Indiana University-Purdue University Indianapolis (IUPUI) / Introduction: Regenerative endodontic procedures (REPs) are a type of endodontic treatment aimed at replacing damaged tooth structures, including dentin and root structures, as well as cells of the pulp-dentin complex. Double antibiotic paste (DAP) has been shown to be efficacious in achieving disinfection of the root canal system while minimizing cytotoxicity to dental pulp stem cells (DPSCs). Hydroxyapatite (HA) is an extracellular, mineralized component of bone that has shown much promise as a scaffold in the field of regenerative medicine. Objective: The objective of this study was to evaluate the effects of HA in a DAP loaded methylcellulose (MC) carrier on the differentiation and mineral deposition of DPSC over time. Materials and Methods: DPSCs were plated in 24-well plates with culture media. The following day, semi-permeable 0.1 m chambers were inserted into the wells to separate the reservoirs and permit delivery of medicaments. 100 L treatment paste composed of MC with 1% DAP and either 0.5% or 1.0% nano-HA was added, followed by additional culture media. After 3 days of treatment, medicaments were removed and DPSCs were cultured for an additional 9 days with replacement of media every 3-4 days. At Day 12, DPSCs were evaluated for alkaline phosphatase (ALP) activity using a biochemical assay and mineral deposition using an Alizarin Red S Ca2+ staining assay (4 wells/group). Comparisons between groups were performed using one-way analysis of variance (ANOVA) with a 5% significance level used for all tests. Results: A trend towards increased ALP and mineral deposition activity was noted among the groups with HA added to DAP with MC. Although these trends were not statistically significant, a trend towards increased ALP and mineral deposition was observed after 3-day medicament exposure. The results were similar to previous findings using 7-day medicament treatments. Conclusion: The addition of HA showed a trend towards improved differentiation and mineral deposition of DPSCs compared to DAP with MC. Although additional studies are required, these results showed suggest that even with a shortened treatment time, increased differentiation and mineral deposition of DPSCs may be possible. This study provides additional support that low concentration DAP in a MC carrier has potential application in regenerative endodontic procedures. The novel addition of HA may provide additional osteogenic potential.

Inkjet printing (jetting) technology, due to its high speed of operation and accuracy, is utilised in Additive Manufacturing (AM) of three dimensional parts. Commercially available AM processes that use jetting technology include three dimensional printing (3DP by Z-Corporation), Polyjet (by Objet), Multi Jet Modelling (MJM by 3D Systems) and three dimensional printing by Solidscape. Apart from 3D Printing by Z-corporation, all the other jetting based processes require a support material to successfully build a part. The support material provides a base to facilitate the removal of the part from the build platform and it helps manufacturing of cavities, holes and overhanging features. These support materials present challenges in terms of their removability and reusability. This research is therefore, aimed towards finding a support material composition that can be used with jetting based AM processes. The support material should be easily removable either by melting or by dissolution and also, if possible, it should be reusable. AM processes often process materials with poor mechanical properties and therefore, the parts produced by these processes have limited functionality. In an attempt to obtain complex shaped, functional parts made of nylon (i.e. Polyamide 6), a new jetting based AM process is under research at Loughborough University. The process uses two different mixtures of caprolactam (i.e. the monomer used to produce polyamide). These mixtures are to be jetted using inkjet heads and subsequently polymerised into polyamide 6. Therefore, another aim of this research was to consider the support material s suitability for jetting of caprolactam. Two different polymers were researched which included Pluronic F-127 and methylcellulose (MC). Both these polymers are known for gel formation upon heating in aqueous solutions. Due to the inhibition of polymerisation of polyamide 6 by the presence of water, non-aqueous solvents such as ethylene glycol, propylene glycol and butylene glycol were studied. Since both F-127 and MC in the glycols mentioned above had not been studied before, all the compositions prepared and investigated in this report were novel. F-127 did not show gel formation in propylene and butylene glycol but formed a gel in ethylene glycol at a concentration of 25% (w/w) F-127. MC, on the other hand, showed gel formation upon cooling in all the three glycols at concentrations as low as 5% for ethylene glycol and 1% for both propylene and butylene glycol. These compositions were characterized using experimental techniques such as Fourier Transform Infrared (FTIR) spectroscopy, hot stage microscopy, differential scanning calorimetry (DSC) and X-ray diffraction (XRD). A mechanism of gelation for both F-127 and MC in glycols is presented based on the results of these characterisation techniques. Viscosity and surface tension measurements along with the texture analysis of selected compositions were also performed to evaluate their suitability for jetting. All these compositions, due to their water solubility and/or low melting temperatures (i.e. near 500C) present the advantage of ease of removal. Removal by melting at low temperatures can also provide reusability of these support materials and thus advantages such as reduction in build cost and environmental effect can be achieved.

A película de amendoim é um resíduo da indústria de alimentos. Esse resíduo é rico em compostos fenólicos como resveratrol e procianidinas e apresenta elevada atividade antioxidante e atividade farmacológica. Apesar de suas atividades farmacológicas, compostos fenólicos apresentam baixa biodisponibilidade devido à glucuronidação catalisada pelas enzimas UDP-glucuronosyltransferases (UGTs), que acontece na primeira passagem no intestino e/ou fígado, dificultando a utilização dos compostos fenólicos como agentes terapêuticos. Filmes de desintegração oral permitem que o princípio ativo seja absorvido no epitélio bucal diretamente pela circulação sistêmica podendo melhorar a biodisponibilidade desses compostos naturais. Nesse contexto, o objetivo desse trabalho foi desenvolver um filme de desintegração oral à base de gelatina e hidroxipropilmetilcelulose (GEL:HPMC) incorporado com extrato de película de amendoim como um carreador de compostos bioativos. O extrato de película de amendoim foi produzido utilizando-se etanol (70%) como solvente (razão sólidos/solvente de 1:20) à temperatura ambiente sob agitação mecânica (10 minutos), sendo realizada três extrações consecutivas. O extrato foi liofilizado para ser caracterizado em relação à atividade antioxidante, fenólicos totais e aflatoxinas. Os filmes de desintegração oral com diferentes concentrações de gelatina e hidroxipropilmetilcelulose (GEL:HPMC) foram produzidos por casting (2g de macromoléculas/100 g de solução filmogênica e 0,4g de sorbitol/100g de solução filmogênica). O extrato de película de amendoim foi incorporado líquido e concentrado nas concentrações de 10, 20 e 30g/100g de solução filmogênica. Os filmes foram caracterizados em relação à propriedades mecânicas, ângulo de contato, tempo de desintegração, mucoadesividade, pH de superfície, microscopia eletrônica de varredura e espectroscopia de infravermelho. O extrato (liofilizado) apresentou concentração fenólica igual a 718,57 mg de equivalente em ácido gálico/g e EC50 igual a 146,07 ± 8.37 µg/mL e 0,37 ng B₁/g. Os filmes sem adição de extrato, independente da formulação, apresentaram homogeneidade e, de um modo geral, os filmes à base de hidroxipropilmetilcelulose apresentaram melhores propriedades mecânicas, hidrofilicidade superior, tempo de desintegração reduzido e mucoadesividade superior em relação aos filmes com gelatina em sua composição. Comportamento similar foi observado para os filmes de desintegração oral com adição de extrato. Entretanto, filmes com adição de extrato e altas concentrações de gelatina (100:0, 75:25) apresentaram formação de complexos insolúveis entre taninos e proteínas, aparentes visualmente. Em função dos resultados obtidos, os filmes à base de hidroxipropilmetilcelulose (0:100) e com 20% de extrato de película de amendoim apresentaram propriedades mecânicas superiores (tensão na ruptura = 26,63 MPa, elongação = 4,97% e módulo elástico = 1284,82 MPa) e menor tempo de desintegração (17,87 segundos) em relação as demais formulações, sendo esta considerada a formulação otimizada como potencial aplicação para filmes de desintegração oral. / Peanut skin is a food industry byproduct which is rich in phenolic compounds, such as resveratrol and procyanidins. Moreover, it has high antioxidant and pharmacological properties. Despite these activities, phenolic compounds have low oral bioavailability due to glucuronidation catalyzed by the enzyme UDP-glucuronosyltransferases (UGTs). This catalyze occurs in the first-pass metabolism (gut and/or liver) difficulting the use of phenolic compounds as therapeutic agents. For oral disintegrating films the active ingredient is directly absorbed into systemic circulation by oral epithelium improving the bioavailability of these natural compounds. The aim of this study was to develop oral disintegrating film composed of gelatin and hydroxypropyl methylcellulose (GEL: HPMC) added of peanut skin extract as a vehicle for bioactive compounds. The peanut skin extract was produced using ethanol (70%) as solvent (solid/solvent ratio 1:20) at room temperature under mechanical stirring (10 minutes) with three consecutive extractions. The extract was lyophilized to be characterized by antioxidant activity, total phenolic and aflatoxins. The oral disintegrating films were produced by casting (2g macromolecules/100 g filmogenic solution and 0.4g of sorbitol/100g of filmogenic solution) with different concentrations of gelatin and hydroxypropylmethylcellulose (GEL: HPMC). The peanut skin extract was added to films liquid and concentrated at concentrations of 10, 20 and 30g / 100g of filmogenic solution. The films were characterized by mechanical properties, contact angle, disintegrating time, mucoadesivity, surface pH, scanning electron microscopy and infrared spectroscopy. The extract (lyophilized) showed phenolic concentration of 718.57 mg of gallic acid equivalent/g, EC50 of 146.07 ± 8.37 µg/mL and 0.37 ng B₁/g. Films without extract, regardless of formulation were homogeneous. In general, hydroxypropyl methylcellulose films exhibited better mechanical properties, higher hydrophilicity and mucoadesivity and reduced disintegration time compared to films with gelatin in its composition. Similar behavior was observed for oral disintegrating films with addition of extract. Films formulation with high gelatin content (100: 0, 75:25) added of extract showed insoluble complexes formed between proteins and tannins. Hydroxypropyl methylcellulose films (0: 100) added of peanut skin extract (20%) showed superior mechanical properties (tensile strength = 26.63 MPa, elongation = 4.97% and elastic modulus = 1284.82 MPa) and lower disintegration time (17.87 seconds) compared with other formulations, which is considered the optimized formulation as a potential application for oral disintegrating films.

O Brasil é hoje o maior produtor de cana-de-açúcar no mundo e a previsão de safra para 2016 é de 658,7 milhões de toneladas. Como o bagaço da cana consiste de 14% de sua massa serão produzidas cerca de 92 milhões de toneladas desse coproduto. Buscando alternativas sustentáveis existem algumas formas de aproveitamento do mesmo, seja na produção de energia, de etanol de segunda geração ou de derivados celulósicos, foco do presente estudo. Objetivou-se através deste trabalho obter metilcelulose por meio de processos sequenciados. Partindo do bagaço de cana in natura, celulose, hemicelulose e lignina foram segregadas por hidrólises, sendo que o foco foi a fração celulósica. A mesma passou por duas diferentes sequências de branqueamento, obtendo celulose purificada, da qual foi produzida a metilcelulose com potencial aplicabilidade industrial. As sequências de branqueamento avaliadas foram uma livre de cloro elementar (ECF) e outra totalmente livre de cloro (TCF), visando reduzir ou suprimir a geração de poluentes tóxicos, principalmente compostos organoclorados. Uma das escolhas para esse objetivo foi o emprego de tecnologia baseada no tratamento enzimático, através da lacase, na sequência TCF. Cada material gerado por etapa de estudo foi analisado. O bagaço de cana, e as celuloses geradas pelas hidrólises foram caracterizadas quanto aos teores de celulose, hemicelulose, lignina, cinzas e extrativos. A celulose gerada antes e após cada etapa de branqueamento foi caracterizada, alcançando por meio da rota ECF uma redução de 80,5% do número kappa, aumento de 3,6 vezes do grau de alvura e pouca variação na viscosidade. Para a rota TCF houve redução de 48,7% do número kappa, aumento de 2,3 vezes do grau de alvura e melhora das propriedades da fibra por meio do aumento da viscosidade. A metilcelulose foi caracterizada por DRX, FTIR, TGA/DTG, MEV e solubilidade. Concluiu-se que os tratamentos foram realizados de maneira eficiente, a otimização das etapas de branqueamento proporcionou uma boa purificação da celulose, a partir da qual pôde ser produzida metilcelulose de boa qualidade, confirmada pelas análises do material. / Brazil is now the largest producer of sugarcane in the world and harvest forecast for 2016 is 658.7 million tons. Such as sugarcane bagasse consists of 14% of its mass will be produced about 92 million tons of this coproduct. Seeking sustainable alternatives there are some ways to use the same, whether in energy production of second-generation ethanol or cellulosic derivatives, focus of this study. The objective was to get through this work methylcellulose through sequenced processes. Starting from sugarcane bagasse, cellulose, hemicellulose and lignin were segregated by hydrolysis, and the focus was the cellulosic fraction. The same underwent two different bleaching sequences, obtaining purified cellulose, which was produced methylcellulose having potential industrial applicability. bleaching sequences evaluated were an elemental chlorine free (ECF) and other totally chlorine free (TCF), to reduce or eliminate the generation of toxic pollutants, organochlorine compounds mainly. One of the choices for this purpose was the use of technology based on enzymatic treatment by Laccase in TCF sequence. Each material generated by step study was analyzed. The sugarcane bagasse, and the pulps generated by hydrolysis were characterized how to cellulose, hemicellulose, lignin, ash and extractives. Cellulose generated before and after each bleaching stage was characterized, by ECF route reaching a reduction of the kappa number 80.5%, an increased of 3.6 times the degree of whiteness and little variation in viscosity. For TCF route was reduced by 48.7% kappa number, increase the degree of whiteness in 2.3 times and a improvement of fiber properties by increasing the viscosity. The methylcellulose was characterized by XRD, FTIR, TGA / DTG, SEM and solubility. It was concluded that the treatments were performed in an efficient manner, optimization of the bleaching stages provided a good purification of the pulp, from which good quality can be produced methylcellulose, confirmed by analysis of the material.

Arthrospira platensis ou Spirulina é uma microalga com alto valor nutricional. Foram preparados extratos de Spirulina, caracterizados e aplicados como estabilizadores de emulsão de óleo de girassol comercial em água (O/A) (10% v/v) na ausência e na presença de quatro tipos de hidroxipropil metilcelulose (HPMC). Os extratos brutos de Spirulina foram preparados em tampões a pH 6 (EB6) e pH 8 (EB8) por sonicação para promover a lise celular e a libertação de proteínas e fosfolípides; Parte dos extratos foi centrifugada (EC6 ou EC8). Independentemente das condições de extração, todos os extratos apresentados apresentaram valores de potencial-&#950 médio variando de - (16 ± 2) mV a - (20 ± 2) mV, tamanho médio variando de (108 ± 52) nm a (306 ± 68) nm e atividade interfacial. As emulsões O/A preparadas com extratos de Spirulina (10 g / L) exibiram partículas com potencial- médio variando de - (16 ± 2) mV a - (27 ± 4) mV, tamanho médio variando de ~ 70 nm (EB6 ou EB8) a ~ 700 nm (EC6 ou EC8). No entanto, o EB6 levou a emulsões ligeiramente mais estáveis do que as outras. A combinação de EB6 (10 g / L) e HPMC (1,0 % m/m) levou a um aumento substancial na estabilidade da emulsão, embora os valores de potencial- diminuíram uma ordem de grandeza. Em particular, a HPMC com a maior massa molar e o maior grau de substituição de grupos metila conduziu a i) camada interfacial mais robusta resultante da formação de complexos entre cadeias HPMC e proteínas EB6 e (ii) meio contínuo mais viscoso. / Arthrospira platensis or Spirulina is a microalga with a high nutritional value. Extracts of Spirulina were prepared, characterized and applied as oil in water (O/W) (10 % v/v) emulsion stabilizers in the absence and presence of four types of hydroxypropyl methylcellulose (HPMC). The emulsions were prepared with edible sunflower oil. Crude extracts of Spirulina were prepared in buffers at pH 6 (CE6-Crude extract pH6) and pH 8 (CE8-Crude extract pH8) by sonication to promote cell lysis and protein and phospholipids release; part of the extracts was centrifuged (CCE6 or CCE8). Regardless of the extraction conditions, all extracts presented mean -potential ranging from (16 ± 2) mV to (20 ± 2) mV, mean diameter ranging from (108 ± 52) nm to (306 ± 68) nm and interfacial activity. The emulsions prepared with Spirulina extracts (10 g/L) displayed particles with mean -potential ranging from (16 ± 2) mV to (27 ± 4) mV, mean diameter ranging from ~ 70 nm (CCE6 or CCE8) to ~ 700 nm (CE6 or CE8). However, CE6 led to emulsions slightly more stable than the others did. The combination of CE6 (10 g/L) HPMC (1.0 wt %) led to substantial increase in the emulsion stability, although the -potential values decreased one order of magnitude. Particularly, the HPMC with the highest molecular weight and highest methyl substitution degree led to the most (i) robust interfacial layer resulting from the complex formation between HPMC chains and CE6 proteins and (ii) viscous continuous medium.

O objetivo do estudo foi avaliar o efeito da utilização de película de metilcelulose e das atmosferas de acondicionamento com ar atmosférico, vácuo e argônio sobre a conservação de batatas minimamente processadas (MP) e também sobre sua qualidade após fritura. Tubérculos foram selecionados, lavados, sanificados, cortados na forma de palitos e tratados com ácido cítrico. As batatas foram imersas em solução filmogênica contendo metilcelulose (1%) e sorbitol (0,75%) como plastificante, com posterior secagem, acondicionadas sob ar atmosférico, e modificada com argônio (20seg. e 230mmHg), além de vácuo (15seg. e 54mmHg). O produto MP armazenado a 8°C durante 12 dias foi avaliado em intervalos de 3 dias mediante análises microbiológicas, fisiológicas, físicoquímicas e físicas. A cada 3 dias as batatas MP foram também fritas e avaliadas quanto à perda de umidade, absorção de óleo, textura instrumental e avaliação sensorial. O acondicionamento sob ar atmosférico foi efetivo em reduzir a perda de massa das batatas MP. As embalagens sob vácuo foram mais efetivas para o produto MP sem película, pois mantiveram o pH, acidez titulável, teor de amido e de açúcares mais próximos do dia do início do experimento, como também mantiveram baixo o índice de escurecimento. O acondicionamento sob vácuo, entretanto, não seria indicado quando a finalidade fosse a fritura, pois foi o tratamento que apresentou maiores perdas de umidade e maior absorção de óleo. O acondicionamento sob atmosfera de argônio também foi mais efetivo nas batatas MP sem película, sendo fator determinante em reduzir os teores de CO2 no interior da embalagem, apresentou menor taxa respiratória, menor índice de escurecimento tanto antes como após a fritura, reduziu a perda de umidade durante a fritura, manteve mais a firmeza do produto frito e também minimizou a absorção de óleo a partir do 3° dia de armazename nto. A utilização de película foi efetiva em reduzir a respiração do produto MP até o 6° dia. Já no produto frito, foi fator determinante na retenção de umidade das batatas, como também na redução, ao longo do armazenamento, da absorção de óleo / The aim of this study was to evaluate the effect of methylcellulose as edible coating and packaging atmospheres with atmospheric air, vacuum and argon on the conservation of minimally processed (MP) potatoes as well as on their quality after frying. Tubers were selected, washed, sanitized, cut in the shape of sticks and treated with citric acid. Potatoes were immersed in a filmogenic solution of methylcellulose (1%) with sorbitol (0,75%) as a plasticizer, dehydrated, and then packaged under atmospheric air, and modified with argon (20seg. e 230mmHg), and vacuum (15seg. e 54mmHg). Stored MP product at 8°C for 12 days was assessed at intervals of 3 days by microbiological, physiological, physicochemical and physical analyses. Every 3 days the MP potatoes were fried and evaluated for moisture loss, oil absorption, instrumental texture and sensory evaluation. Packaging under atmospheric air was effective in reducing the mass loss of MP potatoes. The vacuum packaging was more effective for the MP product without edible coating, because they kept the pH, acidity, starch and sugar level more similar to the first day experiment, as well as low browning rate. The vacuum packaging, however, would not be appropriate when the purpose is frying, because this treatment showed the greatest loss of moisture and increased oil absorption. Packaging under argon atmosphere was also more effective for the MP product without edible coating, and it was an important factor to reduce CO2 levels inside the package, showed lower respiratory rate, lower browning index both before and after frying, reduced moisture loss during frying, kept fried product firmness better and also minimized oil absorption from the 3rd day of storage. The use of edible coating was effective in reducing the respiration of MP product until the 6rd day. For the fried product, the use of coating was a determining factor for moisture retention during frying of potatoes, and also to decrease oil absorption along the potato storage.

<div>Zein is major nitrogen storage protein that accounts for nearly half of the protein content of the corn grain. As a byproduct of starch and ethanol processing, it is generally recognized as safe (GRAS) and soluble in up to 70% ethanol. Historically, zein has been used for films and coatings. However, usage of the corn protein has diminished in recent years. New advances in food nanotechnology has renewed interest in zein. By forming the protein into stable nanoparticles capable of being dispersed in aqueous solution, zein can be used in many applications ranging from improving stability and digestion of functional ingredients or active biodegradable packaging. Developing novel applications for this protein would then add value to a waste product during the processing of corn.</div><div><br></div><div>The formation of hydrophobic zein nanoparticles (ZNPs) would allow for easier dispersion in aqueous systems without further modification to increase hydrophilicity. However, their dispersibility and subsequent stability in aqueous systems is important for its functionality in food. Addition of sufficient ι-carrageenan (ι-CGN) prevented aggregation in the pH range of 5.25 to 6.75 and limited aggregation at pH 7.0. Enhanced stability was attributed to the adhesion of ι-CGN to the nanoparticle surface, as the ZNPs surface charge became significantly negative with introduction of ι-CGN. These particles remained stable for up to 30 days with significantly lower turbidity and greater resistance to gravitational separation when compared to ZNPs alone.</div><div><br></div><div>Lutein was encapsulated in zein nanoparticles, and the bioaccessibility was determined by quantifying lutein content after exposure to in vitro gastric and intestinal conditions. It was found that ZNPs provided a protective environment for lutein in aqueous dispersions and would release the carotenoid into the small intestine by rapid breakdown of ZNP structure during intestinal digestion. However, the process or residual components must have limited uptake of lutein into mixed micelles. ZNPs can be a promising encapsulating agent to improve the digestive stability of lutein.</div><div><br></div><div>Composite films composed of methylcellulose (MC) and zein nanoparticles (ZNPs) were prepared as a potential biodegradable alternative for synthetic packaging. The effects of ZNP aggregation on mechanical and moisture barrier properties as affected by drying temperature, pH, and stabilizers were tested. The phase separation of composite films was determined to be detrimental to both its mechanical and moisture barrier properties. The drying temperature, pH, and composition of the solvent casting solution all affected the distribution of ZNPs dispersed in MC films. Drying films at 23°C or setting the pH to 6.5 resulted in ZNP aggregation and weaker, brittle films that were poor moisture barriers. The presence of CGN was able to provide stability to ZNPs at both pH 4 and 6.5, thus improving its mechanical and moisture barrier properties.</div>

O Brasil é hoje o maior produtor de cana-de-açúcar no mundo e a previsão de safra para 2016 é de 658,7 milhões de toneladas. Como o bagaço da cana consiste de 14% de sua massa serão produzidas cerca de 92 milhões de toneladas desse coproduto. Buscando alternativas sustentáveis existem algumas formas de aproveitamento do mesmo, seja na produção de energia, de etanol de segunda geração ou de derivados celulósicos, foco do presente estudo. Objetivou-se através deste trabalho obter metilcelulose por meio de processos sequenciados. Partindo do bagaço de cana in natura, celulose, hemicelulose e lignina foram segregadas por hidrólises, sendo que o foco foi a fração celulósica. A mesma passou por duas diferentes sequências de branqueamento, obtendo celulose purificada, da qual foi produzida a metilcelulose com potencial aplicabilidade industrial. As sequências de branqueamento avaliadas foram uma livre de cloro elementar (ECF) e outra totalmente livre de cloro (TCF), visando reduzir ou suprimir a geração de poluentes tóxicos, principalmente compostos organoclorados. Uma das escolhas para esse objetivo foi o emprego de tecnologia baseada no tratamento enzimático, através da lacase, na sequência TCF. Cada material gerado por etapa de estudo foi analisado. O bagaço de cana, e as celuloses geradas pelas hidrólises foram caracterizadas quanto aos teores de celulose, hemicelulose, lignina, cinzas e extrativos. A celulose gerada antes e após cada etapa de branqueamento foi caracterizada, alcançando por meio da rota ECF uma redução de 80,5% do número kappa, aumento de 3,6 vezes do grau de alvura e pouca variação na viscosidade. Para a rota TCF houve redução de 48,7% do número kappa, aumento de 2,3 vezes do grau de alvura e melhora das propriedades da fibra por meio do aumento da viscosidade. A metilcelulose foi caracterizada por DRX, FTIR, TGA/DTG, MEV e solubilidade. Concluiu-se que os tratamentos foram realizados de maneira eficiente, a otimização das etapas de branqueamento proporcionou uma boa purificação da celulose, a partir da qual pôde ser produzida metilcelulose de boa qualidade, confirmada pelas análises do material. / Brazil is now the largest producer of sugarcane in the world and harvest forecast for 2016 is 658.7 million tons. Such as sugarcane bagasse consists of 14% of its mass will be produced about 92 million tons of this coproduct. Seeking sustainable alternatives there are some ways to use the same, whether in energy production of second-generation ethanol or cellulosic derivatives, focus of this study. The objective was to get through this work methylcellulose through sequenced processes. Starting from sugarcane bagasse, cellulose, hemicellulose and lignin were segregated by hydrolysis, and the focus was the cellulosic fraction. The same underwent two different bleaching sequences, obtaining purified cellulose, which was produced methylcellulose having potential industrial applicability. bleaching sequences evaluated were an elemental chlorine free (ECF) and other totally chlorine free (TCF), to reduce or eliminate the generation of toxic pollutants, organochlorine compounds mainly. One of the choices for this purpose was the use of technology based on enzymatic treatment by Laccase in TCF sequence. Each material generated by step study was analyzed. The sugarcane bagasse, and the pulps generated by hydrolysis were characterized how to cellulose, hemicellulose, lignin, ash and extractives. Cellulose generated before and after each bleaching stage was characterized, by ECF route reaching a reduction of the kappa number 80.5%, an increased of 3.6 times the degree of whiteness and little variation in viscosity. For TCF route was reduced by 48.7% kappa number, increase the degree of whiteness in 2.3 times and a improvement of fiber properties by increasing the viscosity. The methylcellulose was characterized by XRD, FTIR, TGA / DTG, SEM and solubility. It was concluded that the treatments were performed in an efficient manner, optimization of the bleaching stages provided a good purification of the pulp, from which good quality can be produced methylcellulose, confirmed by analysis of the material.

Este trabajo presenta los resultados de la investigación sobre la preparación y caracterización de las metilcelulosas a partir de las plantas anuales.Las pastas del miscanthus, el cardo, y el eucalipto, se prepararon mediante el proceso IRSP (Impregnation Rapid Steam Pulping) y se blanquearon con las secuencias del TCF (Total Chloride Free), que usan peróxido de hidrógeno y hidróxido de sodio (NaOH). Con el aumento de la severidad del proceso de obtención de las pastas, la accesibilidad y la reactividad de las pastas aumentaron mientras que la viscosidad y el número de la kappa disminuyeron. Se desarrolló un nuevo y sencillo método de metilación para preparar las metilcelulosas a partir de la madera y las plantas anuales en el laboratorio. Cada metilcelulosa de las pastas blanqueadas con las secuencias del TCF se sintetizó en una mezcla de isopropanol con metano de yodo a 600C durante 22 horas después la pasta del TCF se mercerizó en una solución del hidróxido de sodio al 40% durante 1 hora. La mercerización y la metilación se repitieron para obtener un grado de sustitución (DS) más alto. Los resultados de la espectroscopía infrarroja de transformada de Fourier (FTIR) (Fourier Transform Infrared Spectroscopy) mostraron que los grupos del OH de la celulosa habían sido sustituidos parcialmente por grupos del metoxil. Los modelos de sustitución supramolecular de las metilcelulosas se determinaron mediante espectroscopía de resonancia magnética nuclear del carbono-13. La viscosidad intrínseca de las metilcelulosas se midió con agua destilada, una solución al 4% de NaOH, o DMSO. Las propiedades reológicas de las metilcelulosas se midieron con DMSO, una solución al 4% de NaOH o agua destilada. Las metilcelulosas sintetizadas tenían unas propiedades similares a las metilcelulosas comerciales. Los volúmenes hidrosolubles y alcalinosolubles de la metilcelulosas se determinaron mediante extracción con disolventes.Las metilcelulosas se prepararon a partir de pastas de lino, yute, cáñamo, sisal, y abacá mediante metilaciones heterogéneas y homogéneas. Estas pastas se blanquearonmediante el proceso ECF (Elemental Chlorine Free). La mutilación inhomogénea de las pastas blanqueadas mediante el proceso ECF se sintetizó en una mezcla de isopropanol con metano de yodo a 600C durante 22 horas después la pasta del ECF se mercerizó durante 1 hora en una solución de NaOH al 50%. La mutilación homogénea de la pasta blanqueada mediante ECF se realizó en DMSO con metano de yodo a 300C durante 48 horas. Para esta metilación homogénea se usó una metilcelulosa con un grado de sustitución más bajo, que se disolvió completamente en DMSO. La espectroscopía infrarroja de transformada de Fourier (FTIR) de las metilcelulosas mostró la existencia de grupos de metoxiles sobre las moléculas de metilcelulosa. Se utilizó la espectroscopia de resonancia magnética nuclear del carbono 13 para medir los grados de sustitución de las metilcelulosas. Los pesos moleculares de las metilcelulosas hidrosolubles se determinaron con la cromotagrafía de exclusión por tamaños (SEC). Las viscosidades intrínsecas se midieron en una solución de NaOH al 4%. Las metilcelulosas preparadas a partir de pastas de elevadas accesibilidades y reactividades tenían las mejores grados de sustitución, pesos moleculares, viscosidades y viscosidades intrínsecas.Se investigaron las accesibilidades y reactividades de las pastas del ECF. Los volúmenes de glucosa y de xilosa de estas pastas se determinaron mediante HPLC (High performance liquid chromatography) después de la hidrólisis. Las accesibilidades de adsorción de yodo de estas pastas eran bajas y sus fragmentos accesibles estaban entre el 1,31% y el 5,16%. En la región amorfa, sus fragmentos accesibles estaban entre el 5% y el 24%. Las imágenes del SEM (Scanning Electrón Microscopy) mostraron que sus fibrillas tenían distintas estructuras morfológicas. Los resultados de la espectroscopía infrarroja de transformada de Fourier (FTIR) mostraron que, después de los pretratamientos, habían disminuido tanto la media de la intensidad de los enlaces de hidrógeno como los índices de cristalinidad relativos. Sus reactividades aumentaron significativamente después de la mercerización preliminar. Las accesibilidades y reactividades de la pasta del abacá se mejoraron con los tratamientos de impregnación con agua, la mercerización a 15 bares de presión, la explosión de vapor y la mercerización preliminar. La desintegración, el incremento de los huecos, el debilitamiento de la intensidad de los enlaces de hidrógeno, la depolimerización, y la decristalización son esenciales para mejorar las accesibilidades y las reactividades, pero el factor decisivo es la especie de la planta.Hemos estudiado los factores que influyen en el peso molecular (Mw) de las metilcelulosas hidrosolubles preparadas a partir de plantas anuales. El tiempo y la temperatura de impregnación y las condiciones de cocción influyeron de manera diferente en el peso molecular (Mw) de metilcelulosas preparadas a partir de los cardos recogidos en primavera y en verano, el miscanthus y el eucalipto. Se compararon los efectos de los pretratamientos (la impregnación con agua, la mercerización preliminar, la mercerización con presión y la explosión de vapor) en la pasta del abacá. Cuando se pretrató la pasta del abacá, su metilcelulosa hidrosoluble consiguió un peso molecular más alto. De entre los pretratramientos analizados, la explosión de vapor resultó el más adecuado. Para conseguir metilcelulosas con un peso molecular más alto deben perfeccionarse las condiciones de la preparación de las pastas blanqueadas mediante ECF. La especie de las plantas es el factor decisivo para conseguir el peso molecular más alto de las metilcelulosas y para seleccionar los pretratamientos más adecuados.Los parámetros del proceso de obtención de pastas, las condiciones de la metilación, las especies de las plantas, los pretratamientos, y la estructura morfológicas de las pastas influyó en los grados de sustitución de las metilcelulosas preparadas a partir de plantas anuales. Una severidad de impregnación más alta, una temperatura del proceso de obtención de pastas más alta y un incremento del tiempo del mismo proceso consiguieron grados de sustitución más altos. Un aumento de reactivos de la metilación causó un aumento de grado de sustitución. Las pastas obtenidas de distintas especies produjeron grados de sustitución diferentes, trabajando con las mismas condiciones de metilación. Los pretratamientos aumentaron el grado de sustitución de las metilcelulosas.Esta investigación contribuye a encontrar las condiciones apropiadas para metilcelulosas diseñadas a medida, sintetizadas a partir de plantas anuales. Esta investigación demuestra que estas plantas tienen la capacidad de ser preparadas para conseguir metilcelulosas de alta calidad y de alto valor aptas para distintas aplicaciones, como la industria alimentaria, la de la construcción o la farmacéutica. La industria puede utilizar estas plantas anuales de crecimiento rápido para producir metilcelulosas, con lo que, además, se evitará el uso de madera.Palabras clave: abacá, accessibilidad, blanqueo mediante TCF, cáñamo, cardo, eucalipto, grado de sustitución, lino, metilación, metilcelulosa, miscanthus, peso molecular, plantas anuales, proceso de obtención de pasta IRSP, sisal, yute. / Preparation and characterization of methylcelluloses from some annual plantswere investigated.Miscanthus, cardoon, and eucalyptus pulps were produced by Impregnation Rapid Steam Pulping (IRSP) process and bleached by Total Chloride Free (TCF) sequences using hydrogen peroxide and sodium hydroxide. With an increase of pulping severities, accessibilities and reactivities of bleached pulps increased while viscosities and kappa numbers decreased. A novel facile methylation was developed in order to prepare methylcelluloses from wood and annual plants. Each methylcellulose of TCF bleached pulps was synthesized in isopropanol slurry with iodomethane at 600C for 22 hours after the TCF bleached pulp was mercerized in 40% NaOH solution for 1 hour. The mercerization and methylation were repeated in order to obtain a higher degree of substitution (DS). Fourier Transform Infrared (FTIR) spectra showed OH groups of cellulose were partially substituted by methoxyl groups. Supramolecular substitution patterns of methylcelluloses were determined by 13C nuclear magnetic resonance (NMR) spectroscopy. Intrinsic viscosities of methylcelluloses were measured in distilled water, 4% NaOH solution, or dimethyl sulphoxide (DMSO). Rheological properties of methylcelluloses were measured in DMSO, 4% NaOH solution or distilled water, in which the synthesized methylcelluloses had similar properties as commercial methylcelluloses. Watersoluble and alkali-soluble contents of methylcelluloses were determined by solventextraction.We used iodomethane to synthesize methylcelluloses from Elemental Chloride Free (ECF) bleached abaca, hemp, flax, jute, and sisal pulps via heterogeneous and homogeneous methylations. The heterogeneous methylation was carried out in isopropanol with iodomethane at 600C for 22h after a ECF bleached pulp was mercerized in excessive 50% NaOH solution for one hour at ambient temperature. The homogeneous methylation was carried out in dimethyl sulfoxide with iodomethane at 300C for 48h using a methylcellulose of low degree of substitution. Fourier Transform Infrared (FTIR) spectra of the synthesized methylcelluloses showed the existence of methoxyl groups on methylcellulose molecules. The degrees of substitution of the synthesized methylcelluloses were measured by 13C Nuclear Magnetic Resonance (NMR) spectroscopy. The molecular weights of the waterVI soluble methylcelluloses were determined by Size Exclusion Chromatography (SEC). Intrinsic viscosities of the synthesized methylcelluloses were measured in 4% NaOH solution. Methylcelluloses with better properties, such as greater degrees of substitution, molecular weights, viscosities, and intrinsic viscosities, were prepared from the pulps with higher accessibilities and reactivities. The factors influencing the preparation of methylcelluloses from these pulps were discussed.Pretreatments (water-soaking, pre-mercerization, mercerization under a pressure of 15 bars, and steam explosion) were used to improve the accessibilities and reactivities of celluloses of bleached flax, hemp, sisal, abaca, and jute pulps for the synthesis of methylcellulose. Glucose and xylose contents of these pulps were determined by High Performance Liquid Chromatograph (HPLC) after hydrolysis. Degrees of crystallinity of these pulps were determined by X-ray Diffraction (XRD) spectra. Figures of Scanning Electron Microscope (SEM) showed that their fibrils had different morphological structures. The iodine adsorption accessibilities of these pulps were low and accessible fractions ranged from 1.3% to 5.2%. Accessible fractions in amorphous cellulose were calculated in the 5% to 18% range. The accessibilities of these pulps were hemp pulp > flax pulp > sisal pulp > jute pulp > abaca pulp. Fourier Transform Infrared (FTIR) spectra showed that mean hydrogen bond strengths were weakened and relative crystallinity indexes were decreased by pretreatments. The accessibility and reactivity of the abaca pulp were improved by water soaking, mercerization under 15 bars pressure, steam explosion and preliminary mercerization, of which steam explosion and pre-mercerization were thebest treatments. Species was the main factor for the accessibility and reactivity.We studied the factors that influenced the molecular weights (Mw) of watersolublemethylcelluloses prepared from annual plants and juvenile eucalyptus. Miscanthus and cardoon stalks, and bleached pulps of abaca, jute, sisal, hemp, and flax were used as the annual plant materials. A higher concentration of NaOH solution during the impregnation led to a spring cardoon methylcellulose having a lower molecular weight. As the impregnation times increased, so did the molecular weights of the water-soluble methylcelluloses of spring cardoon. The impregnation conditions had less influence on the methylcelluloses of summer cardoon than on the methylcelluloses of spring cardoon. As the cooking times increased, so did the molecular weights of miscanthus methylcelluloses. A lower pulping severity increased the molecular weight of eucalyptus methylcellulose. The preliminary treatments (water soaking, pre-mercerization, mercerization under pressure andsteam explosion) improved the molecular weights of water-soluble abaca methylcelluloses. The steam explosion method was the best of the preliminary treatments for the abaca pulp. Different species led to different molecular weights for methylcelluloses synthesized from ECF bleached pulps, and these were further improved by preliminary mercerization. The molecular weight of &#61537;-cellulose methylcellulose changed as the ratio of the methylation reagent was varied. In order to synthesize an optimum Mw of methylcellulose, the different raw materials can be chosen, the pulping parameters adjusted (including impregnation and cooking), the cellulose pretreated, and the methylcellulose conditions changed. The plant species is the decisive factor for the Mw of methylcellulose.The pulping parameters, the methylation conditions, the species, the pretreatments, and the morphological structures of pulps influenced the degrees of substitution of the methylcelluloses prepared from the annual plants. A higher impregnation severity, a higher pulping temperature, and a longer pulping time caused a higher degree of substitution. An increase of methylation reagents led to an increase of degree of substitution. Methylcelluloses of different degrees of substitution were synthesized from the pulps of different species when a same methylation condition was used. The pretreatments increased the degrees of substitution of methylcelluloses.This investigation contributes to find appropriate conditions for the production of methylcellulose from annual plants. The present investigation demonstrates these annual plants have the capacities to produce upgraded and high quality methylcelluloses for varied applications, such as additives of foods, construction, pharmaceutics, polymerization, paints, and detergents etc. The industry can utilize these annual fast-growth plants to produce methylcelluloses. Therefore, a lot of wood will be saved.Keywords: abaca, accessibility, annual plants, cardoon, degree of substitution, eucalyptus, flax, hemp, IRSP pulping, jute, methylation, methylcellulose, miscanthus, molecular weight, sisal, steam explosion, TCF bleaching.

京都大学 / 新制・課程博士 / 博士(工学) / 甲第23921号 / 工博第5008号 / 新制||工||1782(附属図書館) / 京都大学大学院工学研究科高分子化学専攻 / (主査)教授 古賀 毅, 教授 中村 洋, 教授 竹中 幹人 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM