Carboxymethyl cellulose (CMC) is produced commercially in a two-stage process consisting of a mercerization stage, where the pulp is treated with alkali in a water alcohol solution, followed by an etherification stage in which monochloroacetic acid is added to the pulp slurry. In this thesis an extended mercerization stage of a spruce ether pulp was investigated where the parameters studied were the ratio of cellulose I and II, concentration of alkali, temperature and retention time. The influence of the mercerization stage conditions on the etherification stage, were evaluated as the degree of substitution (DS) of the resulting CMC and the filterability of CMC dissolved in water at a concentration of 1%. The DS results suggested that the NaOH concentration in the mercerization stage was the most important of the parameters studied. When the NaOH concentration in the mercerization step was low (9%), a high cellulose II content in the pulp used was found to have no negative impact on the DS of the resulting CMC compared with pulps with only cellulose I. However, when the NaOH concentration was high (27.5%), pulps with high content of cellulose II showed a lower reactivity than those with only cellulose I with respect to the DS of the CMC obtained after a given charge of NaMCA. The results obtained from the filtration ability study of CMC water solutions suggested that both the amount of cellulose II in the original pulp and the temperature had a negative influence on the filtration ability whereas the NaOH concentration in the mercerization stage had a positive influence. The filtration ability was assumed to be influenced highly by the presence of poorly reacted cellulose segments. A retention time between 1-48 h in the mercerization stage had no effect on either the DS or the filtration ability of the CMC. Using NIR FT Raman spectroscopy molecular structures of CMC and its gel fraction were analyzed with respect to the conditions used in the extended mercerization stage. Here it was found that the alkaline concentration had a very strong influence on the following etherification reaction. FT Raman spectra of CMC samples and their gel fractions prepared with low NaOH concentrations (9%) in the mercerization stage indicated an incomplete transformation of cellulose to Na-cellulose before carboxymethylation to CMC. Low average DS values of the CMC, i.e. between 0.42 and 0.50, were yielded. Such CMC dissolved in water caused very thick and semi solid gum-like gels, probably due to an uneven distribution of substituting groups along the cellulose backbone. FT Raman spectra of CMC mercerized with alkaline concentrations at 18.25 and 27.5% in the mercerization stage indicated, however, that all of the cellulose molecules were totally transferred to CMC of high DS, i.e. between 0.88 and 1.05. When dissolved in water such CMC caused gels when they were prepared from ether pulp with a high fraction of cellulose II.

Universiẗat, Diss., 1999--Duisburg.

Orientador: Prof. Dr. Danilo da Cruz Centeno / Dissertação (mestrado) - Universidade Federal do ABC, Programa de Pós-Graduação em Biotecnociência, 2018. / A recalcitrância da parede celular, associada à presença da lignina nos tecidos vegetais, dificulta e torna mais oneroso o uso da biomassa para a produção de etanol de segunda geração. Para driblar este obstáculo, muitos estudos têm sido realizados para compreender o metabolismo da lignina e encontrar formas alternativas de tratamento da biomassa. Recentemente, o ozônio vem sendo aplicado como uma alternativa de pré-tratamento do material lignocelulósico, devido à ação específica sobre a lignina. O presente trabalho possui dois capítulos independentes, e teve como objetivo principal estudar as alterações no conteúdo de lignina em cana-de-açúcar dado as características inerentes aos colmos das variedades estudadas e ao efeito causado pela fumigação aguda com ozônio. No capítulo I, além da quantificação de lignina, determinamos a concentração de açúcares solúveis totais para quatro variedades ¿ RB72454, RB855156, RB867515 e RB9257. Estes dados foram submetidos a análises de correlação e conectância com dados de metabolismo primário previamente obtidos por nosso grupo de pesquisa. A influência da variação da concentração do ácido chiquímico sobre o conteúdo de lignina não pôde ser confirmada através da correlação encontrada entre os dois compostos. Porém, a análise de rede de conectância mostrou que a lignina e o ácido chiquímico estão mais fortemente conectados nas variedades de colheita tardia RB72454 e RB92579. Estas conexões revelam a influência das fases do desenvolvimento vegetal no metabolismo da lignina. No capítulo II, avaliamos as alterações no conteúdo de lignina de folhas de cana-de-açúcar após exposições sucessivas à fumigação com ozônio. Os resultados mostraram uma reação das plantas (despolimerização) aos danos causados pelo estresse oxidativo quando submetidas a um ciclo de fumigação, e um aumento no conteúdo de lignina como uma resposta de memória ao estresse, amplificando suas defesas contra este estresse. O metabolismo da lignina e sua relação com o metabolismo primário é complexo e, no presente estudo, os resultados mostraram que alterações nesta relação podem ser observadas tanto constitutivamente (i.e., inerentes ao desenvolvimento da planta), quanto induzidas por estresse. Ademais, reportamos que, entre as técnicas utilizadas neste trabalho, a rede de conectância e o FT-Raman mostraram-se importantes ferramentas no estudo da lignina. / The recalcitrance of the cell wall is associated with the presence of lignin in the vegetal tissues, making it difficult and more expensive to use biomass for the production of second-generation ethanol. To overcome this obstacle many studies have been carried out to understand the lignin metabolism and to find alternative forms of biomass treatment. Recently, ozone has been applied as an alternative pretreatment of the lignocellulosic material, due to its specific action on lignin. The present work has two independent chapters, in which the main objective was to study the changes in lignin content in sugarcane due to the inherent characteristics of the stems of the studied varieties and the effect caused by the acute fumigation with ozone. In chapter I, in addition to the quantification of lignin we determined the total soluble sugars of four varieties RB72454, RB855156, RB867515 and RB9257. These data were submitted to correlation analysis and the network connectance analysis with data of primary metabolism, previously obtained in our group. The influence of the variation of the shikimate concentration on the lignin content was not confirmed by the correlation found between the two compounds. However, the network connectance analysis showed that lignin and shikimate are more strongly connected in late harvest varieties RB72454 and RB92579. These connections revealed the influence of plant development phases over lignin metabolism. In chapter II, changes in the lignin content of leaf blades of sugarcane were evaluated after multiple exposures to ozone fumigation. The results showed a reaction of the plants (depolymerization) to the damage caused by oxidative stress when submitted to one fumigation exposure, and an increase in lignin content as a memory response to stress, amplifying their defenses against ozone. The metabolism of lignin and its relation to the primary metabolism is complex and our results showed that alterations in this relationship may be constitutive (i.e., inherent to the plant development), and induced by abiotic stress. In addition, we reported that among the techniques applied in this work, the network connectance and the FT-Raman showed to be useful tools in the study of lignin.

No / The use of Fourier-transform Raman spectroscopy for characterising lignocellulosics has increased significantly over the last twenty years. Here, an FT-Raman spectroscopic study of changes in the chemistry of waterlogged archaeological wood of Pinus sp. and Quercus sp. from a prehistoric assemblage recovered from northern Greece is presented. FT-Raman spectral features of biodeteriorated wood were associated with the depletion of lignin and/or carbohydrate polymers at various stages of deterioration. Spectra from the archaeological wood are presented alongside spectra of sound wood of the same taxa. A comparison of the relative changes in intensities of spectral bands associated with lignin and carbohydrates resulting from decay clearly indicated extensive deterioration of both the softwood and hardwood samples and the carbohydrates appear to be more deteriorated than the lignin. The biodeterioration of the archaeological timbers followed a pattern of initial preferential loss of carbohydrates causing significant loss of cellulose and hemicellulose, followed by the degradation of lignin.

No / Bulk crystallisation of protein therapeutic molecules towards their controlled drug delivery is of interest to the biopharmaceutical industry. The complexity of biotherapeutic molecules is likely to lead to complex material properties of crystals in the solid state and to complex transitions. This complexity is explored using batch crystallised lysozyme as a model. The effects of drying and milling on the solid-state transformations of lysozyme crystals were monitored using differential scanning calorimetry (DSC), X-ray powder diffraction (XRPD), FT-Raman, and enzymatic assay. XRPD was used to characterise crystallinity and these data supported those of crystalline lysozyme which gave a distinctive DSC thermogram. The apparent denaturation temperature (Tm) of the amorphous lysozyme was ∼201 °C, while the Tm of the crystalline form was ∼187 °C. Raman spectra supported a more α-helix rich structure of crystalline lysozyme. This structure is consistent with reduced cooperative unit sizes compared to the amorphous lysozyme and is consistent with a reduction in the Tm of the crystalline form. Evidence was obtained that milling also induced denaturation in the solid-state, with the denatured lysozyme showing no thermal transition. The denaturation of the crystalline lysozyme occurred mainly through its amorphous form. Interestingly, the mechanical denaturation of lysozyme did not affect its biological activity on dissolution. Lysozyme crystals on drying did not become amorphous, while milling-time played a crucial role in the crystalline-amorphous-denatured transformations of lysozyme crystals. DSC is shown to be a key tool to monitor quantitatively these transformations.

Neste trabalho, foram estudadas blendas de poliésteres sintéticos e de fonte renovável - poli(tereftalato de butileno-co-adipato de butileno) - PBAT e poli(ácido láctico) - PLA, respectivamente, utilizados em sacolas de supermercado. Amostras destes materiais foram pesadas e enterradas em solo simulado por quatro meses para simular uma compostagem tradicional. As amostras foram então analisadas por Calorimetria Exploratória Diferencial (DSC), Termogravimetria e Termogravimetria Derivada (TG e DTG, incluindo uma Análise Cinética não isotérmica comparativa com sacolas de PE aditivadas com agente pró-degradante, Espectroscopia Vibracional Raman com Transformada de Fourier (FT-Raman), Difração de Raios X e Cromatografia de exclusão por tamanho. Embora não tenha havido perda de massa significativa no período do envelhecimento por compostagem tradicional, foram constatadas importantes alterações estruturais nas amostras, tais como a redução nas energias de ativação (Ea) para os processos de decomposição térmica, a redução na intensidade da banda relativa ao estiramento da carbonila presente nos poliésteres e também uma drástica redução da massa molecular dos polímeros. Em paralelo, a aceleração do processo de biodegradação com Vermicompostagem foi investigado, com resultados bastante promissores, incluindo a degradação total da amostra após um tratamento prévio de exposição à luz solar. / In this study, blends of the synthetic polyester poly(butylene adipate-cotherephtalate) - PBAT - and the natural one poly(lactic acid) - PLA - used as biodegradable plastic shopping bags were studied. Samples of these materials were weighed and buried in simulated soil for four months to simulate domestic composting. These samples were then studied by Differential Scanning Calorimetry (DSC), Thermogravimetry (TG, including a comparative non-isothermal Kinetic Analysis with PE shopping bags containing prodegradation agents), Transformed Fourier Raman Vibrational Spectroscopy (FT-Raman), Wide Angle X-Ray Diffraction (WAXD) and Gel Permeation Chromatography (GPC). It was observed that even though there was no significant mass loss in the period of the ageing when using conventional home composting, important structural changes were detected in the samples, such as the reduction of activation energies (Ea) for the thermal decomposition processes, the reduction of intensity of the peak associated with the stretching of the carbonyl present in both polyesters and also a dramatic decrease in molecular weights. In parallel, the acceleration of the biodegradation process with vermicomposting was investigated, with very promising results, including the total disintegration of the samples when submitted to a previous treatment of sun light exposure.

This thesis deals with the preparation of chemically and/or enzymatically modified cellulose. This modification can be either irreversible or reversible. Irreversible modification is used to prepare cellulose derivatives as end products, whereas reversible modification is used to enhance solubility in the preparation of regenerated cellulose. The irreversible modification studied here was the preparation of carboxymethyl cellulose (CMC) using extended mercerization of a spruce dissolving pulp. More specifically the parameters studied were the effect of mercerization at different proportions of cellulose I and II in the dissolving pulp, the concentration of alkali, the temperature and the reaction time. The parameters evaluated were the degree of substitution, the filterability and the amount of gel obtained when the resulting CMC was dissolved in water. Molecular structures of CMC and its gel fractions were analysed by using NIR FT Raman spectroscopy. It was found that the alkali concentration in the mercerization stage had an extensive influence on the subsequent etherification reaction. FT Raman spectra of CMC samples and their gel fractions prepared with low NaOH concentrations (9%) in the mercerization stage indicated an incomplete transformation of cellulose to Na-cellulose before carboxymethylation to CMC. Low average DS values of the CMC, i.e. between 0.42 and 0.50 were obtained. Such CMC dissolved in water resulted in very thick and semi solid gum-like gels, probably due to an uneven distribution of substituents along the cellulose backbone. FT Raman spectra of CMC samples and their gel fractions mercerized at higher alkaline concentration, i.e. 18.25 and 27.5% in the mercerization stage, indicated on the other hand a complete transformation of cellulose to Na-cellulose before carboxymethylation to CMC. Higher average DS values of the CMC, i.e. between 0.88 and 1.05 were therefore obtained. When dissolved in water such CMC caused gel formation especially when prepared from dissolving pulp with a high fraction of cellulose II. The reversible modification studied was the dissolution of cellulose in NaOH/ZnO. Here the effect of enzyme pretreatment was investigated by using two mono-component enzymes; namely xylanase and endoglucanase, used in consecutive stages. It was found that although the crystallinity and the specific surface area of the dissolving pulp sustained minimal change during the enzymatic treatment; the solubility of pulp increased in a NaOH/ZnO solution from 29% for untreated pulp up to 81% for enzymatic pretreated pulp. / Baksidetext Cellulose can be chemically and/or enzymatically modified. Irreversible modification is used to prepare cellulose derivatives as end products, reversible modification to enhance solubility in the preparation of regenerated cellulose. The irreversible modification studied here was the preparation of carboxymethyl cellulose (CMC) using extended mercerization of a spruce dissolving pulp. More specifically the parameters studied were the effect of mercerization at different proportions of cellulose I and II in the dissolving pulp, the concentration of alkali, the temperature and the reaction time. It was found that the alkali concentration in the mercerization stage had an extensive influence on the subsequent etherification reaction. The content of cellulose II had little effect on degree of substitution (DS) at low NaOH concentration, but tended to decrease DS at higher NaOH concentration in both cases compared with cellulose I. It was also found that the content of cellulose II correlates with the gel formation obtained when the CMC is dissolved in water. The reversible modification studied was the dissolution of cellulose in NaOH/ZnO. Here the effect of enzyme pretreatment was investigated by using two mono-component enzymes; namely xylanase and endoglucanase, used in consecutive stages. It was found that the solubility of pulp increased in a NaOH/ZnO solution from 29% for untreated pulp up to 81% for enzymatic pretreated pulp.

Neste trabalho, foram estudadas blendas de poliésteres sintéticos e de fonte renovável - poli(tereftalato de butileno-co-adipato de butileno) - PBAT e poli(ácido láctico) - PLA, respectivamente, utilizados em sacolas de supermercado. Amostras destes materiais foram pesadas e enterradas em solo simulado por quatro meses para simular uma compostagem tradicional. As amostras foram então analisadas por Calorimetria Exploratória Diferencial (DSC), Termogravimetria e Termogravimetria Derivada (TG e DTG, incluindo uma Análise Cinética não isotérmica comparativa com sacolas de PE aditivadas com agente pró-degradante, Espectroscopia Vibracional Raman com Transformada de Fourier (FT-Raman), Difração de Raios X e Cromatografia de exclusão por tamanho. Embora não tenha havido perda de massa significativa no período do envelhecimento por compostagem tradicional, foram constatadas importantes alterações estruturais nas amostras, tais como a redução nas energias de ativação (Ea) para os processos de decomposição térmica, a redução na intensidade da banda relativa ao estiramento da carbonila presente nos poliésteres e também uma drástica redução da massa molecular dos polímeros. Em paralelo, a aceleração do processo de biodegradação com Vermicompostagem foi investigado, com resultados bastante promissores, incluindo a degradação total da amostra após um tratamento prévio de exposição à luz solar. / In this study, blends of the synthetic polyester poly(butylene adipate-cotherephtalate) - PBAT - and the natural one poly(lactic acid) - PLA - used as biodegradable plastic shopping bags were studied. Samples of these materials were weighed and buried in simulated soil for four months to simulate domestic composting. These samples were then studied by Differential Scanning Calorimetry (DSC), Thermogravimetry (TG, including a comparative non-isothermal Kinetic Analysis with PE shopping bags containing prodegradation agents), Transformed Fourier Raman Vibrational Spectroscopy (FT-Raman), Wide Angle X-Ray Diffraction (WAXD) and Gel Permeation Chromatography (GPC). It was observed that even though there was no significant mass loss in the period of the ageing when using conventional home composting, important structural changes were detected in the samples, such as the reduction of activation energies (Ea) for the thermal decomposition processes, the reduction of intensity of the peak associated with the stretching of the carbonyl present in both polyesters and also a dramatic decrease in molecular weights. In parallel, the acceleration of the biodegradation process with vermicomposting was investigated, with very promising results, including the total disintegration of the samples when submitted to a previous treatment of sun light exposure.

Dans ce travail de thèse, un spectromètre FT-Raman a été développé dans l'intention de mesurer les substances dangereuses de manière propre et durable permettant à l'utilisateur un cout d'utilisation réduit (approche low cost). Dans ce but, le système FT- Raman a été développé en utilisant une combinaison originale de composants conventionnels d'optoméchatronique avec laquelle nous proposons une méthode d'évaluation du spectre. Ce système FT-Raman proposé n'inclut aucun composants spécialisé coûteux et permet la détection de la diffusion Raman et le suivi du chemin optique. Le dispositif a été testé lors d'analyses d'une série de composants chimiques standards largement utilisés dans la spectroscopie Raman (certains d'entre eux sont connus pour leur impact négatif sur la santé et l'environnement). Les résultats du spectre obtenus avec notre dispositif ont confirmé les valeurs signalées par le spectre Raman standard. Une comparaison des spectres avec des appareils commercialisés mesurant le FT-Raman a été également faite, et les résultats indiquent que notre combinaison de composants conventionnels et l'application de notre méthode d'évaluation peuvent être utilisées dans certaines surveillances d'applications demandant un haut degré de précision et la résolution sans toutefois présenter la charge financière que l'achat d'un instrument classique de mesure pourrait représenter. / In this doctoral research project, a Fourier Trasform Raman spectrometer (FT-Raman spectrometer) instrument has been developed with the intention to perform the monitoring of certain materials having a contaminating and harmful nature, in a clean and sustainable manner, and without significantly affecting the financial aspect of the user (low-cost approach). For this purpose, the proposed FT-Raman system has been developed by using an original combination of conventional hardware (optomechatronics) parts and a method that we propose for spectral evaluations. In this FT-Raman system that we propose no specialized and costly hardware parts for optical path compensation, Raman scattering detection, optical path tracking, etc. have been used. The proposed FT-Raman device has been tested by analyzing a series of chemical components widely used in Raman spectroscopy as standard reference materials (some of them are also known due to their negative impact on health or on environment). The resulting spectra obtained using our proposed device have greatly agreed with the values of the standard Raman spectra. A comparison with spectral outputs from state-of-the-art FT-Raman devices has been also performed. These results indicate that our ``flexible" combination of conventional hardware parts and the applied evaluation method that we propose can be used in certain monitoring applications requiring a high degree of frequency accuracy and spectral resolution, without having the burden of a considerable expenditure that such a non-dispersive "classical" instrument might represent.

No description available.