The primary objective of this study was to obtain nano-emulsion containing polyphenolic compounds extracted from sour cherry pomace and to investigate the effect of degritting of polyphenolic concentrates on the encapsulation efficiency and particle size distribution of capsules and emulsions. It was also aimed to study storage and baking stability of the capsules. Extracted polyphenolic concentrate was degritted at 10,000 rpm for 2 min. Purification reduced Sauter mean diameter (D[32]) of concentrated extract from 5.76 &mu / m to 0.41 &mu / m. Unpurified and purified concentrates were freeze dried for 48 h to obtain extracted phenolic powder (EPP) and purified extracted phenolic powder (PEPP), respectively. Powders were entrapped in two types of coating materials which contain 10% maltodextrin (MD) or 8% MD-2% gum arabic (GA). Samples were prepared by ultrasonication (160 W, 50% pulse) for 20 min. Emulsions containing EPP had D[32] of 1.65 and 1.61 &mu / m when they were entrapped in 10% MD and 8% MD-2% GA coating material solutions, respectively. It was possible to obtain nano-emulsions when purification step was performed. Emulsions prepared with PEPP and coated with 10% MD and 8% MD-2% GA had D[32] of 0.396 and 0.334 &mu / m, respectively. Encapsulation efficiency of the capsules increased significantly from 86.07-88.45% to 98.01-98.29% by means of degritting (p&le / 0.001). Loss of total phenolic content during storage at 43% and 85% relative humidities was smaller for encapsulated powders when compared to powders not entrapped in coating material. In addition, encapsulation significantly increased retention of phenolic compounds from 15.1-22.2% to 30.4-30.7% during baking (p&le / 0.05).

The effects of two types of cryopreservation, conventional freezing and vitrification, on the in vitro and in vivo function of a pancreatic substitute were investigated. Conventional freezing uses low concentrations of cryoprotective agents (CPAs), slow cooling and rapid warming and allows ice formation. Vitrification requires high concentrations of CPAs coupled with rapid cooling and warming to achieve a vitreous, or ice-free, state. A previously published mathematical model describing the mass transfer of CPAs through the alginate matrix of the substitute and the cell membrane was expanded to incorporate heat transfer as well as CPA cytotoxicity. Our results indicate that temperature of exposure is the most critical parameter for the proper design of CPA addition and removal protocols. The use of a mathematical model is critical to ensure CPA equilibration and minimize CPA exposure. Properly designed CPA addition and removal protocols were used for vitrification. The effects of cryopreservation on the biomaterial and the cellular function of a pancreatic substitute consisting of murine insulinomas encapsulated in calcium alginate/poly-L-lysine/alginate beads were assessed. In vitro results indicate that both vitrification and conventionally frozen perform comparably to fresh. However, in vivo studies reveal that vitrified beads perform worse than both conventionally frozen and fresh beads. With adjustments, it may be possible to improve the performance of the vitrified beads. Nevertheless, for this pancreatic substitute, conventional freezing is the better method and allows successful cryopreservation.

Puisque le cancer du sein reste l'une des premières causes de mortalité chez la femme, le diagnostic et le traitement de cette maladie ont plus que jamais besoin d'être améliorés. L'intérêt des composés organométalliques robustes, ciblant le récepteur des œstrogènes, est qu'on peut moduler leurs applications en fonction du métal introduit. Pour la première fois, une entité organométallique stable et lipophilique, le groupement ferrocénique, a été substituée à la chaîne-clé aminée du squelette triphényléthylénique de l'antiœstrogène hydroxytamoxifène, tenue pour être responsable de l'activité du médicament. La chaîne amine des ferrocifènes a également été remplacée par une fonction acide carboxylique. Différentes variations structurelles ont été explorées, afin d'optimiser les propriétés biologiques de ces composés ferrocéniques, qui peuvent être cytotoxiques. Cependant certains de ces composés ont non seulement une activité antiproliférative, mais peuvent aussi servir de précurseurs stables pour la synthèse de radiopharmaceutiques. Il est en effet possible de remplacer le Fer par le Rhénium ou le Technétium suivant la réaction d'échange de ligands, qui est chimiosélective. Les composés organométalliques résultants peuvent être de bons agents ciblés pour la radiothérapie (188Re) ou pour l'imagerie médicale (99mTc). Finalement, afin d'améliorer leur biodisponibilité, deux composés ferrocéniques ont été incorporés dans deux types de nanovecteurs : les nanosphères et les nanocapsules. Leur petite taille et la libération tardive des principes actifs, associés à une activité apoptotique exacerbée sont en accord avec une persistance accrue dans la circulation sanguine, et une activité anticancéreuse prometteuse.

Thèse doctorat : Informatique : INSA LYON : 2002. / Titre provenant de l'écran-titre. Bibliogr. p. 144-149.

Thèse de doctorat : Chimie et physico-chimie des polymères : Paris 12 : 2005. / Version électronique uniquement consultable au sein de l'Université Paris 12 (Intranet). Titre provenant de l'écran-titre. Bibliogr. : 281 réf.

This research focuses on the modeling of dendrimer molecules for their application as delivery vectors within drug and gene therapy systems. We examine how the architecture and composition of dendrimers affect their drug and gene binding efficacies along with their interactions with anionic bilayers. We specifically focus on how the weakly basic nature of dendrimer monomers and the addition of neutral grafts to dendrimer surface groups affect their interactions with drugs, linear polyelectrolytes, and bilayers. By using polymer self-consistent field theory (SCFT) to model such systems, we develop a computationally efficient means to provide physical insights into these systems, which are intended to guide dendrimer design for delivery applications.We study the conformational properties of weakly basic (annealed) polyelectrolyte dendrimers by developing a SCFT model that explicitly accounts for the acid-base equilibrium reaction of the weakly basic monomers. We specifically focus on the role of local counterion concentration upon the charge and conformations of the annealed polyelectrolyte dendrimers. We compare our results to existing polymer scaling theories and develop a strong stretching theory for the dendrimer molecules.We extend the previous study to model the interactions between weakly basic dendrimers and weakly acidic, hydrophobic drug molecules. We specifically examine the effects of excluded volume, electrostatic, and enthalpic interactions on the binding efficacies between dendrimers and drugs under a variety of dendrimer generations, solution pOH conditions, drug sizes, and Bjerrum length values.We study the role of neutral dendrimer grafts on the conformations and drug binding efficacies of dendrimers. We then elucidate how the observed conformational changes affect the charge of the dendrimers. Furthermore, we examine how the presence of grafts affects the steric, electrostatic, and hydrophobic interactions between the drugs and dendrimers under a variety of solution conditions. We compare our results with the binding efficacies observed for non-grafted dendrimers to delineate the conditions under which the grafted dendrimers are better suited as drug hosts.We include semi-flexible, anionic linear polyelectrolyte (LPE) molecules in our grafted dendrimer SCFT framework to model the interactions between dendrimers and negatively charged genetic materials. Specifically, we examine how neutral dendrimer grafts, LPE stiffness, and solution pOH affect the interactions between dendrimers and LPEs. We then use our SCFT potential fields as input into Monte Carlo simulations in order to determine the dendrimer-LPE potentials of mean force and the resulting loop and tail statistics of the dendrimer-adsorbed LPE chains.We incorporate a negatively charged bilayer into our grafted dendrimer SCFT framework to model dendrimer interactions with a cellular membrane. We specifically examine the role of dendrimer grafting length, solution pH, and membrane tension on such interactions. By comparing our results with SCFT calculations of fixed dendrimer conformations and hard sphere nanoparticles in the presence of membranes, we delineate the role of dendrimer flexibility and porosity on the interactions between dendrimers and anionic bilayers. / text

Predictive models for diffusion-controlled particle dissolution are important for designing advanced and efficient solid products for controlled release applications. A computer-aided modeling framework was developed to derive the effective dissolution rates of multiple particles as the solid surface material eroded gradually into the surrounding liquid phase. The mathematical models were solved with numerical methods using the computational software MATLAB. Results from the models were imported into COMSOL Script to create three-dimensional plots of the particle size data as a function of time. The release model found for the monodispersed particles was manipulated to incorporate polydisperse solids, as these are found more frequently in chemical processes. The program was further developed to calculate the particle size as a function of time for particles encapsulated for use in controlled release. The parameters, such as radius size, coating material and encapsulation thickness, can be altered in the computer models to aid in the design of particles for different desired applications. Simulations produced conversion profiles and three-dimensional visualizations for the dissolution processes. Experiments for the dissolution of citric acid in water were performed using a reaction microcalorimeter to verify results found from the computer models.

This thesis focuses on the forensic analysis of ten full-scale post-tensioned beam specimens after four years of aggressive exposure testing. The research was funded by FHWA and TxDOT. Post-tensioned structures have been under scrutiny due to their vulnerability to corrosion damage. Recent corrosion failures have been traced to inadequate materials and construction procedures. The purpose of this research project is to evaluate the corrosion performance of new and upcoming post-tensioning materials and systems and to determine their suitability for preventing durability issues which were found in older structures. The following variables were tested in the full-scale beam specimens: strand type, duct type, duct coupler type, anchorage type, tendon encapsulation. Non-destructive and destructive testing methods for evaluating corrosion damage were examined. Cost analysis of each material was conducted using tendon quantities from a typical post-tensioned bridge for comparison. Galvanized steel ducts performed poorly, showing substantial pitting and area loss. Plastic ducts were intact, but elevated grout chloride levels indicate that moisture was able to enter the ducts at the locations of couplers and grout vents. Strand corrosion was minor and uniform for all the types which were examined, suggesting that chloride traveled the length of the tendons through strand interstices. Stainless steel strands were nearly corrosion-free. Pourback quality was found to protect anchorages more than galvanization of bearing plates. The electrically isolated tendon did not completely prevent strand corrosion, but the system resulted in much lower chloride concentrations along the tendon than the conventional systems. / text

The capacity of four mineral sorbents to retain arsenic under simulated mature landfill conditions was tested using semi-batch and continuous flow columns. The sorbents tested were Fe-, Ti-, La-, and Zr- based oxi(hydroxides). The Fe sorbent was included as a positive control to compare the release of As from a substrate subject to reduction to those of the, non-sensitive to reduction under typical mature landfill conditions, Ti, La, and Zr media. It has been proved that under mature landfill conditions, As(V) preloaded on ferric sorbents is prompt to be released at high levels. Our results indicate that Ti, La, and Zr sorbents can release As at a similar or higher degree than a ferric sorbent. In a second phase, the capacity of the same sorbents to retain As was evaluated after being subject to polymeric encapsulation in an epoxic resin. Landfill conditions were simulated by use of semi-batch column systems packed with compost and fed with actual landfill leachate. Results obtained indicated that encapsulation highly enhanced As retention of the media under simulated landfill conditions. In our research regarding soil contamination by atmospheric transport from mine tailings, a previously developed deposition forecasting model (DFM) that is designed to model the transport of particulate As and Pb from mine tailing impoundments is verified using dust collection and topsoil measurements. The forecast deposition patterns are compared to dust collected by inverted-disc samplers through gravimetric, chemical composition and lead isotopic analysis. The DFM is capable of predicting dust deposition patterns from the tailings impoundment to the surrounding area. Finally, the bioaccessibility of As and Pb were on samples collected at Iron King Mine Tailing was evaluated through chemical extractions using simulated the gastric and the lung fluids of the human body. Results obtained indicate that extractions using simulated gastric fluid lead to As concentrations one order of magnitude higher to those obtained with lung fluid. For Pb concentration the difference was greater than 2 orders of magnitude.

The objective of the present work is the analysis of coextrusion processes by numerical simulation based on phase-field modeling of stratified confined flows. The study of such flows is motivated by the presence of complex phenomena appearing in a vast range of industrial operational coextrusion conditions due to the differences in the components properties and their viscoelastic behavior. The basic idea in coextrusion is to combine several layers of different polymers in a common die, to form a unique product with enhanced properties. However, the existence of fluid stratification in the die is responsible of a severe distortion of the interface between the fluid components, causing a loss of efficiency for the whole process. Experimental data show that, even if a stratified initial configuration is imposed at the die entry, one fluid eventually encapsulates the other in most of the flow condition analyzed. The intrinsically three-dimensional nature of this phenomenon has required the development of a three-dimensional flow solver based on the finite volume discretization of the Navier-Stokes equations for incompressible and isothermal flow, together with differential nonlinear constitutive equations (Giesekus, PTT models). The presence of two fluid phases is taken into account by a phase field model that implies the solution of an additional scalar equation to describe the evolution of the interface on a fixed Eulerian grid. This model, unlike others of the same family, has a thermodynamic derivation and can be physically interpreted. The proposed method is tested against experimental data and solutions already available in literature and a study of coextrusion in rectangular dies is performed to identify the dependence of encapsulation on the flow parameters