Thèse numérisée par la Division de la gestion de documents et des archives de l'Université de Montréal.

El propósito de la presente tesis doctoral es estudiar el efecto de la degradación térmica, biológica y fotolítica en la polilactida (PLA) para contribuir a la caracterización de este polímero biodegradable bajo diferentes condiciones o entornos. Este polímero procede de fuentes renovables y está considerado un excelente candidato para sustituir a otros materiales poliméricos con escasa degradabilidad. En este estudio se describen los mecanismos que regulan cada tipo de degradación y, lo que es más importante, cómo cada uno de ellos afecta a la variación de la masa molar del PLA. La monitorización del descenso de masa molar de polilactida se realizó tanto mediante Cromatografía de Permeación en Gel (GPC) como por Viscosimetría. Adicionalmente se utilizó la Espectroscopía Infrarroja con Transformada de Fourier (FTIR) para establecer los mecanismos que controlan la degradación y su efecto en la estructura química de la polilactida. Asimismo, se ha determinado el impacto de cada tipo de degradación en la morfología y en las propiedades térmicas y mecánicas del PLA. La Termogravimetría (TGA) permitió monitorizar los cambios en la estabilidad térmica del material debidos a los diferentes tipos degradación, ulilizando parámetros como la temperatura de máxima velocidad de degradación térmica o la energía de activación. El resultado de la bio y la foto degradación en la superficie del material fue evaluado mediante Microscopía Electrónica de Barrido (SEM), observándose únicamente cambios debidos a la degradación biológica. Las propiedades viscoelásticas y térmicas se analizaron mediante Análisis Dinámico-Mecánico-Térmico (DMTA), Calorimetría Diferencial de Barrido (DSC) y Microscopía Óptica (OM). Se ha obtenido que los parámetros más relevantes para discernir las diferencias entre los tres procesos de degradación son los relativos al fenómeno de cristalización. Los resultados muestran que cada degradación está controlada por un mecanismo que afecta de diferente forma a la / Santonja Blasco, L. (2012). Contribution to the study of thermal, biological and photo degradation of polylactide [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/16470 / Palancia

This diploma thesis deals with chemical recyclation polylactide to lactide. In the theory is summarized actual state of knowledge about chemical recyclation of polylactides, their properties, preparations a possibilities of characterization. Experimental part of work verify ethanolysis of PLA withthe samples of granulate, waste filaments and textiles. In the experimental work is suggested an optimalization of alcoholysis to direct yield of oligomer suitable for depolymerization to lactide. This method was verified for 5 different samples of PLA, which 4 of them was made of waste PLA. The time needed for depolymerization was evaluated and the effect of catalysis. Lactide and PLA recyclates was further analyzed by NMR, FTIR, DSC and GPC.

Quartz Crystal Microbalance (QCM) is a sensitive and effective technique to analyze mass changes at the interface between a solid material and a liquid environment. In this Master thesis, QCM was employed for evaluating the interactions between selected degradable polymers and nanodiamond particles (nDP), fibronectin and the growth factor BMP-2.   Many parameters must be adapted to allow QCM measurements involving degradable polymers. These parameters were then tailored to allow QCM measurements with PLA, poly(LLA-co-CL), poly(TMC-D-LA) and PS.   Moreover, QCM provides quantitative measurements of protein adsorption on degradable polymers. The behavior of PLA and poly(LLA-co-CL) was further evaluated and compared with respect to protein adsorption. This behavior was demonstrated to be different for the two polymers considered and to be dependent on protein concentration in solution.   Eventually, exploiting QCM it was also possible to assess the relationship between nDP and the adsorption of fibronectin and BMP-2 onto PLA and poly(LLA-co-CL).

In view of current interest in several oligopeptide drugs currently being investigated for controlled implantable delivery, glycine, diglycine, triglycine, tetraglycine and pentaglycine were chosen as model compounds for encapsulation in biodegradable microspheres of DL-polylactide (DL-PLA) by a technique based on oil-in-oil emulsion and the solvent evaporation principle. A DL-polylactide concentration of 10.3% w/w and emulsifier (sorbitan sesquioleate) concentration of 0.3% v/v produced good yields of microspheres with excellent entrapment when processed under following conditions: emulsion time, 1 min; solvent evaporation time, 2 min; internal phase-external phase ratio, 1:7; stirring speed, 1100 rpm; emulsion temperature, 5$\sp\circ$C; and maximum processing temperature, 35$\sp\circ$C. Microspheres prepared as above at four different loadings (2.5, 5.0, 7.5, and 10.0% w/w) were analyzed for morphological and in vitro release characteristics. Analysis of the release data and scanning electron photographs suggested that the release of glycine and its homopeptides from DL-PLA microspheres was most likely by diffusion through the matrix. However, for models having low aqueous solubility, e.g., tetra- and pentaglycine, dissolution played a rate-limiting role. Microspheres of glycine prepared with DL-PLA plasticized with 10% triacetin demonstrated the slowest release, with the first 50% entrapped glycine released over four days and next 25% released at a constant rate over 17 days. This was in sharp contrast to unplasticized microspheres from which glycine was completely leached out in 24 h. Interestingly, while the plasticizer decreased the rate of release of glycine, it appeared to promote the degradation of the polymer DL-PLA.

yes / Sequential ring-opening and reversible addition–fragmentation chain transfer (RAFT) polymerization was used to form a triblock copolymer of tetrahydropyran acrylate (THPA), 5-methyl-5-allyloxycarbonyl-1,3-dioxan-2-one (MAC) and L-lactide. Concurrent deprotection of the THPA block and crystallization-driven self-assembly (CDSA) was undertaken and allowed for the formation of cylindrical micelles bearing allyl handles in a short outer core segment. These handles were further functionalized by different thiols using photo-initiated thiol–ene radical reactions to demonstrate that the incorporation of an amorphous PMAC block within the core does not disrupt CDSA and can be used to load the cylindrical nanoparticles with cargo. / Royal Society (Great Britain), Engineering and Physical Sciences Research Council (EPSRC), European Research Council (ERC)

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Utilization of DNA vaccines in aquaculture has been gaining interest and recent efforts have been focused on methods of delivering DNA vaccines to fish. In the present study, a methodology was sought that could protect DNA vaccines such that they could be orally administered. The main objective of the study was to determine if a DNA vaccine could be effectively compounded into an orally administrable formulation with chitosan or polylactide-co-glycolide (PLG). The immune response of hybrid striped bass (Morone saxatilis x Morone chrysops) following oral delivery of a DNA vaccine containing Mycobacterium marinum Ag85A plasmid in either chitosan or PLG nanoparticle encapsulation was evaluated. Hybrid striped bass were divided into four experimental groups: IM immunization of the DNA vaccine as a positive control, oral delivery of uncomplexed DNA vaccine, oral delivery of chitosan or PLG alone as a negative control, and oral delivery of complexed chitosan or complexed PLG DNA vaccine. Fish were bled at regular intervals and an ELISA was used to evaluate antibody levels in individual fish. While the chitosan /plasmid DNA complex containing the Mycobacterium marinum Ag85A gene failed to produce a significant antibody response, the PLG/plasmid DNA matrix stimulated humoral immune response in the fish. / Master of Science