This thesis covers the design of an automated multiunit composting system (AMUCS) that was constructed to meet the experimental apparatus requirements of the ASTM D5338 standard. The design of the AMUCS is discussed in full detail and validated with two experiments. The first experiment was used to validate the operation of the AMUCS with a 15 day experiment. During this experiment visual observations were made to visually observe degradation. Thermal properties and stability tests were performed to quantify the effects of degradation on the polymer samples, and the carbon metabolized from the degradation of samples was measured. The second experiment used the AMUCS to determine the effect of synthetic clay nanofiller on the aerobic biodegradability behavior of poly (3-hydroxybutyrate-co-3-hydroxyvalerate).

Orientador: Antonio Wilson Sallum / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Odontologia de Piracicaba / Made available in DSpace on 2018-08-26T23:52:25Z (GMT). No. of bitstreams: 1 Moura_LucasAlves_D.pdf: 4231687 bytes, checksum: ec30a84348074c7f0f52d37535f57bbe (MD5) Previous issue date: 2015 / Resumo: O objetivo deste estudo foi avaliar o efeito da associação da administração local de nanoesferas contendo doxiciclina (DOX) com o debridamento periodontal no tratamento da periodontite crônica avançada. As nanoesferas foram preparadas pelo método da dupla emulsão (W/O/W), e caracterizadas quanto à morfologia através da microscopia eletrônica de varredura (MEV), e quanto à interação polímero (PLGA) e DOX através da espectroscopia infravermelha da transformada de Fourier (FTIR). A avaliação da liberação controlada de DOX foi feita através da cromatografia líquida de alta eficiência (HPLC), a partir do fluido gengival sulcular (GCF) coletado nos períodos: 2, 5, 7, 10, 15 e 20 dias após aplicação das nanoesferas. Foi realizado um ensaio clínico randomizado controlado duplo cego, incluindo 30 pacientes diagnosticados com periodontite crônica que apresentavam sete sítios com sangramento à sondagem e profundidade de sondagem (PS) ? 5 mm, sendo 2 dentes com PS ? 7 mm. Os pacientes foram aleatoriamente divididos em 2 grupos e receberam os seguintes tratamentos: debridamento periodontal por 45 minutos associado à administração local de nanoesferas contendo doxiciclina nos sítios com PS ? 5 mm (DB+DOX) ou debridamento periodontal por 45 minutos associado à aplicação de nanoesferas vazias (DB). Foram avaliados os seguintes parâmetros clínicos: Índice de Placa (IP), Sangramento à Sondagem (SS), Profundidade de Sondagem (PS) e Nível de Inserção Clínica (NIC), no baseline, 3 e 6 meses após a terapia. A avaliação microbiológica foi feita por meio da reação de cadeia de polimerase ¿ tempo real ("real time" - PCR) para detecção das bactérias: Porphyromonas gingivalis, Tannerella forsythia, Treponema denticola, Aggregatibacter actinomycetemcomitans e Prevotella intermedia, provenientes do biofilme subgengival coletado no baseline, 1, 3 e 6 meses após o tratamento. Os resultados foram comparados por meio do teste de análise de variância com medidas repetidas, com nível de significância de 5%. Foram obtidas nanoesferas variando de 700 nm a 4 um. Através do FTIR observou-se boa interação da DOX com o PLGA, sem alterações das propriedades químicas de nenhum dos compostos. Após a aplicação das nanoesferas observou-se uma liberação de DOX constante no GCF até o vigésimo dia pós-tratamento, acima da concentração inibitória mínima. No grupo DB+DOX houve redução significativa da PS e ganho de inserção clínica nas bolsas profundas e moderadas em relação ao baseline e entre grupos. Observou-se redução significativa dos níveis bacterianos pós-tratamento, sendo o grupo DB+DOX mais eficaz em manter os níveis mais baixos após 6 meses do tratamento. Dentro das limitações deste trabalho, os resultados sugerem que as nanoesferas de PLGA são efetivas como sistema de liberação controlada local de DOX e quando associadas ao debridamento periodontal podem promover resultados superiores em relação à terapia mecânica isoladamente / Abstract: The aim of this study was to assess the effect of the association of local administration of nanospheres loading doxycycline (DOX) with the periodontal debridement treating advanced chronic periodontitis. Nanospheres were made by double-emulsion method (W/O/W) and characterized regarding morphology, by scaning eléctron microscopy (SEM); and drug/polymer interaction, by Fourier transform infrared spectroscopy (FTIR). The DOX controlled release was assessed by high performance liquid chromatography (HPLC) of gingival crevicular fluid (GCF) samples collected 2, 5, 7, 10, 15 and 20 days after treatment. It was performed randomized double-blinded clinical trial, with thirty patients diagnosed with chronic periodontitis presenting at least seven sites with bleeding on probing and probing depth (PD) ? 5 mm, and 2 sites with PD ? 7 mm. The patients were randomly allocated in two groups receiving interventions as followed: 45 minutes periodontal debridement + subgengival nanospheres loading DOX (DB+DOX); and 45 minutes periodontal debridement + subgengival void nanospheres (DB). Plaque index (IP), bleeding on probing (BP), probing depth (PD) and clinical attachment level (CAL) were evaluated on baseline, 3, and 6 months after therapy. Real-time polymerase chain reaction (real-time PCR) was used to quantify Porphyromonas gingivalis, Tannerella forsythia, Treponema denticola, Aggregatibacter actinomycetemcomitans and Prevotella intermedia from subgingival biofilm samples collected on baseline, 1, 3 and 6 months after treatment. The results were compared by variance analyses test for repeated measures, with significance of 5%. Nanospheres varying from 700 nm to 4 um were obtained. There was a good interaction between DOX and PLGA, with no chemical properties alterations. After local administration of the nanospheres, it was observed constant DOX release in the GCF until 20th day post-treatment, with concentration above the minimum inhibitory concentration. DB+DOX group showed significant PD reduction and CAL gain in deep and moderates pockets comparing to baseline and between groups. It was observed significant reduction of bacteria levels along follow up period, and DB+DOX group was more eficiente in keeping lower levels of bacteria after 6 months from treatment. Within limitations of this study, the results can suggest that PLGA nanospheres are effective carriers for controlled release of DOX and when used adjunctively to periodontal debridement, improved results can be achieved compared to mechanical therapy alone / Doutorado / Periodontia / Doutor em Clínica Odontológica

We live in a time of many challenges. The ‘Great Acceleration’ (Steffen et al., 2015) is a trend that can be observed in numerous fields in our world: be it the development of CO2 emissions, the land use or the enormous amount of produced plastics accompanied by massive environmental pollution. This ‘phenomenon’ is obviously directly linked to the way we live and how our society works. To meet these developments, we need to move away from the big, prone concepts that got us here in the first place, and instead build on a variety of dynamic and changing solutions.

This thesis has an approved one-year embargo applied to it. Please, refer to the corresponding forms, and please, so not publish immediately until the embargo has been sorted out. The thesis contains two unpublish papers and patents pending. Thank you! / Conventional single-use plastic packaging has contributed significantly to the health and well-being of our society but also negatively impacted our environment due to its persistence after use. Since recycling is not a complete solution, rapidly biodegradable materials like thermoplastic starch (TPS) blends offer a more sustainable alternative. Additionally, to stave off the premature breakdown of starch-containing materials as well as extend the shelf life of enclosed foods, microbial control strategies need to be developed. To overcome the inherent brittleness of TPS, this work explores the potential of xylitol and erythritol as melt plasticizers for waxy corn starch (̴100% amylose). Characterizations revealed that both xylitol and erythritol can gelatinize and plasticize starch under 25% wt. Particularly, xylitol demonstrated superior plasticizing and compatibilizing effects, leading to a ductile TPS packaging film with uncharacteristically high elongation at break (EB, 422% ± 48%). The ductile TPS was blended with up to 70% Ecovio bioplastic without requiring compatibilizers and retaining much of its EB value (298 ± 24%). Using xylitol as a melt plasticizer also enhanced the mechanical and hydrophobic qualities of the TPS/Ecovio film as well as its oxygen permeability and puncture extension. Furthermore, polymerized curcumin copolymer (PCEG) was investigated as a grafted coating onto the developed TPS/Ecovio® blend. The antimicrobial activity of PCEG and PCEG coating film was evaluated against foodborne bacteria. The polymerized curcumin by itself demonstrated antimicrobial activity against the gram-negative bacteria Escherichia coli BL21 and Pseudomonas aeruginosa PA01, as well as the gram-positive bacterium Staphylococcus aureus. Additionally, the PCEG-coated films showed surface inhibition of Glutamicibacter soli (IAI-3), a gram-positive bacterium making polymerized curcumin copolymer coatings a suitable approach to add antimicrobial features in thermoplastic starch composites for biodegradable food packaging. / Thesis / Master of Applied Science (MASc) / Canada's Zero Plastics initiative represents a commitment to the environment while upholding the advancements in food safety and public health that come with single-use food packaging. Achieving this balance demands the creation of novel materials. These materials should mimic the qualities of synthetic polymers but have the added ability to decompose naturally in the environment upon reaching the end of their utility. A significant challenge in this effort is preventing the premature degradation of starch-containing packaging materials. Moreover, extending the shelf life of the food they enclose is equally crucial. To solve this paradox, the development of microbial control strategies becomes imperative. This study highlights the antimicrobial potential of a polymerized curcumin copolymer (PCEG) as a coating on a blend of thermoplastic starch (TPS)/xylitol/Ecovio®, creating an innovative packaging film. The curcumin copolymer coating exhibited antimicrobial properties, suggesting its potential use in thermoplastic starch composites for biodegradable food packaging.

O sistema de mobilização intracelular de poli-3-hidroxibutirato (P3HB) em Burkholderia sacchari foi analisado. A busca em genomas de Burkholderia spp. identificou duas oligômero hidrolases (PhaY1 e PhaY2) e pelo menos três P3HB despolimerases intracelulares (PhaZa1, PhaZa2 e PhaZd1). Mutantes de B. sacchari afetados na mobilização de P3HB e complementados com genes de Ralstonia eutropha apresentaram um aumento expressivo nas taxas de mobilização de P3HB, especialmente quando o gene phaZa1 foi superexpresso. A superexpressão dos genes phaZa2 ou phaZa3 também conduziu a aumentos nas taxas de mobilização embora em um grau menor que os valores obtidos com phaZa1. Dois mutantes afetados na mobilização de P3HB foram obtidos utilizando o transposon mini-Tn5 (NAM03 e NAM04). NAM03 apresentou interrupção em gene que codifica uma P3HB despolimerase intracelular (PhaZa1). NAM04 apresentou interrupção em gene anotado como serino peptidase LonA. Este pode representar um ativador da mobilização ou uma nova P3HB despolimerase intracelular. / The intracellular poly-3-hydroxybutyrate (P3HB) mobilization system in Burkholderia sacchari was analyzed. A search in Burkholderia spp. genomes identified two oligomer hydrolases (PhaY1 and PhaY2) and at least three intracellular P3HB depolymerase (PhaZa1, PhaZa2 e PhaZd1). B. sacchari mutants affected on P3HB mobilization and complemented by Ralstonia eutropha genes showed an expressive increase on P3HB mobilization rates, especially when phaZa1 was overexpressed. The overexpression of phaZa2 or phaZa3 also increased the mobilization rates though to a lesser extent than phaZa1. Two mutants affected on P3HB mobilization were obtained using the transposon mini-Tn5 (NAM03 and NAM04) .NAM03 was disrupted in a gene encoding an intracellular P3HB depolymerase (PhaZa1). NAM04 was disrupted in a gene annotated as a serine peptidase LonA. This could be a mobilization activator or a new intracellular P3HB depolymerase.

Environmental concerns arising from the use of non-degradable plastics have resulted in search for suitable substitutes. The thesis deals with new nanostructured composites based on reinforcement of nanocellulose whiskers in "green" polymers such as xylan. Since the reinforcement filler and the matrix are both biobased and are thereby environmental friendly. Xylan incorporated with cellulose whiskers films provided with improved water and oxygen barrier properties. It appears that the high degree of crystallinity of cellulose whiskers, dense composite structure formed by the whiskers and rigidly hydrogen-bonded cellulose whiskers can cause cellulose whiskers to form integrated matrix which contribute to substantial benefit in the overall reduction of transmission rate. The spectral data obtained for the NCW/xylan nanocomposite films showed that the amount of xylan adsorbed to cellulose increases with the addition of NCW in the matrix. In addition, NMR T2 relaxation experiments studies were conducted to investigate the change in the nature of carbohydrate-water interactions as a result of NCW incorporation. These results facilitated an improved understanding of the mechanisms involved in the superior barrier and mechanical properties of xylan-whisker nanocomposite films. XRD studies show that when a xylan-whisker nanocomposite films is formed the mixing occurs on the atomic scale and NCW loading increases the matrix crystallinity.

We studied PLA-microcrystalline cellulose composites, focusing on the effects of processing, particle size and surface modification. The thermal and mechanical properties of these PLA based composites were studied and the effect of cellulose addition on PLA degradation was analyzed. For our system, the degradation rate was found to depend on initial sample crystallinity, pH of the degradation media and cellulose content of the composite. Composites were prepared using solution processing and melt mixing methods. The processing methods influenced the polymer's ability to crystallize affecting the mechanical properties. Isothermal crystallization studies carried out to study the kinetics of crystallization showed melt processed samples to have lower half time for crystallization and higher value for the Avrami exponent. The crystallization rate of PLA was also found to depend on surface chemical composition of cellulose particles and the particle size. Influence of filler surface modification on the composite properties was studied via grafting of lactic acid and polylactic acid to cellulose particles and the effect of filler size was studied using hydrolyzed microcrystalline cellulose particles. A simple esterification reaction that required no external catalyst was used for surface modification of cellulose particles. Surface modification of cellulose particles enhanced the static and dynamic mechanical properties of the composite samples due to improvement in the PLA-cellulose compatibility that resulted in better interfacial interactions. The utility of cellulose, available from a renewable resource, as an effective reinforcement for PLA is demonstrated.

The prevention and treatment of cancer and infectious diseases requires vaccines that can mediate cytotoxic T lymphocyte-based immunity. A promising strategy is protein subunit vaccines composed of purified protein antigens and immunostimulatory adjuvants, such as Toll-like receptor (TLR) agonists. In this research, we developed two new biodegradable polymeric delivery vehicles for protein antigens and TLR agonists, as model vaccine delivery systems. This work was guided by the central hypothesis that an effective vaccine delivery system would have stimulus-responsive degradation and release, biodegradability into excretable non-acidic degradation products, and the ability to incorporate various TLR-inducing adjuvants. The first vaccine delivery system is a cross-linked polyion complex micelle which efficiently encapsulates proteins, DNA, and RNA. The micelle-based delivery system consists of a block copolymer of poly(ethylene glycol) (PEG) and poly(L-lysine), cross-linked by dithiopyridyl side groups to provide transport stability and intracellular release. The second delivery system consists of solid biodegradable microparticles encapsulating proteins, nucleic acids, and hydrophobic compounds. The microparticles are composed of pH-sensitive polyketals, which are a new family of hydrophobic, linear polymers containing backbone ketal linkages. Polyketals are synthesized via a new polymerization method based on the acetal exchange reaction and degrade into non-acidic, excretable degradation products. In addition, the technique of hydrophobic ion pairing was utilized to enhance the encapsulation of ovalbumin, DNA, and RNA in polyketal microparticles via a single emulsion method. Using in vitro and in vivo immunological models, we demonstrated that the micelle- and polyketal-based vaccine delivery systems enhanced the cross-priming of cytotoxic T lymphocytes. The model vaccines were composed of ovalbumin antigen and various TLR-inducing adjuvants including CpG-DNA, monophosphoryl lipid A, and dsRNA. The results demonstrate that the cross-linked micelles and polyketal microparticles have considerable potential as delivery systems for protein-based vaccines.

O sistema de mobilização intracelular de poli-3-hidroxibutirato (P3HB) em Burkholderia sacchari foi analisado. A busca em genomas de Burkholderia spp. identificou duas oligômero hidrolases (PhaY1 e PhaY2) e pelo menos três P3HB despolimerases intracelulares (PhaZa1, PhaZa2 e PhaZd1). Mutantes de B. sacchari afetados na mobilização de P3HB e complementados com genes de Ralstonia eutropha apresentaram um aumento expressivo nas taxas de mobilização de P3HB, especialmente quando o gene phaZa1 foi superexpresso. A superexpressão dos genes phaZa2 ou phaZa3 também conduziu a aumentos nas taxas de mobilização embora em um grau menor que os valores obtidos com phaZa1. Dois mutantes afetados na mobilização de P3HB foram obtidos utilizando o transposon mini-Tn5 (NAM03 e NAM04). NAM03 apresentou interrupção em gene que codifica uma P3HB despolimerase intracelular (PhaZa1). NAM04 apresentou interrupção em gene anotado como serino peptidase LonA. Este pode representar um ativador da mobilização ou uma nova P3HB despolimerase intracelular. / The intracellular poly-3-hydroxybutyrate (P3HB) mobilization system in Burkholderia sacchari was analyzed. A search in Burkholderia spp. genomes identified two oligomer hydrolases (PhaY1 and PhaY2) and at least three intracellular P3HB depolymerase (PhaZa1, PhaZa2 e PhaZd1). B. sacchari mutants affected on P3HB mobilization and complemented by Ralstonia eutropha genes showed an expressive increase on P3HB mobilization rates, especially when phaZa1 was overexpressed. The overexpression of phaZa2 or phaZa3 also increased the mobilization rates though to a lesser extent than phaZa1. Two mutants affected on P3HB mobilization were obtained using the transposon mini-Tn5 (NAM03 and NAM04) .NAM03 was disrupted in a gene encoding an intracellular P3HB depolymerase (PhaZa1). NAM04 was disrupted in a gene annotated as a serine peptidase LonA. This could be a mobilization activator or a new intracellular P3HB depolymerase.

En el Perú, la industria del plástico abarca un 4 % del PBI nacional y produce más de 52 000 empleos. En la actulidad, la productividad de una empresa es un referente de su competitividad en el sector. El sector de plásticos, el cúal esta siendo golpeado por regulaciones gubernamentales, necesita cambios rápidos en materia prima y procesos productivos, en donde la productividad y calidad del producto puede ser un diferenciador trascendente para su adaptación al nuevo mercado eco amigable. Ante la problemática de productividad en la mayoría de los sectores económicos, se ha trabajado en desarrollar metodologías y herramientas que permitan solucionar este problema. La importancia radica en que las empresas deben trabajar eficientemente en sus procesos así como, análogamente, aumentar su disponibilidad y mejorar el desempeño del trabajo para aumentar la productividad de la empresa. Por lo tanto, se propone establecer un modelo para la administración de la producción en base a la metodología de Manufactura Esbelta hacienda uso de sus diversas herramientas, como SMED y 5’s. Para validar la efectividad de nuestro modelo propuesto, se realizará la simulación en el programa Arena Simulation e Input Analyzer, lo cual representa una oportunidad de mejora factible en la actualidad. Esto nos permitirá aumentar la productividad a un 61% y la calidad de los productos, obteniendo un aumento en la utilidad neta de 25 mil soles. Por lo cual, sirve como una guía inicial para las empresas que buscan aumentar la productividad de sus procesos. / In Peru, the plastics industry accounts for 4% of the national GDP and produces more than 52,000 jobs. Currently, the productivity of a company is a benchmark of its competitiveness in the sector. The plastics sector, which is being hit by government regulations, needs rapid changes in raw materials and production processes, where productivity and product quality can be a transcendent differentiator for its adaptation to the new eco-friendly market. Faced with the productivity problem in most economic sectors, work has been done to develop methodologies and tools to solve this problem. The importance lies in the fact that companies must work efficiently in their processes as well as, similarly, increase their availability and improve work performance to increase the productivity of the company. Therefore, it is proposed to establish a model for production management based on the Lean Manufacturing methodology using its various tools, such as SMED and 5's. To validate the effectiveness of our proposed model, the simulation will be carried out using the Arena Simulation and Input Analyzer program, which represents an opportunity for improvement that is currently feasible. This will allow us to increase productivity to 61% and the quality of the products, obtaining an increase in net income of 25 thousand soles. Therefore, it serves as an initial guide for companies seeking to increase the productivity of their processes. / Trabajo de investigación