O presente trabalho tem como objetivo estudar as modificações ocorridas na cana-de-açúcar, com diferentes composições químicas e estruturais, pelo pré-tratamento sulfito alcalino. A remoção de lignina e hemicelulose, bem como a introdução de grupos sulfônicos em cana-de-açúcar que ocorrem durante o pré-tratamento sulfito alcalino tornam mais fácil a hidrólise da celulose. A compreensão das modificações químicas e físicas em materiais lignocelulósicos que ocorrem durante este pré-tratamento é fundamental para a geração de processos mais eficazes. Neste trabalho, bagaço e entrenós de cana-de-açúcar, selecionados de plantas híbridas com composição química variada, foram pré-tratados em condições brandas com 10% de sulfito e 5% de hidróxido de sódio por diferentes tempos. No início do pré-tratamento, a deslignificação aumentou rapidamente, o mesmo não aconteceu com a hemicelulose. Nos primeiros 30 min de pré-tratamento do bagaço de cana-de-açúcar houve remoção de 50% da lignina inicial e 30% da hemicelulose, o que ocasionou uma melhora significativa na conversão de celulose, atingindo 64%. Mesmo sem remoção adicional de lignina e hemicelulose, o processo continuou a introduzir os grupos ácidos, o que contribuiu para o inchamento da fibra. A largura da fibra do bagaço não tratado aumentou de 10,4 ?m para 30 ?m no material pré-tratado com 120 min. Estas modificações na fibra foram responsáveis pelo aumento na eficiência da hidrólise enzimática da celulose, a qual atingiu 92%. Híbridos experimentais com teores reduzidos de lignina apresentaram taxas iniciais de hidrólise mais elevadas e um menor tempo de pré-tratamento para alcançar a conversão total de celulose do que a cana de referência. Diferentes regiões (medula, interface, córtex e fração externa) dos entrenós das canas foram hidrolisadas por celulases. O pré-tratamento da interface, córtex e fração externa com sulfito-alcalino produziu substratos menos recalcitrantes com o aumento do tempo de reação e resultou na melhora da hidrólise enzimática. Foram utilizadas várias técnicas para avaliar as mudanças que ocorreram durante o pré-tratamento, as quais foram capazes de estudar a morfologia da superfície e as características químicas das amostras. O tratamento químico ocasionou uma intensa deslignificação e alterações morfológicas nas superfícies das fibras da cana-de-açúcar. A redução na absorção a 285 nm e 315 nm das paredes celulares das fibras, parênquima e dos vasos aumentou substancialmente os valores de conversão enzimática da celulose e da hemicelulose. Microscopia eletrônica de varredura por emissão de campo (FE-SEM) revelou que as fibras da região do córtex e, especialmente, da interface mostrou paredes celulares colapsadas após a parcial deslignificação. Após o tratamento sulfito alcalino, os dados de espectroscopia fotoelétrica de raio-X (XPS) e espectrometria de massa de íons secundários por tempo de vôo (TOF-SIMS) apresentaram um aumento das intensidades dos sinais nas superfícies das fibras, os quais foram atribuídos à presença de carboidratos em algumas amostras. Em conformidade, os sinais de lignina diminuíram nas superfícies das fibras das mesmas amostras. / The present work aims to study the changes occurring in sugar cane, with different in structure and chemical compositions, by sulfite-alkaline pre-treatment. Removing lignin and hemicellulose as well as introducing sulfonic groups in sugar cane pretreated with alkaline sulfite made cellulose hydrolysis easier. Understanding the chemical and physical alterations occurring during this pretreatment of lignocellulosic materials is fundamental for the generation of effective pretreatment methods. In the present work, sugarcane bagasse and also sugar cane internodes, selected from experimental hybrid plants, were pretreated with the alkaline-sulfite process under mild conditions with varied cooking times. The first 30 min of pretreatment of sugar cane bagasse, which removed approximately half of the initial lignin and 30% of hemicellulose seemed responsible for a significant enhancement of the cellulose conversion level, which reached 64%. After the first 30 min of pretreatment, delignification increased slightly and hemicellulose removal was not enhanced. However, the process continued to introduce acid groups into the residual lignin that enhanced the fiber swelling up to 120 min of cooking. The fiber widths increased from 10,4 ?m in the untreated bagasse to 30 ?m in the 120 min-pretreated material. These changes were responsible for an additional increase in the efficiency of enzymatic hydrolysis of the cellulose, which reached 92%. Experimental hybrids with less original lignin presented higher initial hydrolysis rates than reference sugar cane and required lower time of pretreatment to achieve the total cellulose conversion. Different regions (pith, interface, rind and outermost fraction) of the internodes of types of sugarcanes were hydrolyzed by cellulases. The pretreatment of the interface, rind and outermost fraction with alkaline sulfite produced less recalcitrant substrates with increasing reaction time and resulted in improvement enzymatic hydrolysis. Several techniques enabling the study of surface morphological and chemical characteristics were used to evaluate the changes occurring during the pretreatment step. The chemical treatment caused intense delignification and morphological changes on the sugar cane fiber surfaces. The reduction in the absorption at 285 nm and 315 nm of the cell walls of the fibers, parenchyma and vessel, substantially increased the values of enzymatic conversion of cellulose and hemicellulose. Field emission scanning electron microscopy (FE-SEM) indicated that the fibers from rind regions and especially from the interface showed collapsed cell walls after partial delignification. After the alkaline sulfite treatment, X-ray photoelectrom spectroscopy (XPS) and time-of-flight-secondary ion mass spectrometry (ToF-SIMS) data showed increased signal intensities on the fibers surfaces assigned to carbohydrates of some samples. In accordance, the lignin signals diminished on the fiber surfaces of the same samples.

O presente trabalho tem como objetivo estudar as modificações ocorridas na cana-de-açúcar, com diferentes composições químicas e estruturais, pelo pré-tratamento sulfito alcalino. A remoção de lignina e hemicelulose, bem como a introdução de grupos sulfônicos em cana-de-açúcar que ocorrem durante o pré-tratamento sulfito alcalino tornam mais fácil a hidrólise da celulose. A compreensão das modificações químicas e físicas em materiais lignocelulósicos que ocorrem durante este pré-tratamento é fundamental para a geração de processos mais eficazes. Neste trabalho, bagaço e entrenós de cana-de-açúcar, selecionados de plantas híbridas com composição química variada, foram pré-tratados em condições brandas com 10% de sulfito e 5% de hidróxido de sódio por diferentes tempos. No início do pré-tratamento, a deslignificação aumentou rapidamente, o mesmo não aconteceu com a hemicelulose. Nos primeiros 30 min de pré-tratamento do bagaço de cana-de-açúcar houve remoção de 50% da lignina inicial e 30% da hemicelulose, o que ocasionou uma melhora significativa na conversão de celulose, atingindo 64%. Mesmo sem remoção adicional de lignina e hemicelulose, o processo continuou a introduzir os grupos ácidos, o que contribuiu para o inchamento da fibra. A largura da fibra do bagaço não tratado aumentou de 10,4 ?m para 30 ?m no material pré-tratado com 120 min. Estas modificações na fibra foram responsáveis pelo aumento na eficiência da hidrólise enzimática da celulose, a qual atingiu 92%. Híbridos experimentais com teores reduzidos de lignina apresentaram taxas iniciais de hidrólise mais elevadas e um menor tempo de pré-tratamento para alcançar a conversão total de celulose do que a cana de referência. Diferentes regiões (medula, interface, córtex e fração externa) dos entrenós das canas foram hidrolisadas por celulases. O pré-tratamento da interface, córtex e fração externa com sulfito-alcalino produziu substratos menos recalcitrantes com o aumento do tempo de reação e resultou na melhora da hidrólise enzimática. Foram utilizadas várias técnicas para avaliar as mudanças que ocorreram durante o pré-tratamento, as quais foram capazes de estudar a morfologia da superfície e as características químicas das amostras. O tratamento químico ocasionou uma intensa deslignificação e alterações morfológicas nas superfícies das fibras da cana-de-açúcar. A redução na absorção a 285 nm e 315 nm das paredes celulares das fibras, parênquima e dos vasos aumentou substancialmente os valores de conversão enzimática da celulose e da hemicelulose. Microscopia eletrônica de varredura por emissão de campo (FE-SEM) revelou que as fibras da região do córtex e, especialmente, da interface mostrou paredes celulares colapsadas após a parcial deslignificação. Após o tratamento sulfito alcalino, os dados de espectroscopia fotoelétrica de raio-X (XPS) e espectrometria de massa de íons secundários por tempo de vôo (TOF-SIMS) apresentaram um aumento das intensidades dos sinais nas superfícies das fibras, os quais foram atribuídos à presença de carboidratos em algumas amostras. Em conformidade, os sinais de lignina diminuíram nas superfícies das fibras das mesmas amostras. / The present work aims to study the changes occurring in sugar cane, with different in structure and chemical compositions, by sulfite-alkaline pre-treatment. Removing lignin and hemicellulose as well as introducing sulfonic groups in sugar cane pretreated with alkaline sulfite made cellulose hydrolysis easier. Understanding the chemical and physical alterations occurring during this pretreatment of lignocellulosic materials is fundamental for the generation of effective pretreatment methods. In the present work, sugarcane bagasse and also sugar cane internodes, selected from experimental hybrid plants, were pretreated with the alkaline-sulfite process under mild conditions with varied cooking times. The first 30 min of pretreatment of sugar cane bagasse, which removed approximately half of the initial lignin and 30% of hemicellulose seemed responsible for a significant enhancement of the cellulose conversion level, which reached 64%. After the first 30 min of pretreatment, delignification increased slightly and hemicellulose removal was not enhanced. However, the process continued to introduce acid groups into the residual lignin that enhanced the fiber swelling up to 120 min of cooking. The fiber widths increased from 10,4 ?m in the untreated bagasse to 30 ?m in the 120 min-pretreated material. These changes were responsible for an additional increase in the efficiency of enzymatic hydrolysis of the cellulose, which reached 92%. Experimental hybrids with less original lignin presented higher initial hydrolysis rates than reference sugar cane and required lower time of pretreatment to achieve the total cellulose conversion. Different regions (pith, interface, rind and outermost fraction) of the internodes of types of sugarcanes were hydrolyzed by cellulases. The pretreatment of the interface, rind and outermost fraction with alkaline sulfite produced less recalcitrant substrates with increasing reaction time and resulted in improvement enzymatic hydrolysis. Several techniques enabling the study of surface morphological and chemical characteristics were used to evaluate the changes occurring during the pretreatment step. The chemical treatment caused intense delignification and morphological changes on the sugar cane fiber surfaces. The reduction in the absorption at 285 nm and 315 nm of the cell walls of the fibers, parenchyma and vessel, substantially increased the values of enzymatic conversion of cellulose and hemicellulose. Field emission scanning electron microscopy (FE-SEM) indicated that the fibers from rind regions and especially from the interface showed collapsed cell walls after partial delignification. After the alkaline sulfite treatment, X-ray photoelectrom spectroscopy (XPS) and time-of-flight-secondary ion mass spectrometry (ToF-SIMS) data showed increased signal intensities on the fibers surfaces assigned to carbohydrates of some samples. In accordance, the lignin signals diminished on the fiber surfaces of the same samples.

[Truncated abstract] The aims of the study were twofold; firstly, to describe the inequality in infant mortality in Indonesia namely, to look at the extent and magnitude of the problem in terms of the estimated number of infant deaths, the differentials in infant mortality rates, the probability of infant deaths across provinces, urban and rural areas, and across regions of Indonesia. Secondly, to examine the effect of family welfare status and maternal educational levels on the probability of infant deaths. The study design was that of a population-based multistage stratified survey of the 1997 Indonesian Demographic and Health Survey. Results of the study were obtained from a sample of 28,810 reproductive women aged 15 to 49 years who belonged to 34,255 households. A binary outcome variable was selected, namely, whether or not each of the live born infant(s) from the interviewed women was alive or dead prior to reaching one year of age. Of interest were the variables related to socio-economic status, measured by Family Welfare Status Index and maternal educational levels. The following risk factors were also investigated: current contraceptive methods; birth intervals; maternal age at first birth; marital duration; infants’ size perceived by the mothers; infants’ birth weight; marital status; prenatal care by health personnel; antenatal TT immunization; place of delivery; and religion. Geographical strata (province) and residence (urban and rural areas) were also considered. Both descriptive and multivariate analyses were undertaken. Descriptive analysis was aimed at obtaining non-biased estimates of the infant mortality rates at the appropriate levels of aggregation. Multivariate analysis involved a logistic regression model using the Generalized Estimating Equations (GEE) model-fitting technique. The procedure, a multilog-cumlogit , uses the Taylor Series Linearization methods to compute modelbased variance, and which adjusts for the complex sampling design. Results of descriptive analysis indicate that, indeed, there are inequalities in infant mortality across administrative divisions of the country, represented by provinces and regions, as well as across residential areas, namely urban and rural areas. Also, the results suggested that there is socio-economic inequality in infant mortality, as indicated by a dose-response effect across strata of family welfare and maternal educational levels, both individually and interactively. These inequalities varied by residence (urban and rural), provinces and regions (Java Bali, Outer Java Bali I and Outer Java Bali II). Furthermore, the probability of infant mortality was significantly greater among highrisk mothers, characterized by a number of risk factors used in the study

The National Academy of Sciences recently published a report which calls for improvements to the field of forensic science. Their report criticized many forensic disciplines for failure to establish rigorously-tested methods of comparison, and encouraged more research in these areas to establish limitations and assess error rates. This study applies chemometric and statistical methods to current and developing analytical techniques in fiber analysis. In addition to analysis of commercially available dyed textile fibers, two pairs of dyes are selected based for custom fabric dyeing on the similarities of their absorbance spectra and dye molecular structures. Visible absorption spectra for all fiber samples are collected using microspectrophotometry (MSP) and mass spectra are collected using electrospray ionization (ESI) mass spectrometry. Statistical calculations are performed using commercial software packages and software written in-house. Levels of Type I and Type II error are examined for fiber discrimination based on hypothesis testing of visible absorbance spectra using a nonparametric permutation method. This work also explores evaluation of known and questioned fiber populations based on an assessment of p-value distributions from questioned-known fiber comparisons with those of known fiber self-comparisons. Results from the hypothesis testing are compared with principal components analysis (PCA) and discriminant analysis (DA) of visible absorption spectra, as well as PCA and DA of ESI mass spectra. The sensitivity of a statistical approach will also be discussed in terms of how instrumental parameters and sampling methods may influence error rates.

Indiana University-Purdue University Indianapolis (IUPUI) / Microspectrophotometry is a quick, accurate, and reproducible method to compare colored fibers for forensic purposes. The use of chemometric techniques applied to spectroscopic data can provide valuable discriminatory information especially when looking at a complex dataset. Differentiating a group of samples by employing chemometric analysis increases the evidential value of fiber comparisons by decreasing the probability of false association. The aims of this research were to (1) evaluate the chemometric procedure on a data set consisting of blue acrylic fibers and (2) accurately discriminate between yellow polyester fibers with the same dye composition but different dye loadings along with introducing a multivariate calibration approach to determine the dye concentration of fibers. In the first study, background subtracted and normalized visible spectra from eleven blue acrylic exemplars dyed with varying compositions of dyes were discriminated from one another using agglomerative hierarchical clustering (AHC), principal component analysis (PCA), and discriminant analysis (DA). AHC and PCA results agreed showing similar spectra clustering close to one another. DA analysis indicated a total classification accuracy of approximately 93% with only two of the eleven exemplars confused with one another. This was expected because two exemplars consisted of the same dye compositions. An external validation of the data set was performed and showed consistent results, which validated the model produced from the training set. In the second study, background subtracted and normalized visible spectra from ten yellow polyester exemplars dyed with different concentrations of the same dye ranging from 0.1-3.5% (w/w), were analyzed by the same techniques. Three classes of fibers with a classification accuracy of approximately 96% were found representing low, medium, and high dye loadings. Exemplars with similar dye loadings were able to be readily discriminated in some cases based on a classification accuracy of 90% or higher and a receiver operating characteristic area under the curve score of 0.9 or greater. Calibration curves based upon a proximity matrix of dye loadings between 0.1-0.75% (w/w) were developed that provided better accuracy and precision to that of a traditional approach.