Thesis (Ph. D.)--University of Wisconsin, 1964. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Bibliography: leaves [357]-365.

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Η λιγνοκυτταρίνη είναι, περίπου, η μισή από τη συνολική ποσότητα ύλης που παράγεται από τη φωτοσύνθεση. Αποτελείται από τρία είδη πολυμερών: την κυτταρίνη, την ημικυτταρίνη και τη λιγνίνη. Η κυτταρίνη είναι το απλούστερο από τα συστατικά που βρίσκονται σε λιγνοκυτταρινικά υλικά. Είναι η πιο διαδεδομένη οργανική ένωση στη φύση. Μεγάλα ποσοστά κυτταρίνης συναντάμε στα διάφορα είδη χαρτιού. Έχει βρεθεί πως το 80% των αποβλήτων ενός σπιτιού σχετίζεται με την κατανάλωση χαρτιού. Τίθεται, λοιπόν, άλλο ένα ερώτημα πως μπορεί να γίνει δυνατή η αξιοποίηση αυτής της οργανικής ύλης. Αρκεί να διασπαστεί η κυτταρίνη σε γλυκόζη. Η παραγωγή γλυκόζης είναι το πιο ακριβό βήμα κατά την παραγωγή αιθανόλης από βιομάζα. Συνεπώς, κρίνεται απαραίτητη η μείωση του κόστους της παραγωγής της γλυκόζης για την βιομηχανική εκμετάλλευση της μεθόδου. Κατά τη διάρκεια της πειραματικής διαδικασίας διερευνήθηκε η βέλτιστη απόδοση 2 συγκεκριμένων βιομηχανικών ενζύμων για την παραγωγή γλυκόζης από 5 διαφορετικά είδη χαρτιού: Α4, ανακυκλωμένο, χαρτοπετσέτα, χαρτί κουζίνας και χαρτόκουτο. Τα ένζυμα αυτά είναι μια κυτταρινάση (Celluclast 1.5 L FG) και μια κελλοβιάση (Novozym 188), τα οποία πρέπει να χρησιμοποιηθούν μαζί γιατί δρουν συνεργειακά, το πρώτο αποικοδομώντας τη μεγαλομοριακή κυτταρίνη σε μικρού μεγέθους ολιγοσακχαρίτες και κυρίως κελλοβιόζη, και το δεύτερο υδρολύοντας την κελλοβιόζη σε γλυκόζη. Τα είδη χαρτιού επιλέχθηκαν λόγω της ευρείας χρήσης τους, αλλά και της αδυναμίας πολλαπλής ανακύκλωσής τους ή ακόμα απλής (χαρτοπετσέτα, χαρτί κουζίνας) ανακύκλωσής τους. Το πρόβλημα υπό εξέταση σε αυτά τα πειράματα ήταν διττό: η διερεύνηση, και κατά πόσο είναι απαραίτητη, ειδικής επεξεργασίας των χαρτιών πριν την εφαρμογή τους προς παραγωγή γλυκόζης και η χρήση διασυνδεδεμένων ενζύμων για τη μείωση του κόστους εφαρμογής τους Αρχικά μελετήθηκε η απόδοση αυτών των ενζύμων, σε ελεύθερη μορφή (μη διασυνδεδεμένα), στην παραγωγή γλυκόζης από απόβλητα χαρτιού. Παρόλα αυτά, συνέχισαν να υπάρχουν 2 βασικά μειονεκτήματα: α. η ενζυμική δραστικότητα χάνονταν με γρήγορο ρυθμό, με αποτέλεσμα να περιορίζεται η παραγωγή της γλυκόζης, β. αρκετά μεγάλο οικονομικό κόστος των ενζύμων. Γι’ αυτό στη συνέχεια μελετήθηκε η απόδοση των ενζύμων αφού αυτά είχαν μερικώς ακινητοποιηθεί μέσω διασύνδεσης, το Celluclast με EDAC και το Novozym με γλουταραλδεϋδη, όπως είχε διαπιστωθεί από προηγούμενες μελέτες ότι είναι ο καλύτερος συνδυασμός, ο οποίος μάλιστα επιτρέπει σε υψηλό ποσοστό τη διατήρηση της ενζυμικής δραστικότητας. Κάτω από αυτές τις συνθήκες επιτεύχθηκε σταθεροποίηση των ενζύμων και μείωση της χρονικής διάρκειας της κατεργασίας σε δύο ημέρες από πέντε που απαιτούνταν με τη χρήση μη διασυνδεδεμένων ενζύμων. / The ligno is about half the total quantity of matter produced by photosynthesis. It consists of three types of polymers: cellulose, the hemicellulose and lignin. Cellulose is the simplest of ingredients are ligno-cellulosic materials. It is the most common organic compound in nature. Large percentages of cellulose found in different types of paper. It found that 80% of waste a house associated with the consumption of paper. The question, then, another question that may be possible to use this organic matter. Just to break the cellulose into glucose. The production of glucose is the most expensive step in the production of ethanol from biomass. Therefore, it is necessary to reduce the cost of production of glucose for the industrial exploitation of the method. During the experimental procedure to investigate the optimal performance of these 2 enzymes for industrial production of glucose from 5 different types of paper: A4, recycled, napkin, kitchen paper and cardboard box. The enzyme is a cellulase (Celluclast 1.5 L FG) and a kelloviasi (Novozym 188), which must be used together because they act synergistic, the first deconstructing the macromolecular cellulose into small oligosaccharides and especially cellobiose, and the second hydrolyzing the cellobiose glucose. The paper items were selected because of their widespread use, and the inability of multiple recycling or even simple (napkin, kitchen paper) recycling. The problem under consideration in these experiments was twofold: to investigate, and whether it is needed, special processing of papers prior to their use for glucose production and use of enzyme grid to reduce the cost of their implementation First, the performance of these enzymes in free form (not connected), the glucose production from waste paper. Nevertheless, they continued to have 2 main drawbacks: a. The enzyme activity lost at a rapid pace, thereby limiting the production of glucose, b. sizable economic cost of enzymes. So then we studied the efficiency of enzymes after they had been partially paralyzed by liaison with the Celluclast EDAC and Novozym with glutaraldehyde, as found by previous studies that the best combination, which allows even high conservation enzyme activity. Under these conditions achieved stabilization of enzymes and reducing the duration of treatment in two days from five required the use of non-connected enzymes.

Made available in DSpace on 2018-08-01T21:58:48Z (GMT). No. of bitstreams: 1 tese_10611_Flavia Tosato.pdf: 3350639 bytes, checksum: 70973978751713caf9a8020e18b13280 (MD5) Previous issue date: 2016-12-09 / Análises rápidas, baratas e eficientes são necessárias para as rotinas laboratoriais, principalmente quando aplicada em química forense. As utilizações de fontes ambientes permitem que as análises sejam diretas e rápidas. Assim, são opções inovadoras para melhorar a sensibilidade e seletividade. Neste trabalho, foi desenvolvida uma metodologia utilizando a espectrometria de massas ambiente por paper spray ionization mass spectrometry (PS-MS) para diferentes matrizes de dados: (i) identificar e quantificar cocaína e seus adulterantes a partir da cromatografia em camada delgada acoplada ao PS-MS; (ii) realizar a discriminação ou classificação de dez marcas brasileiras de cervejas em pilsen e lager; e (iii) identificar a falsificação controlada de Uisque com cachaça visando quantificar o volume de cachaça adicionado na mistura. Na análise de cocaína e adulterantes, os padrões foram identificados na CCD e analisados por PS-MS, e uma curva de calibração foi otimizada. A cerveja foi previamente fracionada usando a metodologia de extração em fase sólida (SPE) com água/metanol e os quatro extratos foram caracterizados no modo positivo de ionização, PS(+)MS. Para ambos os casos, foram aplicados de 20 µL do analito sobre a superfície do papel do PS-MS. Na quantificação de cachaça em misturas de whisk-cachaça. Os resultados indicam que, utilização da CCD acoplado ao PS-MS possibilita a identificação de cocaína e seus adulterantes uma ótima linearidade paras as curvas foi encontrada (cocaína (R2 = 0,9989), benzocaína, (R2 = 0,9934), a cafeína (R2 = 0,9988), a fenacetina (R2 = 0,9966), e a lidocaína (R2 = 0,9987)) e LOD inferior ao da técnica de CCD. Para as amostras de cerveja os sinais de açúcares se sobressaem sobre os demais grupos, e após a extração com água/metanol foi possível distinguir os espectros das diferentes marcas de cervejas e classifica-las em pilsen e lager pela técnica de PCA. Utilizando o PS(±)-MS e PLS com seleção de variáveis foi possível estimar quantitativamente o teor de cachaça misturado ao uísque. Com isso, utilização de fontes ambientes, como PS mostra-se eficaz para identificação de diversas matrizes, facilitando as análises de rotina.

Made available in DSpace on 2018-08-01T21:58:59Z (GMT). No. of bitstreams: 1 tese_11518_Tese_eloilson_Domingos_VERSÃO IMPRESSÃO.pdf: 3568693 bytes, checksum: cd4564d6013c45b3ddc32e2ccd0a7957 (MD5) Previous issue date: 2017-11-30 / Com o advento de uma nova família de técnicas de ionização, a espectrometria de massas (MS) ambiente foi introduzida como uma maneira simples de gerar íons na MS. Entre elas, a técnica de ionização por paper spray (PS) demonstrou-se versátil para resolver inúmeros problemas. Neste trabalho, a técnica de PS-MS no modo de ionização positiva (PS(+)-MS) foi aplicada em três subáreas da química forense: drogas de abuso e documentoscopia e ervas fitoterápicas. Na primeira, a técnica PS-(+)-MS determinou o perfil químico de drogas sintéticas tais como selos contendo 25I-NBOMe (2-(4-iodo-2,5-dimetoxifenil)-n-[(2-Metoxifenil) metil] etamina), extratos e folhas de canabinóides naturais (&#916;9-THC) e canabinóides sintéticos (JWH-073; 5F-AKB48; JWH-122; JWH-250; e JWH-210). Em todos os casos, as moléculas foram facilmente detectadas na sua forma protonada ([M+H]+) com resolução, m/&#916;m50% = 67,000 e uma precisão de massa menor que <2 ppm. O desempenho da técnica PS(+)-MS foi comparado com o de outras fontes de ionização: leaf Spray (LS-MS) e eletrospray (ESI-MS). Além disso, um método foi desenvolvido para quantificar uma série de drogas ilícitas (de 1 a 110 &#120583;g L-1, com linearidade de R2> 0,99). Em documentoscopia, a técnica PS(+)-MS foi capaz de obter com sucesso o perfil químico de diferentes canetas vendidas no comercio. A intensidade relativa (RII372) do corante azul de metileno foi monitorada para discriminar os cruzamentos de traços de canetas e, até a data, os documentos questionados. O perfil químico das notas brasileiras de segunda geração de R$ 100,00 (reais) também foi explorado. A técnica PS(+)-MS foi capaz de classificar as notas em autêntico ou falsificadas. Constatando que amostras falsas possuem um perfil químico similar às notas caseiras da impressora Deskjet®. Finalmente, aplicamos PS(+)-MS para verificar a autenticidade de ervas usadas para perda de peso. Quinze diferentes medicamentos à base destas ervas foram analisados por PS(+)-MS. Encontrando diferentes tipos de compostos: sibutramina (m/z 280), cafeína (m/z 195), glicose (m/z 203 [M+Na], m/z 219 [M+K] e sacarose (m/z 381 [M+K]). Todas essas substâncias não estavam listadas em seus rótulos. Em geral, a técnica PS(+)-MS mostrou ser uma excelente ferramenta analítica em química forense. O segundo estudo abordado foi o controle de qualidade de combustíveis com aplicação do micro-espectrômetro portátil na região do infravermelho próximo (MICRONIR). Neste trabalho, verificou-se a potencialidade do MICRONIR no controle da qualidade do combustível. Assim, modelos quimiométricos (usando o PLS - regressão por mínimos quadrados parciais) foram desenvolvidos para quantificar biodiesel em Diesel (LD=0,5 wt%; LQ=1,8 wt%, e RMSEP=1.8 wt%); enxofre em Diesel (LD=2,4 mg L-1; LQ=8,0 mg L-1, e RMSEP=13,2 mg L-1); gasolina, etanol e metanol em gasolina tipo C (LDgas=0,55 wt%; LQgas=1,84 wt%, e RMSEPgas=0,81 wt%; LDet=0,75 wt%; LQgas=2,50 wt%, e RMSEPeth=3,81 wt%; LDmet = 0,85 wt%; LQmet = 2,84 wt%, e RMSEPmet = 1,80 wt%); e água, metanol e etanol em etanol combustível hidratado (LDH2O = 0,04 wt%; LQH2O=1,29 wt%, e RMSEPH2O=1,05 wt%; LDmet= 0,52 wt%; LQmet = 1,73 wt%, e RMSEPmet =2,78wt %; LDet=1,22 wt%; LQet=4,07 wt%, e RMSEPet= 4,41 wt%). O método proposto apresentou alta precisão e exatidão em todos os casos, e os resultados mostraram que a técnica MICRONIR teve excelente desempenho no controle da qualidade do combustível.

Abstract Axially moving material problems are concerned with the dynamic response, vibration and stability of slender members which are in a state of translation. In Finland these are particularly important in the functioning of paper machines, in which out of plane vibration in the paper web, known as flutter, which from the point of view of mechanics is a phenomenon typical of an axially moving material, limits operation speeds and therefore the productivity of the machines. This subject links together a number of physical phenomena associated with aerodynamics, web movement, material behaviour and the geometry of the system. The aim of this research is to present a theoretical and numerical formulation of the nonlinear dynamic analysis of an axially moving web. The theoretical model is based on a mixed description of the continuum problem in the context of the dynamics of initially stressed solids. Membrane elasticity is included via a finite strain model, and the membrane transport speed through a kinematical study. Hamilton's principle provides nonlinear equations which describe the three-dimensional motion of the membrane. The incremental equations of Hamilton's principle are discretized by the finite element method. The formulation includes geometrically nonlinear effects: large displacements, variations in membrane tension and variations in transport velocity due to deformation. This novel numerical model was implemented by adding an axially moving membrane element to a FEM program which contains acoustic fluid elements and contact algorithms. This allowed analysis of problems including interaction with the surrounding air field and contact between supporting structures. The model was tested by comparing previous experiments and present nonlinear description of the dynamic behaviour of an axially moving web. The effects of contact between finite rolls and the membrane and interaction between the surrounding air and the membrane were included in the model. The results show that nonlinearities and coupling phenomena have a considerable effect on the dynamic behaviour of the system. The nonlinearities cause a noticeable stiffening of the membrane, and the vibration frequency of nonlinear system increases as the amplitude grows. At high values of transport velocity the first mode frequency passes over the second linear harmonic, and even the third. The results also show that the cylindrical supports have a distinct influence on the behaviour of an axially moving sheet. The boundary of the contact region clearly moves and weakens the nonlinear hardening phenomena that otherwise increase the fundamental frequency. This influence strengthens as the radius of the cylinders increases.

M.Tech. (Chemical Engineering) / Please refer to full text to view abstract

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