kapslar som inte bara är akustiskt aktiva, utan som även har en kemiskt modifierbar yta. Detta möjliggör användning inom nya områden, så som målinriktade läkemedel och theanostics. För detta syfte studeras luftfyllda mikrobubblor med ett skal av polyvinylalkohol (PVA). Ultrasound imaging velocimetry (UIV) är en teknik som används för att analysera olika typer av vätskeflöden genom att spåra mönster orsakade av ultraljudskontrastmedel över ett antal ultraljudsbilder. Metoden har visats ha stor potential för flödesmätningar, och hög noggrannhet har uppnåtts. Detta projekt syftade till att implementera ett grundläggande UIV-program i Matlab för att undersöka flödesbeteenden hos luftfyllda PVA-mikrobubblor som pumpas genom en modell av ett blodkärl. Ultraljudsbilderna togs med hjälp av det programmerbara forskningssystemet Verasonics, genom att använda planvågsavbildning och coherent compounding, och UIV implementerades som ett efterbearbetningsprogram. Tre parametrar varierades för att studera hur prestandan av UIV-programmet och flödesbeteendet hos mikrobubblorna påverkades: koncentrationen av mikrobubblor, flödeshastigheten, och spänningsamplituden hos ultraljudsproben. De resulterande hastighetsvektorfälten visade det möjligt att evaluera flödesbeteenden hos PVA-mikrobubblor med hjälp av det implementerade UIV-programmet. Bäst resultat erhölls genom att använda koncentrationen 5·106 mikrobubblor/ml, av de fem testade koncentrationerna. De genererade hastighetsvektorfälten indikerade ett turbulent och pulserande flöde, vilket överensstämde med teorin, trots att det fanns skillnader mellan genomsnittliga uppmätta flödeshastigheter och den beräknade flödeshastigheten. Det kunde också observeras att mikrobubblorna trycktes i den axiella riktningen när spänningsamplituden ökade, vilket överensstämde med teorin. Trots att metodens noggrannhet skulle kunna ökas genom att använda ett mer avancerat UIV-program, visade resultaten på möjligheten att använda luftfyllda PVA-mikrobubblor i kombination med UIV.

A artrose, também chamada de osteoartrose ou osteoartrite (OA), é a terceira doença de maior incidência no Mundo. Nesse trabalho, buscou-se criar uma lesão osteocartilaginosa em joelhos de ratos Wistar machos com seis meses de vida, objetivando constituir um modelo animal para estudo da OA humana e, a partir desse modelo, avaliar biomateriais de forma isolada ou associados entre si e avaliados quanto à sua segurança biológica e potencial de reparação tecidual. Além disto, foi analisado o efeito reparador de células-tronco mesenquimais da polpa do dente de leite humano (MSC) isoladamente e em associação com o biomaterial formado por: Titânio + Poli Vinil Álcool + Ac. Hialurônico, nesse estudo denominado de TRIGEL (TRG). O Ac. Hialurônico (HA), por suas propriedades visco elásticas, o pó de Titânio (Ti), devido às suas propriedades biológicas únicas de ostoeintegração e o polímero Poli Vinil Álcool (PVA), com suas propriedades hidrofílicas, promovendo a formação do Hidrogel, os quais associados entre si formam um compósito, o TRG, que foi aplicado sobre uma lesão padrão no joelho da pata pélvica direita de ratos Wistar machos de seis meses de idade. Para a obtenção da lesão padrão, os animais foram divididos em três grupos de cincoanimais e cada grupo foi submetido a uma intervenção cirúrgica em seus joelhos direitos, utilizando três técnicas cirúrgicas diferentes, a saber: Grupo (I): Remoção cirúrgica dos meniscos medial e lateral mais perfuração do platô tibial seguido da aspiração da medula óssea através dessa perfuração por meio de seringa e agulha. Grupo (II): Remoção dos meniscos mais perfuração, sem aspiração, Grupo (III): Apenas a perfuração. Todos os animais foram autopsiados após 30 dias. Os joelhos dos quinze animais que constituíam os três grupos foram devidamente catalogados e enviados para a empresa Histotech, para a confecção das lâminas, tendo sido eleito, por análise histológica, o Grupo (I), por demonstrar menor reparo tecidual espontâneo. Em tese, o TRG teria as seguintes propriedades: Uma fonte de reparação tecidual (visco terapia) dada pelo HA e a capacidade amortecedora e carreadora de células-tronco do polímero PVA, que se hidrata, formando o hidrogel. O Ti, pela sua propriedade de osteointegração formaria um tampão sobre as áreas de matriz óssea exposta o que possibilitaria o afluxo de novos condrócitos, que também pode ocorrer pela ação das células-tronco. Livrar a superfície articular das áreas com exposição da matriz óssea é fundamental para o bloqueio das proteases que perpetuam a fisiopatologia da OA. Após tratamento estatístico dos diversos ensaios, utilizando-se os diversos biomateriais no tratamento da lesão, o TRG foi o biomaterial que apresentou o melhor resultado de força entre os grupos. No estudo histológico, foi evidenciada a presença de tecido cartilaginoso supra- lesional, o que só ocorreu nos animais dos grupos que receberam: apenas TRG, TRG associado com células-tronco e aquele que recebeu apenas MSCs. No entanto, mais estudos, com animais de maior porte e mais velhos, devem ser realizados para melhor analisar a segurança e o potencial terapêutico do compósito Trigel. / Osteoarthritis, or osteoarthritis (OA) is the third most debilitating disease in the world. In this study, we attempted to create an osteocartilaginous lesion in the knees of six months old male Wistar rats, aiming to constitute an animal model for the study of human OA and to use this model to evaluate the therapeutic potential of biomaterials, which are already well known for their biocompatibility properties in the clinical practice. The biomaterials were used in isolation or associated with each other and then evaluated for their biological safety and tissue repair capacity. Mesenchymal stem cells, obtained from human dental pulp from deciduous teeth (MSC) were evaluated alone and in association with the biomaterial formed by: Titanium + Poly Vinyl Alcohol + Ac. Hyaluronic, here called TRIGEL (TRG). Due to its visco-elastic properties, the Ti powder, due to its unique biological properties of ostointegration and the polymer PVA, with its hydrophylic properties, forming a hydrogel, were associated to form the composite named TRIGEL, (TRG), which was applied to a standard knee injury of the right hind leg of male Wistar rats. In order to elect the standard lesion, the animals were divided into three groups with five animals each and each group underwent a surgical intervention in their right knees, with three different surgical techniques being applied, namely: Group (1): Surgical removal ofmedial and lateral meniscus plus perforation of the tibial plateau, followed by aspiration of the bone marrow through this perforation using syringe and needle. Group (2): Removal of the meniscus plus perforation, without aspiration, Group (3): Drilling only. All groups were autopsied 30 days after the procedure and all groups were autopsied at 30 days post-procedure. The knees of the 15 animals that constituted the three groups were analyzed histologically and Group (1) (meniscus removed, perforated and aspirated), was elected as the standard lesion since it demonstrated less spontaneous tissue repair. TRG has the following properties: HA is used as a source of tissue repair (visco therapy) and hydration of the polymer; PVA, forms a hydrogel\", with damping action and as a stem cells carrier, whereas Ti was used due to its ósseo-integration, which would allow coating of the exposed bone matrix and this intra-osseous osteo-integration response would form an intercalating buffer. The healthy cartilage surfaces around this structural buffer would allow the reception of new chondrocytes or the action of the cells on TRG properties. Freeing the articular surface of the areas with bone matrix exposure is critical for blocking the proteases that perpetuate the pathophysiology of OA. In the various biomaterial tests in the treatment of the standard lesions, TRG was statistically shown to be the one that better mimicked the non-injured group. The histological study demonstrated the presence of a supra-lesional cartilagenous tissue, which only occurred in the groups which received: only TRG, mesenchymal stem cells associated with TRG and that which received only MSCs. However, further studies with larger and older animals should be pursued to better assess the safety and therapeutic potential of the Trigel composite.