Characterization of cellulose by its molecular weight distribution is afforded after polymeranalogeous dissolution. Additionally, a molecular dispersion of the polymer is a prerequisite. Common processes are dissolution of cellulose in dimethylacetamide-lithiumchloride, nitration and carbanilation. Degradation of the polysaccharide chains can occur in each of the mentioned processes. It is shown that degradation in pyridine occurs via beta-elimination at carbonyl groups along the cellulose chains. Carbanilierung in DMSO is much more pronounced. It comprises oxidation along the Pfitzner-Moffatt-mechanism and subsequent beta-elimination at the thus formed carbonyl-groups. This was elucidated with model systems and by investigation of the carbanilation in different media. Carbonyl groups of cellulose are masked through reaction with phenylisocyanate. This was shown with model. Therefore, the determination of carbonyl groups in cellulose-tricarbanilates is not possible. The separation of low-molecular weight byproducts was optimised. The influence of pretreatment and preactivation of cellulose-samples on the completeness of the conversion was studied. A standard protocol for the carbanilation of cellulose is provided. / Cellulose wird u.a. durch ihre Molmassenverteilung charakterisiert, deren Ermittlung ein polymeranaloges Verfahren zur molekulardispersen Auflösung des Polymers erfordert. Hierfür sind die Direktlösung, die Nitrierung und die Carbanilierung in Gebrauch. Bei allen Prozessen kann es zum Abbau der Polysaccharidketten kommen, wobei diesen Prozessen wenig Beachtung geschenkt wurde. In der Arbeit wird gezeigt, daß der Abbau bei der Carbanilierung in Pyridin durch Beta-Eliminierung an vorhandenen Carbonylgruppen erfolgt. Die Carbanilierung in DMSO fällt stets stärker aus als bei Einsatz von Pyridin und umfasst die Prozesse Oxidation nach dem Pfitzner-Moffatt-Mechanismus und anschließende Beta-Eliminierung an den neu gebildeten Carbonylgruppen. Dies wird durch Untersuchungen an Modellsystemen und am Polymer herausgearbeitet. Carbonylgruppen an Cellulose werden durch die Umsetzung mit Phenylisocyanat maskiert, was an Modellverbindungen gezeigt wurde (Bildung von Endioldicarbanilaten und carbanilierten Halbacetalen). Ihre Bestimmung in Cellulosecarbanilaten ist daher nicht möglich. Die Abtrennung von niedermolekularen Nebenprodukten der Umsetzung wurde optimiert. Der Einfluss der Vorbehandlung und Voraktivierung von Celluloseproben auf die Vollständigkeit der Umsetzung wurde eingehend untersucht. Es wird ein Standardverfahren zur Carbanilierung von Cellulose angegeben.

No description available.

Made available in DSpace on 2014-06-11T19:22:32Z (GMT). No. of bitstreams: 0 Previous issue date: 2010-08-31Bitstream added on 2014-06-13T20:09:44Z : No. of bitstreams: 1 estremote_mm_me_ilha.pdf: 1708238 bytes, checksum: b2b9251aec47823d0f93f23f57209dcb (MD5) / Neste trabalho descreve-se um sistema constituído por duas plataformas de forças e seus respectivos circuitos de condicionamento e interfaceamento de sinais, projetado para medir a distribuição de descarga de peso na região plantar de pacientes. Em cada plataforma de força foram acopladas 24 células de carga construídas com extensômetros. As características estáticas do sistema foram determinadas em laboratório utilizando pesos conhecidos. O sistema apresentou linearidade, com coeficiente de determinação de 0,9997, baixa histerese, precisão de 0,84% e resolução de 0,5 N. As medidas são apresentadas na tela de um computador facilitando a visualização para especialistas da área, principalmente médicos, fisioterapeutas e terapeutas ocupacionais. Utilizando o sistema foram medidas as distribuições de peso na região plantar de 87 indivíduos sem hemiplegia (sem histórico de queixas de dores ou problemas no sistema neuromusculoesquelético) e de 10 hemiplégicos crônicos, com mais de um ano de hemiplegia. Estes foram submetidos à avaliação utilizando a Escala de Equilíbrio de Berg. Entre os indivíduos se hemiplegia, estudou-se mais detalhadamente um grupo de 15 bailarinos e um de 12 ginastas rítmicas. Determinou-se a relação entre a distribuição de pesos nos antepés esquerdo e direito de indivíduos sem hemiplegia e hemiplégicos com o sistema implementado. Através do sistema constatou-se que a relação entre a distribuição de pesos no antepé esquerdo e direito dos indivíduos hemiplégicos é muito mais elevada que a dos indivíduos sem hemiplegia. Este resultado era de se esperar, uma vez que o hemiplégico descarrega seu peso predominantemente no lado não plégico / This work describes a system consisting of two force platforms and their conditioning circuits and interfacing signals, designed to measure the distribution of weight load on the plantar region of patients. Each force platform was constructed with 24 load cells with strain gages. The static characteristics of the system were determined in laboratory using known weights. The system showed linearity with determination coefficient of 0.9997, low hysteresis, accuracy of 0.84% and resolution of 0.5 N. The measurements are presented in a computer screen in a friend way for specialists in the health field, mainly doctors, physiotherapists and occupational therapists. Using the system we measured the weight distributions in the plantar region of 87 normal patients (no history of complaints of pain or problems in the neuromuscular system) and 10 hemiplegic, with more than a year of hemiplegia. The latter were evaluated using the Berg Balance Scale. Among normal subjects, we studied a further group of 15 dancers and one of 12 rhythmic gymnasts. The relationship between the distribution of weights in the left and right forefeet of patients with normal and hemiplegic was determined with the implemented system. Through the system we found that the relationship between weight distribution on the left and right forefoot of hemiplegic patients is much higher than that of normal patients. This result was expected, since the hemiplegic unloads his weight predominantly in non-paralyzed side

O impacto da oxidação com ozônio na transformação de compostos orgânicos de elevada massa molar (HMW) para o aumento da biodegradabilidade dos efluentes da indústria de celulose e papel foi investigado sob diferentes doses de ozônio. Os experimentos foram realizados utilizando-se os efluentes primário e de extração alcalina de duas indústrias de celulose sob dois valores iniciais de pH (12 e 7). Utilizou-se um reator em escala de laboratório equipado com um difusor de bolhas finas para a aplicação do ozônio. Os resultados revelaram o potencial da aplicação de ozônio como uma etapa de tratamento anterior ao processo biológico convencional. Para o efluente primário, a aplicação de 0,70 mg\'O IND.3\'/mL efluente elevou a razão DBO5/DQO de 0,18 para 0,35 e foi alcançada uma remoção de cor na ordem de 87%. Para o efluente de extração alcalina da indústria Howe Sound, a razão DBO5/DQO foi elevada de 0,07 para 0,15 (pH inicial 12) e para 0,20 (pH inicial 7) e obteve-se uma remoção de cor por volta de 44% com a aplicação de 0,80 mg\'O IND.3\'/mL efluente. Para o efluente de extração alcalina da indústria Catalyst Paper, obteve-se uma remoção de cor por volta de 78% e a razão DBO5/DQO foi elevada de 0,07 para 0,16 após a aplicação de uma dose de ozônio de 0,80 mg\'O IND.3\'/mL efluente. Essas modificações foram alcançadas por uma redução nas frações de elevada massa molar durante a aplicação de ozônio. Para o efluente primário, observou-se uma elevada redução da faixa de maior massa molecular ( > 2kDa) após a aplicação de 0,72 mg\'O IND.3\'/mL efluente. Alcançaram-se 85% e 61% de remoção da faixa superior a 5 kDa para os efluentes de extração alcalina da indústria Howe Sound sob pH inicial 7 e 12, respectivamente, com a aplicação de cerca de 0,72 mg\'O IND.3\'/mL efluente. A faixa de maior massa molar ( > 10 kDa) dos efluentes de extração alcalina da indústria Catalyst Paper foi removida com a aplicação de aproximadamente 0,80 mg \'O IND.3\'/mL efluente. O papel do ozônio molecular disponível sob pH neutro parece ser de fundamental importância quando o objetivo é a redução dos compostos de elevada massa molecular. / The impact of ozone oxidation in transforming high molecular weight (HMW) organic compounds in order to improve the biodegradability of pulp and paper effluents was investigated under different ozone doses. The experiments were conducted uppon a primary treated effluent and an alkaline bleach plant effluent taken from two pulp mills. The effluents were investigated under different initial pH (7 and 12). Ozone was applied using a semi-batch reactor equipped with fine bubble diffuser. The results showed the potential for using ozone as a pre-treatment to the conventional biological process. Applying 0.70 mg\'O IND.3\'/mLww to the primary treated effluent enhanced the ratio of BOD5/COD was from 0.18 to 0.35 and decreased the colour by 87%. The ratio of BOD5/COD was increased from 0.07 to 0.15 (initial pH 12) and to 0.20 (initial pH 7) and colour was reduced by 44% after applying 0.80 mg\'O IND.3\'/mLww to the alkaline bleach effluent from Howe Sound\'s mill. A similar behavior was observed after 0.80 mg\'O IND.3\'/mLww was applied to the alkaline bleach effluent from Catalyst\'s mill. The ratio of BOD5/COD was increased from 0.07 to 0.16 and the effluent colour decreased by 78%. These changes were primarily driven by reductions of the HMW fractions of the effluent during ozonation. Organics with molecular range higher than 2 kDa were completely removed from the primary treated effluent. Aproximately 85% and 61% of the organics higher than 5 kDa were removed from the Howe Sound\'s alkaline bleach effluent under initial pH 7 and 12, respectively, after applying 0.72 mg\'O IND.3\'/mLww. Organic compounds with molecular weight higher than 10 kDa were completely removed from the Catalyst\'s alkaline bleach effluent after applying 0.80 mg\'O IND.3\'/mLww. Molecular ozone available under neutral conditions seems to play an important role when the removal of the high molecular weight organic compounds is the main objective.

Les propriétés hydrophobes des polymères extracellulaires (PEC) exercent l’influence profonde sur les propriétés de la surface cellulaire. Cependant, de nombreux facteurs tels que les méthodes d'extractions, le type de substrat influencent les caractéristiques des PEC et les informations concernant des caractéristiques hydrophobes sont rarement documentées. L'objectif principal de cette étude est de développer une méthode appropriée pour étudier l'hydrophobicité des PEC, puis d'étudier les caractéristiques hydrophobes des PEC.Le fractionnement hydrphobe par la résine Supelite™ DAX-8 a d'abord été appliqué sur les PEC extraits de boues granulaires anaérobies, deux conditions de pH d'élution (pH 2 et 5) ont été testées. L'impact de sept méthodes d'extraction sur les caractéristiques hydrophobes des PEC a été évalué. Les résultats ont montré que les méthodes d'extraction et le pH de la solution extraitante ont influencé la composition des PEC et leur hydrophobicité. En outre, les extraitants des PEC, par exempe le formaldéhyde, l'éthanol, le dodécylsulfate de sodium (SDS) et Tween 20, ont non seulement introduit une teneur supplémentaire en carbone pendant la mesure du carbone organique total (COT), mais ils ont également interagit avec la résine DAX-8. En comparant la répartition du poids moléculaire apparent (aMW) des échantillons des PEC non traités et ajustés au pH détectés par chromatographie d'exclusion stérique (en anglais SEC), l’information plus complète d’aMW a été préservée à pH 5. Ainsi, le fractionnement hydrophobe par la résine DAX-8 à pH 5 et les méthodes physiques d'extraction PEC ont été préférés dans cette étude.Une analyse qualitative détaillée des caractéristiques hydrophobes des EPS a été étudiée par la technique de la matrice de fluorescence d’excitation-emission (EEM). Les résultats ont montré que les substances de type humique (HS-like) représentaient la majorité des composés organiques des PEC extraits de la boue granulaire anaérobie, et constituaient également le principal support moléculaire de l'hydrophobicité des extraits. Ces composés hydrophobes de type HS étaient essenciellement des molécules petites tailles de 8 kDa à <1 kDa. L’hydrophobité contributée par les protéines (PN) et les polysaccharides (PS) présentait un moindre rapport.Afin d’explorer les propriétés hydrophobes de PN et de PS, ainsi évaluer l'impact de l'addition de Ni(II) sur l'hydrophobicité des extraits des champignons, fongi Phanerochaete chrysosporium a été choisi. Les résultats ont montré que la teneur de PN et de PS dans les PEC extrait de ce type de fongi variait en fonction de la concentration de Ni(II). Avec une augmentation de la concentration de Ni de 0 mg/L à 25 mg/L, la teneur en PN a diminué alors que celle de PS a été augmentée. L'hydrophobicité des PEC du fongi, déterminée par le traitement de la résine DAX-8, a diminué lors que la concentration de Ni augmentait. Par ailleurs, l'intensité du pic de SEC correspondant aux molécules PN-like (Ex/Em = 225/345 nm) de 1,9 × 103 à 10 kDa a été augmentée par l'addition Ni; en même temps, la distribution d’aMW des composés organiques totaux (UV/210) dans les PEC restait presque stable. Ces résultats ont indiqué que les composés de type PN-like peuvent avoir déterminé l'hydrophobicité des PEC fongique dans des conditions de stress.Dans l’extrait plus hétérogène des PEC de boues granulaires anaérobies, des composés HS-like représentaient le composant organique majeur, ainsi le principal support moléculaire de l'hydrophobicité des PEC. En étudiant les caractéristiques hydrophobes des PEC extrait du champignon Phanerochaete chrysosporium, le PN et le PS des PEC jouaient un rôle actif dans la protection du champignon sous le Ni. La concentration élevée de Ni a diminué l'hydrophobicité des PEC fongique, mais elle a augmenté l'hydrophobicité de la surface cellulaire du champignon. Il semble que la présence de Ni favorise l'apparition d'un champignon plus hydrophobe / The hydrophobic properties of extracellular polymeric substances (EPS) exert a profound influence on the cell surface properties. However, many factors such as EPS extractions methods, substrate type influence EPS characteristics, and limited information regarding to the hydrophobic features of EPS can be found. The main aim of this study is to develop a proper method to study EPS hydrophobicity, and then investigate the hydrophobic features of EPS.The hydrophobic fractionation by Supelite™ DAX-8 resin was first applied on the EPS extracted from anaerobic granular sludge, two elution pH conditions i.e. pH 2 and 5 were tested. The impact of seven EPS extraction methods on the hydrophobic features of EPS was assessed. The results showed that the extraction methods and bulk solution pH dramatically influenced the EPS composition and their hydrophobicity. Besides, the EPS extracting reagents namely formaldehyde, ethanol, sodium dodecyl sulfate (SDS) and Tween 20 not only introduced extra carbon content during total organic carbon (TOC) measurement, but also interacted with the DAX-8 resin. By comparing the apparent molecular weight (aMW) distribution of the untreated and pH-adjusted EPS samples detected by size exclusion chromatography, more complete EPS aMW information was preserved at pH 5. Thus, the hydrophobic fractionation by DAX-8 resin at pH 5 and physical EPS extraction methods were preferred in this study.After identifying the proper conditions for DAX-8 resin fractionation, detailed qualitative analysis of the EPS hydrophobic features was further investigated. The results showed that the humic-like substances (HS-like) were the major organic constituent of the EPS extracted from the anaerobic granular sludge, and they were also the main molecular support of the EPS hydrophobicity. Those hydrophobic HS-like compounds were mainly small molecules ranging from 8 kDa to <1 kDa. Proteins (PN) and polysaccharides (PS) contributed to the EPS hydrophobicity to a lesser extent.The role of PN and PS in the EPS hydrophobicity was difficult to be shown. It is known that the major organic constituents of the EPS extracted from bacteria, algae and fungi are PN and PS. Therefore, to explore the hydrophobic features of PN and PS, as well as to investigate the impact of Ni(II) addition, on the EPS hydrophobicity, the fungus Phanerochaete chrysosporium was chosen. The results showed that the contents of PN and PS in the extracted fungal EPS varied with the Ni(II) concentration. With an increase in the Ni concentration from 0 mg/L to 25 mg/L, the PN content was decreased whereas the PS content was increased. The fungal EPS hydrophobicity, determined by the DAX-8 resin treatment, was decreased as the Ni concentration increased.Besides, the peak intensity on the size exclusion chromatography (SEC) corresponding to the PN-like molecules (Ex/Em = 225/345 nm) ranging from 1.9×103 to 10 kDa were intensified by the Ni addition, while the aMW distribution of the total organics (UV/210) in the EPS remained almost stable. These results indicated that those PN-like compounds may determine the hydrophobicity of fungal EPS under stress conditions.For the more heterogeneous EPS extracted from anaerobic granular sludge, HS-like compounds were identified as the major organic component, as well as the main molecular support of the EPS hydrophobicity. By studying the hydrophobic features of the EPS extracted from the fungus Phanerochaete chrysosporium, it showed that the PN and PS in the EPS played an active role in protecting the fungus under Ni stress. The increased Ni concentration decreased the hydrophobicity of fungal EPS, but it increased the cell surface hydrophobicity of the fungus. It seems that the presence of Ni promoted the fungus becoming more hydrophobic

Diplomová práce se zabývá návrhem zařízení pro měření parametrů podvozku závodního vozidla (sbíhavost/rozbíhavost, příklon/odklon, světlá výška vozu, rozložení hmotnosti), které následně slouží pro jeho seřízení. Úvodní teoretická část uvádí přehled nejdůležitějších parametrů podvozku, které mají podstatný vliv na chování a ovladatelnost vozu a které jsou tak nejčastěji předmětem zájmu. Následující kapitola shrnuje metody a zařízení, které se dnes pro měření parametrů podvozku využívají a uvádí jejich výhody a nevýhody. Předposlední kapitola teoretické části je věnována obecným doporučením pro měření parametrů podvozku vozidla a jeho seřizování. Poslední kapitola teoretické části uvádí požadavky na zařízení, jehož návrh je předmětem této práce. Úvod praktické části práce je věnován popisu konstrukce dvou navržených variant pro měření parametrů podvozku vozidla. Následující kapitola pak popisuje přípravu a průběh měření s využitím navržených souborů zařízení. Další kapitola je věnována výběru snímačů a zařízení pro měření. Závěr této kapitoly pak shrnuje přibližné celkové náklady na výrobu obou navržených variant. Poslední kapitolou je napěťová a deformační analýza navržené podpěry automobilu, která podepírá automobil namísto jeho kol. Závěr diplomové práce shrnuje dosažené cíle a zároveň uvádí návrhy a doporučení dalšího vývoje navržených zařízení.

Artificial neural networks have been widely used for machine learning and optimization. A neuro ensemble is a collection of neural networks that works cooperatively on a problem. In the literature, it has been shown that by combining several neural networks, the generalization of the overall system could be enhanced over the separate generalization ability of the individuals. Evolutionary computation can be used to search for a suitable architecture and weights for neural networks. When evolutionary computation is used to evolve a neuro ensemble, it is usually known as evolutionary neuro ensemble. In most real-world problems, we either know little about these problems or the problems are too complex to have a clear vision on how to decompose them by hand. Thus, it is usually desirable to have a method to automatically decompose a complex problem into a set of overlapping or non-overlapping sub-problems and assign one or more specialists (i.e. experts, learning machines) to each of these sub-problems. An important feature of neuro ensemble is automatic problem decomposition. Some neuro ensemble methods are able to generate networks, where each individual network is specialized on a unique sub-task such as mapping a subspace of the feature space. In real world problems, this is usually an important feature for a number of reasons including: (1) it provides an understanding of the decomposition nature of a problem; (2) if a problem changes, one can replace the network associated with the sub-space where the change occurs without affecting the overall ensemble; (3) if one network fails, the rest of the ensemble can still function in their sub-spaces; (4) if one learn the structure of one problem, it can potentially be transferred to other similar problems. In this thesis, I focus on classification problems and present a systematic study of a novel evolutionary neuro ensemble approach which I call cooperative coevolutionary mixture of experts (CCME). Cooperative coevolution (CC) is a branch of evolutionary computation where individuals in different populations cooperate to solve a problem and their fitness function is calculated based on their reciprocal interaction. The mixture of expert model (ME) is a neuro ensemble approach which can generate networks that are specialized on different sub-spaces in the feature space. By combining CC and ME, I have a powerful framework whereby it is able to automatically form the experts and train each of them. I show that the CCME method produces competitive results in terms of generalization ability without increasing the computational cost when compared to traditional training approaches. I also propose two different mechanisms for visualizing the resultant decomposition in high-dimensional feature spaces. The first mechanism is a simple one where data are grouped based on the specialization of each expert and a color-map of the data records is visualized. The second mechanism relies on principal component analysis to project the feature space onto lower dimensions, whereby decision boundaries generated by each expert are visualized through convex approximations. I also investigate the regularization effect of learning by forgetting on the proposed CCME. I show that learning by forgetting helps CCME to generate neuro ensembles of low structural complexity while maintaining their generalization abilities. Overall, the thesis presents an evolutionary neuro ensemble method whereby (1) the generated ensemble generalizes well; (2) it is able to automatically decompose the classification problem; and (3) it generates networks with small architectures.

Background: The relevance of conducting this thesis is evident by the fact that bus and coach casualties have been “stubbornly stable” in Europe recent years and a need for investigating if a similar trend could be found in Sweden is therefore obvious. It was also important to add new knowledge to the bus and coach research in Sweden, since many areas were scarcely addressed. Aims: To describe bus and coach occupants’ injuries, crash and injury mechanisms generated in a traffic environment based on data from the medical sector. Additional aims were to investigate the injury reducing effect of a 3-point belt, the effect of cross-winds, and crucial factors in the emergency- and rescue response. Material and methods: Injury data analyses were based on a complete ten-year medical data set from a catchment-area with about 130,000 inhabitants. A number of crash studies with the scope in different crash phases were conducted by applying and elaborating the Haddon matrix as a framework. An additional framework, Protocol for Major Incidents was used in order to investi-gate the emergency- and rescue response to a severe coach crash. Results: Between the first and second five-year period, the incidence of injured in non-crash in-cidents was increased by 24%. In non-crash incidents, 54% were injured; 2/3 while alighting from a bus or coach. The pre-crash factor cross-wind, in addition to vehicle design, vehicle speed and road friction, was investigated in ten crashes. It was confirmed that cross-wind, in relation to vehicle speed and slippery road conditions, needs more attention. The importance of goods load-ing and passengers’ position in the bus, was indicated by the fact that a displacement of the cen-tre of mass rearwards with 10% increased the necessary coefficient of friction with, on average 45%, which in many cases corresponded to dry road conditions. Three Swedish rollover crashes were analysed with regard to the injury outcome, mechanisms and the possible injury reduction for occupants using a safety belt. A considerable increase in safety for occupants belted with 3-point belts was shown through limiting interior contacts, occupant interaction and the possibility of ejection. Crucial post-crash factors in the emergency- and rescue response showed that ordi-nary ways of working and equipment are not always useful and proper equipment for lifting a coach body is essential in the case of a rollover. Finally, the communication between the hospitals is important, and the telephone systems may be overloaded by calls from worried relatives and media. Conclusions: In non-crash events: Non-crash events constitute a majority of all bus and coach casualties with a high proportion of elderly female occupants among the MAIS 2+ injury cases. Boarding and, especially alighting causes many injuries to the lower extremities. In the pre-crash phase: Cross-winds do affect the safety of buses and coaches and requires more at-tention. Seat belt usage among bus and coach occupants has to be increased. In the crash phase: Rollover and ejection are the major causes behind serious and fatal injuries to bus and coach occupants, consequently, retentive glazing, pillars or rails need more attention. An upgrade from 2-point seat belts to 3-point seat belts yields an increase in the estimated injury re-duction from approximately 50% up to 80% for the MAIS 2+ casualties in a rollover crash. In the post-crash phase: In order to be able to lift a coach body proper equipment originated from experience and development is essential in a rescue operation of a crashed bus or coach. Fur-thermore, to improve the emergency response inside crashed coaches proper methods originated from experience need to be developed. Euro NBAP: Based on the results and conclusions generated in this thesis, a European New Bus and Coach Assessment Programme is suggested, which would provide bus and coach occupants with a assessment programme similar to the Euro NCAP.

Made available in DSpace on 2015-03-26T13:45:36Z (GMT). No. of bitstreams: 1 texto completo.pdf: 1755688 bytes, checksum: 33e268f82618cf29e2d1fa6df5c6fa6c (MD5) Previous issue date: 2013-07-30 / Fundação de Amparo a Pesquisa do Estado de Minas Gerais / A poset metric is the generalization of the Hamming metric. In this work we make a detailed study of poset spaces, hierarchy of I -weights and I -distribution of P P weights, emphasizing the non-degenerate poset codes. We verify the duality relation between the hierarchy weights of poset code and its dual. In the sequel two new parameters are defined to a class of poset codes non-degenerate with dual code is too non-degenerate in the environment. As a result enunciated in the Minimality Theorem, the Variance Theorem and the Minimality Identity in the poset spaces. / Uma generalização da métrica de Hamming é a métrica poset. Faremos um estudo detalhado dos espaços poset, hierarquia de I-pesos e a I-distribuição de pesos, dando ênfase aos códigos poset não degenerados. Verificamos a relação de dualidade poset entre as hierarquias de um código e seu dual. Definimos dois novos parâmetros para a classe de códigos dualmente não degenerados no ambiente poset. Como consequência, enunciamos e mostramos o Teorema da Minimalidade, o Teorema da e Variância e a Identidade de Minimalidades no espaço poset.

Characterization of cellulose by its molecular weight distribution is afforded after polymeranalogeous dissolution. Additionally, a molecular dispersion of the polymer is a prerequisite. Common processes are dissolution of cellulose in dimethylacetamide-lithiumchloride, nitration and carbanilation. Degradation of the polysaccharide chains can occur in each of the mentioned processes. It is shown that degradation in pyridine occurs via beta-elimination at carbonyl groups along the cellulose chains. Carbanilierung in DMSO is much more pronounced. It comprises oxidation along the Pfitzner-Moffatt-mechanism and subsequent beta-elimination at the thus formed carbonyl-groups. This was elucidated with model systems and by investigation of the carbanilation in different media. Carbonyl groups of cellulose are masked through reaction with phenylisocyanate. This was shown with model. Therefore, the determination of carbonyl groups in cellulose-tricarbanilates is not possible. The separation of low-molecular weight byproducts was optimised. The influence of pretreatment and preactivation of cellulose-samples on the completeness of the conversion was studied. A standard protocol for the carbanilation of cellulose is provided. / Cellulose wird u.a. durch ihre Molmassenverteilung charakterisiert, deren Ermittlung ein polymeranaloges Verfahren zur molekulardispersen Auflösung des Polymers erfordert. Hierfür sind die Direktlösung, die Nitrierung und die Carbanilierung in Gebrauch. Bei allen Prozessen kann es zum Abbau der Polysaccharidketten kommen, wobei diesen Prozessen wenig Beachtung geschenkt wurde. In der Arbeit wird gezeigt, daß der Abbau bei der Carbanilierung in Pyridin durch Beta-Eliminierung an vorhandenen Carbonylgruppen erfolgt. Die Carbanilierung in DMSO fällt stets stärker aus als bei Einsatz von Pyridin und umfasst die Prozesse Oxidation nach dem Pfitzner-Moffatt-Mechanismus und anschließende Beta-Eliminierung an den neu gebildeten Carbonylgruppen. Dies wird durch Untersuchungen an Modellsystemen und am Polymer herausgearbeitet. Carbonylgruppen an Cellulose werden durch die Umsetzung mit Phenylisocyanat maskiert, was an Modellverbindungen gezeigt wurde (Bildung von Endioldicarbanilaten und carbanilierten Halbacetalen). Ihre Bestimmung in Cellulosecarbanilaten ist daher nicht möglich. Die Abtrennung von niedermolekularen Nebenprodukten der Umsetzung wurde optimiert. Der Einfluss der Vorbehandlung und Voraktivierung von Celluloseproben auf die Vollständigkeit der Umsetzung wurde eingehend untersucht. Es wird ein Standardverfahren zur Carbanilierung von Cellulose angegeben.