Manufacturing techniques and surface engineering of polymer based nanoparticles for targeted drug delivery to cancer

The evolution of polymer based nanoparticles as a drug delivery carrier via pharmaceutical nano/microencapsulation has greatly promoted the development of nano- and micro-medicine in the past few decades. Poly(lactide-co-glycolide) (PLGA) and chitosan, which are biodegradable and biocompatible polymers, have been approved by both the Food & Drug Administration (FDA) and European Medicine Agency (EMA), making them ideal biomaterials that can be advanced from laboratory development to clinical oral and parental administrations. PLGA and chitosan encapsulated nanoparticles (NPs) have successfully been developed as new oral drug delivery systems with demonstrated high efficacy. This review aims to provide a comprehensive overview of the fabrication of PLGA and chitosan particulate systems using nano/microencapsulation methods, the current progress and the future outlooks of the nanoparticulate drug delivery systems. Especially, we focus on the formulations and nano/micro-encapsulation techniques using top-down techniques. It also addresses how the different phases including the organic and aqueous ones in the emulsion system interact with each other and subsequently influence the properties of the drug delivery system. Besides, surface modification strategies which can effectively engineer intrinsic physicochemical properties are summarised. Finally, future perspectives and potential directions of PLGA and chitosan nano/microencapsulated drug systems are outlined.

Improving hydrogen storage properties of magnesium based alloys by equal channel angular pressing

Equal channel angular pressing was applied to a commercial magnesium alloy ZK60 in order to improve its hydrogen storage properties. The microstructure refinement and increase in the density of crystal lattice defects caused by equal channel angular pressing increase hydrogen desorption pressure, change the slope of the pressure plateau in pressure-composition isotherms, decrease the pressure hysteresis, and accelerate the hydrogen desorption kinetics. It is argued that a proper design of the defect structure of materials is a key element in the search for economically viable and environmentally acceptable solutions for mobile hydrogen storage based on metal hydrides.

Applications of electrospun nanofibers for electronic devices

In recent decades, electrospinning of nanofibers has progressed very rapidly in both scientific and technological aspects, and electrospun nanofibers have shown enormous potential for various applications. In particular, electrospun nanofibers have significantly enhanced the application performance of many electronic devices, such as solar cells, mechanical-to-electric energy harvesters, rechargeable batteries, supercapacitors, sensors, field-effect transistors, diodes, photodetectors, and electrochromic devices. This chapter provides a comprehensive summary on the recent progress in the application of electrospun nanofibers in electronic devices.

Comparison of Computer-Based and Optical Face Recognition Paradigms

The main objectives of this thesis are to validate an improved principal components analysis (IPCA) algorithm on images; designing and simulating a digital model for image compression, face recognition and image detection by using a principal components analysis (PCA) algorithm and the IPCA algorithm; designing and simulating an optical model for face recognition and object detection by using the joint transform correlator (JTC); establishing detection and recognition thresholds for each model; comparing between the performance of the PCA algorithm and the performance of the IPCA algorithm in compression, recognition and, detection; and comparing between the performance of the digital model and the performance of the optical model in recognition and detection. The MATLAB © software was used for simulating the models. PCA is a technique used for identifying patterns in data and representing the data in order to highlight any similarities or differences. The identification of patterns in data of high dimensions (more than three dimensions) is too difficult because the graphical representation of data is impossible. Therefore, PCA is a powerful method for analyzing data. IPCA is another statistical tool for identifying patterns in data. It uses information theory for improving PCA. The joint transform correlator (JTC) is an optical correlator used for synthesizing a frequency plane filter for coherent optical systems. The IPCA algorithm, in general, behaves better than the PCA algorithm in the most of the applications. It is better than the PCA algorithm in image compression because it obtains higher compression, more accurate reconstruction, and faster processing speed with acceptable errors; in addition, it is better than the PCA algorithm in real-time image detection due to the fact that it achieves the smallest error rate as well as remarkable speed. On the other hand, the PCA algorithm performs better than the IPCA algorithm in face recognition because it offers an acceptable error rate, easy calculation, and a reasonable speed. Finally, in detection and recognition, the performance of the digital model is better than the performance of the optical model.

Development of Physics-based Models and Design Optimization of Power Electronic Conversion Systems

The main objective for physics based modeling of the power converter components is to design the whole converter with respect to physical and operational constraints. Therefore, all the elements and components of the energy conversion system are modeled numerically and combined together to achieve the whole system behavioral model. Previously proposed high frequency (HF) models of power converters are based on circuit models that are only related to the parasitic inner parameters of the power devices and the connections between the components. This dissertation aims to obtain appropriate physics-based models for power conversion systems, which not only can represent the steady state behavior of the components, but also can predict their high frequency characteristics. The developed physics-based model would represent the physical device with a high level of accuracy in predicting its operating condition. The proposed physics-based model enables us to accurately develop components such as; effective EMI filters, switching algorithms and circuit topologies [7]. One of the applications of the developed modeling technique is design of new sets of topologies for high-frequency, high efficiency converters for variable speed drives. The main advantage of the modeling method, presented in this dissertation, is the practical design of an inverter for high power applications with the ability to overcome the blocking voltage limitations of available power semiconductor devices. Another advantage is selection of the best matching topology with inherent reduction of switching losses which can be utilized to improve the overall efficiency. The physics-based modeling approach, in this dissertation, makes it possible to design any power electronic conversion system to meet electromagnetic standards and design constraints. This includes physical characteristics such as; decreasing the size and weight of the package, optimized interactions with the neighboring components and higher power density. In addition, the electromagnetic behaviors and signatures can be evaluated including the study of conducted and radiated EMI interactions in addition to the design of attenuation measures and enclosures.

Meshfree Method for Prediction of Thermal Properties of Porous Ceramic Materials

In the presented thesis work, meshfree method with distance fields is applied to create a novel computational approach which enables inclusion of the realistic geometric models of the microstructure and liberates Finite Element Analysis(FEA) from thedependance on and limitations of meshing of fine microstructural feature such as splats and porosity.Manufacturing processes of ceramics produce materials with complex porosity microstructure.Geometry of pores, their size and location substantially affect macro scale physical properties of the material. Complex structure and geometry of the pores severely limit application of modern Finite Element Analysis methods because they require construction of spatial grids (meshes) that conform to the geometric shape of the structure. As a result, there are virtually no effective tools available for predicting overall mechanical and thermal properties of porous materials based on their microstructure. This thesis is a separate handling and controls of geometric and physical computational models that are seamlessly combined at solution run time. Using the proposedapproach we will determine the effective thermal conductivity tensor of real porous ceramic materials featuring both isotropic and anisotropic thermal properties. This work involved development and implementation of numerical algorithms, data structure, and software.

Acceptance of smartphone-based mobile shopping:mobile benefits, customer characteristics, perceived risk and the impact of application context

Despite their generally increasing use, the adoption of mobile shopping applications often differs across purchase contexts. In order to advance our understanding of smartphone-based mobile shopping acceptance, this study integrates and extends existing approaches from technology acceptance literature by examining two previously underexplored aspects. Firstly, the study examines the impact of different mobile and personal benefits (instant connectivity, contextual value and hedonic motivation), customer characteristics (habit) and risk facets (financial, performance, and security risk) as antecedents of mobile shopping acceptance. Secondly, it is assumed that several acceptance drivers differ in relevance subject to the perception of three mobile shopping characteristics (location sensitivity, time criticality, and extent of control), while other drivers are assumed to matter independent of the context. Based on a dataset of 410 smartphone shoppers, empirical results demonstrate that several acceptance predictors are associated with ease of use and usefulness, which in turn affect intentional and behavioral outcomes. Furthermore, the extent to which risks and benefits impact ease of use and usefulness is influenced by the three contextual characteristics. From a managerial perspective, results show which factors to consider in the development of mobile shopping applications and in which different application contexts they matter.

Effects of plasticizing and crosslinking on the mechanical and barrier properties of coatings based on blends of starch and poly(vinyl alcohol)

In the last decades, intensive research has been carried out in order to replace oil-based polymers with bio-based polymers due to growing environmental concerns. So far, most of the barrier materials used in food packaging are petroleum-based materials. The purpose of the barrier is to protect the packaged food from oxygen, water vapour, water and fat. The mechanical and barrier properties of coatings based on starch-plasticizer and starch-poly(vinyl alcohol) (PVOH)-plasticizer blends have been studied in the work described in this thesis. The plasticizers used were glycerol, polyethylene glycol and citric acid. In a second step, polyethylene coatings were extruded onto paperboard pre-coated with a starch-PVOH-plasticizer blend. The addition of PVOH to the starch increased the flexibility of the film. Curing of the film led to a decrease in flexibility and an increase in tensile strength. The flexibility of the starch-PVOH films was increased more when glycerol or polyethylene glycol was added than citric acid. The storage modulus of the starch-PVOH films containing citric acid increased substantially at high temperature. It was seen that the addition of polyethylene glycol or citric acid to the starch-PVOH blend resulted in an enrichment of PVOH at the surface of the films. Tensile tests on the films indicated that citric acid acted as a compatibilizer and increased the compatibility of the starch and PVOH in the blend. The addition of citric acid to the coating recipe substantially decreased the water vapour transmission rate through the starch-PVOH coated paperboard, which indicated that citric acid acts as a cross-linker for starch and/or PVOH. The starch-PVOH coatings containing citric acid showed oxygen-barrier properties similar to those of pure PVOH or of a starch-PVOH blend without plasticizer when four coating layers were applied on a paperboard. The oxygen-barrier properties of coatings based on a starch-PVOH blend containing citric acid indicated a cross-linking and increase in compatibility of the starch-PVOH blends. Polyethylene extrusion coating on a pre-coated paperboard resulted in a clear reduction in the oxygen transmission rate for all the pre-coating formulations containing plasticizers. The addition of a plasticizer to the pre-coating reduced the adhesion of polyethylene to pre-coated board. Polyethylene extrusion coating gave a board with a lower oxygen transmission rate when the paperboard was pre-coated with a polyethylene-glycol-containing formulation than with a citric-acid-containing formulation. The addition of polyethylene glycol to pre-coatings indicated an increase in wetting of the pre-coated paperboard by the polyethylene melt, and this may have sealed the small defects in the pre-coating leading to low oxygen transmission rate. The increase in brittleness of starch-PVOH films containing citric acid at a high temperature seemed to have a dominating effect on the barrier properties developed by the extrusion coating process. 

Mechanical characterisation of advanced biomedical materials

Biocompatible Ti, Nb and Mo alloy was fabricated in search of a novel biomaterial for bone regeneration. A series of Ti-based alloys were prepared from elemental powders via powder metallurgy technique. The effects of ball milling variables and the agglomerated particles on mechanical properties of the bulk and porous structures were investigated.

Validation of thigh-based accelerometer estimates of postural allocation in 5-12 year-olds

OBJECTIVES: To validate activPAL3™ (AP3) for classifying postural allocation, estimating time spent in postures and examining the number of breaks in sedentary behaviour (SB) in 5-12 year-olds. DESIGN: Laboratory-based validation study. METHODS: Fifty-seven children completed 15 sedentary, light- and moderate-to-vigorous intensity activities. Direct observation (DO) was used as the criterion measure. The accuracy of AP3 was examined using a confusion matrix, equivalence testing, Bland-Altman procedures and a paired t-test for 5-8y and 9-12y. RESULTS: Sensitivity of AP3 was 86.8%, 82.5% and 85.3% for sitting/lying, standing, and stepping, respectively, in 5-8y and 95.3%, 81.5% and 85.1%, respectively, in 9-12y. Time estimates of AP3 were equivalent to DO for sitting/lying in 9-12y and stepping in all ages, but not for sitting/lying in 5-12y and standing in all ages. Underestimation of sitting/lying time was smaller in 9-12y (1.4%, limits of agreement [LoA]: -13.8 to 11.1%) compared to 5-8y (12.6%, LoA: -39.8 to 14.7%). Underestimation for stepping time was small (5-8y: 6.5%, LoA: -18.3 to 5.3%; 9-12y: 7.6%, LoA: -16.8 to 1.6%). Considerable overestimation was found for standing (5-8y: 36.8%, LoA: -16.3 to 89.8%; 9-12y: 19.3%, LoA: -1.6 to 36.9%). SB breaks were significantly overestimated (5-8y: 53.2%, 9-12y: 28.3%, p<0.001). CONCLUSIONS: AP3 showed acceptable accuracy for classifying postures, however estimates of time spent standing were consistently overestimated and individual error was considerable. Estimates of sitting/lying were more accurate for 9-12y. Stepping time was accurately estimated for all ages. SB breaks were significantly overestimated, although the absolute difference was larger in 5-8y. Surveillance applications of AP3 would be acceptable, however, individual level applications might be less accurate.

Effect of elemental metals and strontium coated surface on biocompatibility of titanium-based biomaterials.

This thesis developed a two-step hydrothermal treatment to modify titanium materials,which is very useful for improving the osteointegration of titanium materials. The cellular responses of SaOS2 cells to seventeen element discs were assessed across the different elements. The cell responses to different elemental metals showed that using appropriate concentrations of these elements are critical for designing good Ti-based biomaterials for implants due to the dose-dependent cytotoxicity of each element.

Development of nanostructured polymeric materials using polymerizable lyotropic liquid crystals.

This thesis was focused on the development of nanostructured polymers for CO2 capture and energy storage applications, using polymerizable lyotropic liquid crystal. A combination of polarized optical microscopy, differential scanning calorimetry and Small-angle x-ray scattering has been used to characterize and understand the structure retention of these systems during photo-polymerization.

Applications of perceptual sparse representation (Spikegram) for copyright protection of audio signals

Chaque année, le piratage mondial de la musique coûte plusieurs milliards de dollars en pertes économiques, pertes d’emplois et pertes de gains des travailleurs ainsi que la perte de millions de dollars en recettes fiscales. La plupart du piratage de la musique est dû à la croissance rapide et à la facilité des technologies actuelles pour la copie, le partage, la manipulation et la distribution de données musicales [Domingo, 2015], [Siwek, 2007]. Le tatouage des signaux sonores a été proposé pour protéger les droit des auteurs et pour permettre la localisation des instants où le signal sonore a été falsifié. Dans cette thèse, nous proposons d’utiliser la représentation parcimonieuse bio-inspirée par graphe de décharges (spikegramme), pour concevoir une nouvelle méthode permettant la localisation de la falsification dans les signaux sonores. Aussi, une nouvelle méthode de protection du droit d’auteur. Finalement, une nouvelle attaque perceptuelle, en utilisant le spikegramme, pour attaquer des systèmes de tatouage sonore. Nous proposons tout d’abord une technique de localisation des falsifications (‘tampering’) des signaux sonores. Pour cela nous combinons une méthode à spectre étendu modifié (‘modified spread spectrum’, MSS) avec une représentation parcimonieuse. Nous utilisons une technique de poursuite perceptive adaptée (perceptual marching pursuit, PMP [Hossein Najaf-Zadeh, 2008]) pour générer une représentation parcimonieuse (spikegramme) du signal sonore d’entrée qui est invariante au décalage temporel [E. C. Smith, 2006] et qui prend en compte les phénomènes de masquage tels qu’ils sont observés en audition. Un code d’authentification est inséré à l’intérieur des coefficients de la représentation en spikegramme. Puis ceux-ci sont combinés aux seuils de masquage. Le signal tatoué est resynthétisé à partir des coefficients modifiés, et le signal ainsi obtenu est transmis au décodeur. Au décodeur, pour identifier un segment falsifié du signal sonore, les codes d’authentification de tous les segments intacts sont analysés. Si les codes ne peuvent être détectés correctement, on sait qu’alors le segment aura été falsifié. Nous proposons de tatouer selon le principe à spectre étendu (appelé MSS) afin d’obtenir une grande capacité en nombre de bits de tatouage introduits. Dans les situations où il y a désynchronisation entre le codeur et le décodeur, notre méthode permet quand même de détecter des pièces falsifiées. Par rapport à l’état de l’art, notre approche a le taux d’erreur le plus bas pour ce qui est de détecter les pièces falsifiées. Nous avons utilisé le test de l’opinion moyenne (‘MOS’) pour mesurer la qualité des systèmes tatoués. Nous évaluons la méthode de tatouage semi-fragile par le taux d’erreur (nombre de bits erronés divisé par tous les bits soumis) suite à plusieurs attaques. Les résultats confirment la supériorité de notre approche pour la localisation des pièces falsifiées dans les signaux sonores tout en préservant la qualité des signaux. Ensuite nous proposons une nouvelle technique pour la protection des signaux sonores. Cette technique est basée sur la représentation par spikegrammes des signaux sonores et utilise deux dictionnaires (TDA pour Two-Dictionary Approach). Le spikegramme est utilisé pour coder le signal hôte en utilisant un dictionnaire de filtres gammatones. Pour le tatouage, nous utilisons deux dictionnaires différents qui sont sélectionnés en fonction du bit d’entrée à tatouer et du contenu du signal. Notre approche trouve les gammatones appropriés (appelés noyaux de tatouage) sur la base de la valeur du bit à tatouer, et incorpore les bits de tatouage dans la phase des gammatones du tatouage. De plus, il est montré que la TDA est libre d’erreur dans le cas d’aucune situation d’attaque. Il est démontré que la décorrélation des noyaux de tatouage permet la conception d’une méthode de tatouage sonore très robuste. Les expériences ont montré la meilleure robustesse pour la méthode proposée lorsque le signal tatoué est corrompu par une compression MP3 à 32 kbits par seconde avec une charge utile de 56.5 bps par rapport à plusieurs techniques récentes. De plus nous avons étudié la robustesse du tatouage lorsque les nouveaux codec USAC (Unified Audion and Speech Coding) à 24kbps sont utilisés. La charge utile est alors comprise entre 5 et 15 bps. Finalement, nous utilisons les spikegrammes pour proposer trois nouvelles méthodes d’attaques. Nous les comparons aux méthodes récentes d’attaques telles que 32 kbps MP3 et 24 kbps USAC. Ces attaques comprennent l’attaque par PMP, l’attaque par bruit inaudible et l’attaque de remplacement parcimonieuse. Dans le cas de l’attaque par PMP, le signal de tatouage est représenté et resynthétisé avec un spikegramme. Dans le cas de l’attaque par bruit inaudible, celui-ci est généré et ajouté aux coefficients du spikegramme. Dans le cas de l’attaque de remplacement parcimonieuse, dans chaque segment du signal, les caractéristiques spectro-temporelles du signal (les décharges temporelles ;‘time spikes’) se trouvent en utilisant le spikegramme et les spikes temporelles et similaires sont remplacés par une autre. Pour comparer l’efficacité des attaques proposées, nous les comparons au décodeur du tatouage à spectre étendu. Il est démontré que l’attaque par remplacement parcimonieux réduit la corrélation normalisée du décodeur de spectre étendu avec un plus grand facteur par rapport à la situation où le décodeur de spectre étendu est attaqué par la transformation MP3 (32 kbps) et 24 kbps USAC.

Stability of clay-based catalysts in contact with water vapour

The search for cleaner processes is one of the major challenges in modern chemical industries. In this context clay derived materials are environmentally friendly catalysts that can be easily tailored to optimize their catalytic activity for a precise reaction of interest. Furthermore, clay-based catalysts can be easily separated, recovered and reused and their versatility, low cost, high catalytic activity and/or selectivity render them very attractive materials. Considering that the stability towards water vapour is a crucial aspect for catalytic performance and reuse of the catalysts, we present a study of the pore structure stability, in the presence of water vapour, of clay catalysts prepared by acid activation with HCl solutions and ion-exchange with sodium, aluminium and iron, from a natural clay collected at Serra de Dentro (Porto Santo Island, Portugal) [1]. For elucidating the influence of water vapour on the pore structure stability, water vapour adsorption- -desorption isotherm, at 298 K, was determined on each sample by gravimetric method as well as n-pentane adsorption−desorption isotherms, at 298 K, which were determined before and after the corresponding water adsorption-desorption isotherms. Prior to the measurements, the samples were outgassed during 5 h at 473 K and the adsorptives were outgassed by repeated freeze–thaw cycles. The results to be reported in the communication allow us to state that, upon contact with water vapour, the less acid activated catalysts suffered some reduction in pore volume reflecting changes in the pore structure, while the more acid activated catalysts and those prepared by ion-exchange presented excellent stability upon one cycle of water vapour adsorption-desorption. The results are corroborated by nitrogen adsorption-desorption isotherms determined, at 77 K, before and after the water and n-pentane adsorption-desorption measurements.

Characterization of traditional raw materials used in housing construction in Huambo Region - Angola

The sustainability of buildings associated to the use of raw earth has motivated the studies and the development of techniques and methods in the context of this type of construction. In the region of Huambo, Angola, these construction techniques are widely used, especially for low-income families who represent the majority of the population. Much of the buildings in Huambo province are built with adobe. Due to the climate in this region, subtropical, hot and humid, with altitudes above 1000 meters and extensive river system, these buildings are particularly vulnerable to the action of water and develop, in many situations, early degradation. The Huambo Province is located in central Angola, has 36 km2 area and approximately 2 million inhabitants. This work aims to evaluate, by conducting in-situ tests, physical and mechanical properties of adobe blocks typically used in the construction of those buildings. The methodology is based on field campaigns where in-situ expeditious tests were performed in soils (smell test, color, touch, brightness, sedimentation, ball, hardness, etc.) and tests on adobes blocks made with traditional procedures, particularly in terms of durability and erodibility (erosion test at Geelong method; evaluation test of wet / dry cycle, applying the New Zealand standards 4297: 1998; 4297: 1998 and 4297: 1999). The results will contribute to the characterization of the geomaterials and methods used in construction with earth in Huambo Province, contributing to the improvement of these sustainable solutions, with a strong presence in this region. The results of this study will also contribute to the proposal of constructive solutions with improved performance characteristics, comfort, safety and durability.