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Two approaches for creating a new all-cellulose composite material have been studied: the biosynthesis of compartmentalised bacterial cellulose fibril aggregates and the compression moulding of commercial chemical wood pulps processed with only water. The objective was to study the structural changes during processing and the complexity of relating the mechanical properties of the final biocomposites to the nanoscale structure was highlighted. Solid-state CP/MAS 13C NMR spectroscopy was utilised to determine both the fibril aggregate width and the content of the different crystalline cellulose forms, cellulose I and cellulose II. Using this method, the quantities of hemicellulose present inside the fibre wall and localised at the fibre surfaces could be determined. The formation of cellulose fibrils was affected by the addition of hydroxyethylcellulose (HEC) to a culture medium of Acetobacter aceti, and the fibrils were coated with a thin layer of HEC, which resulted in loose bundles of fibril aggregates. The HEC coating, improved the fibril dispersion in the films and prevented fractures, resulting in a biocomposite with remarkable mechanical properties including improved strength (289 MPa), modulus (12.5 GPa) and toughness (6%). The effect of press temperature was studied during compression moulding of sulphite dissolving-grade pulps at 45 MPa. A higher press temperature yielded increases in the fibril aggregation, water resistance (measured as the water retention value) and Young’s modulus (12 GPa) in the final biocomposite. The high pressure was important for fibril aggregation, possibly including cellulose-cellulose fusion bonds, i.e., fibril aggregation in the fibre-fibre bond region. The optimal press temperature was found to be 170°C because cellulose undergoes thermal degradation at higher temperatures. The effect of hemicellulose was studied by comparing a softwood kraft paper-grade pulp with a softwood sulphite paper and a softwood sulphite dissolving-grade pulp. A significant fibril aggregation of the sulphite pulps suggested that the content and distribution of hemicellulose affected the fibril aggregation. In addition, the hemicellulose structure could influence the ability of the hemicellulose to co-aggregate with cellulose fibrils. Both sulphite pulp biocomposites exhibited Young’s moduli of approximately 12 GPa, whereas that of the kraft pulp was approximately half that value at 6 GPa. This result can be explained by a higher sensitivity to beating in the sulphite pulps. The effect of mercerisation, which introduces disordered cellulose, on the softwood sulphite dissolving-grade pulp was also studied under compression moulding at 170°C and 45 MPa. The mechanisms causing an incomplete transformation of cellulose I to II in a 12 wt% NaOH solution were discussed. The lower modulus of cellulose II and/or the higher quantity of disordered cellulose likely account for the decrease in Young’s modulus in the mercerised biocomposites (6.0 versus 3.9 GPa). / Två metoder för att skapa ett nytt kompositmaterial baserat på enbart cellulosa har studerats, biosyntes av fibrillaggregat bestående av bakteriecellulosa och varmpressning av kommersiella träfiberbaserade massor med vatten som den enda processkemikalien. Målet var att studera de strukturella förändringarna som sker under tillverkningsprocessen. Även komplexiteten i att relatera strukturen på nanonivå till de mekaniska egenskaperna hos de slutliga biokompositerna belystes. Med fastfas CP/MAS 13C NMR-spektroskopi var det möjligt att bestämma både fibrillaggregattjockleken och mängden av cellulosakristallformerna; cellulosa I och cellulosa II. Det var också möjligt att bestämma mängden hemicellulosa dels närvarande inuti fiberväggen och dels mängden lokaliserad på fiberytor. Tillsats av hydroxyetylcellulosa (HEC) i odlingsmediet för Acetobacter aceti påverkade bildandet av cellulosafibriller som blev belagda med ett tunt skikt av HEC, vilket också resulterade i löst bundna fibrillaggregat. HEC-beläggningen förbättrade fibrilldispersionen i filmerna och minskade sprickbildningen, vilket gav en biokomposit med mycket goda mekaniska egenskaper med kombinerad hög styrka (289 MPa), styvhet (12.5 GPa) och seghet (6%). Effekten av presstemperatur vid varmpressning (45 MPa tryck) studerades på sulfit dissolvingmassor. Högre presstemperatur gav ökad fibrillaggregering, ökat vattenmotstånd (mätt som vattenretentionsvärde) och högre styvhet (12 GPa) för biokompositen. Det höga trycket var också viktigt för fibrillaggregeringen, som troligen omfattar cellulosa-cellulosa samkristallisation dvs. fibrillaggregering i fiber-fiber-bindningsregionen. Den optimala presstemperaturen föreslogs vara 170° C pga. termisk nedbrytning av cellulosa vid högre temperaturer. Effekten av hemicellulosa studerades genom att jämföra sulfat pappersmassa med sulfit pappersmassa och sulfit dissolvingmassa. Mängden och fördelningen av hemicellulosa föreslogs ligga till grund för skillnaden i fibrillaggregering, som var mera uttalad i sulfitmassorna. Även hemicellulosans struktur kan påverka förmågan hos hemicellulosa att sam-aggregera med cellulosafibriller. Biokompositerna baserade på sulfitmassorna hade en styvhet på ca. 12 GPa, medan sulfatmassan bara hade hälften av den nivån ca. 6 GPa, vilket förklarades av sulfitmassornas högre känslighet för malning. Även effekten av mercerisering av sulfit dissolvingmassa varmpressad vid 170° C och 45 MPa studerades. Mercerisering introducerar oordnad cellulosa och mekanismerna som endast ger en partiell omvandling av cellulosa I till II i en 12 vikt% NaOH-lösning diskuterades. Den sämre styvheten hos den merceriserade biokompositen (6.0 resp. 3.9 GPa) förklaras troligen genom cellulosa II kristallens lägre styvhet och/eller den högre mängden av oordnad cellulosa. / <p>QC 20121106</p> / Wallenberg Wood Science Center / Biomime

Submitted by Sandra Maria Neri Santiago (sandra.neri@ufpe.br) on 2016-04-15T17:16:20Z No. of bitstreams: 2 license_rdf: 1379 bytes, checksum: ea56f4fcc6f0edcf0e7437b1ff2d434c (MD5) TESE FREDERICO JOSÉ DE SANTANA PONTES.pdf: 8816475 bytes, checksum: 491ea52531215d35d3aa1e14e72232c1 (MD5) / Made available in DSpace on 2016-04-15T17:16:20Z (GMT). No. of bitstreams: 2 license_rdf: 1379 bytes, checksum: ea56f4fcc6f0edcf0e7437b1ff2d434c (MD5) TESE FREDERICO JOSÉ DE SANTANA PONTES.pdf: 8816475 bytes, checksum: 491ea52531215d35d3aa1e14e72232c1 (MD5) Previous issue date: 2013-12-19 / Aspectos estruturais, dinâmicos e de mudanças no estado físico e forma de agregação de bicamadas de Lipídio A foram investigadas utilizando a técnica de simulação computacional por dinâmica molecular com um campo de força atomístico. Sistematicamente diferentes cátions (Na+e Mg2+), em diferentes temperaturas (278K, 300 K e 328 K) e variações fenotípicas (lipídios hexa-, penta- e tetracilados) foram testadas em bicamadas de Lipídio A de duas diferentes bactérias (Pseudomonas aeruginosa e Escherichia coli). Dessa maneira, conseguimos caracterizar fases distintas de bicamadas de Lipídio A de P. aeruginosa, além de obter resultados consistentes com as temperaturas de transição de fase para as membranas das duas espécies de bactéria Gram-negativas. As simulações apontaram também que íons monovalentes induzem um rearranjo na membrana da fase lamelar para uma fase não-lamelar. O estado de agregação das bicamadas de Lipídio A mostrou-se uma combinação importante de dois fatores: a conformação adotada pelo lipídio (se tem um formato mais cônico ou cilíndrico) e a habilidade do contraíon presente em realizar pontes entre os grupos fosfatos de unidades lipídicas distintas. A correlação entre o ângulo de inclinação entre os anéis de glucosamina e o plano da membrana – proposição experimental utilizada para explicar a endotoxicidade e forma de agregação do Lipídio A – não foi observada de maneira quantitativa em nossos cálculos. / Structure, dynamics, phase transition and general assembly of Lipid A bilayers were investigated in this work through atomistic molecular dynamics simulations. A range of temperature (278K, 300K e 328K), cations (mono- and bivalentes: Mg2+ and Na+) and phenotypes of Lipid A (hexa-, penta- and tetraacilated) of two different Gram-negative bacterias (Pseudomonas aeruginosa e Escherichia coli) have been tested in order to characterize the membranes and its properties. Validation for model systems included the appropriate description of area per lipid, order parameter, spatial chemical group distribution and membrane solvation and structure as a function of temperature variation. Moreover, our findings show that Lipid A bilayers undergo from a lamellar to non-lamellar arrangement in the presence of monovalent ions. This is due to the inability of these ions to crosslink phosphate groups from neighboring Lipid A units. Our findings support two dominant aspects governing Lipid A bilayer membrane assembly: the shape of Lipid A units (conical vs cylindrical) and the ability of the counter ion to crosslink between different phosphate groups. Analysis of simulated trajectories do not support quantitatively the experimental proposition that correlates the tilt angle between the glucosamines rings of Lipid A and the membrane plane with acyl chain phenotypical variation

京都大学 / 0048 / 新制・課程博士 / 博士(農学) / 甲第22502号 / 農博第2406号 / 新制||農||1077(附属図書館) / 学位論文||R2||N5282(農学部図書室) / 京都大学大学院農学研究科応用生命科学専攻 / (主査)教授 梅澤 俊明, 教授 矢﨑 一史, 教授 渡邊 隆司 / 学位規則第4条第1項該当 / Doctor of Agricultural Science / Kyoto University / DGAM

Nanocellulose is a nascent and promising material with many exceptional properties and a broad spectrum of potential applications; hence, it has drawn increasing research interests in the past decade.  A new type of nanocellulose -- with mono- or bi-layer cellulose molecular sheet thickness -- was synthesized through a combined chemical-mechanical process (TEMPO-mediated oxidation followed by intensive sonication), and this new material was named molecularly thin nanocellulose (MT nanocellulose).  The overarching objective of this study was to understand the formation and supramolecular structure of MT nanocellulose and contribute to the knowledge of native cellulose structure. The research involved four major bodies of study: preparation of MT nanocellulose, characterization of MT nanocellulose, modeling wood pulp-derived cellulose microfibril cross section structure, and a comparative life cycle assessment (LCA) of different nanocellulose fabrication approaches.  The results revealed that MT nanocellulose with mono- to bi-layer sheet thickness (~0.4-0.8 nm), three to six chain width (~2-5 nm), and hundreds of nanometers to several microns length, can be prepared through TEMPO-mediated oxidation followed by 5-240 min intensive sonication.  The thickness, width, and length of MT nanocellulose all decreased with extended sonication time and leveled off after 1 or 2 h sonication.  Crystallinity, hydrogen bonding, and glycosidic torsion angles were evaluated by XRD, FTIR, Raman, and NMR.  These experiments revealed systematic changes to structure with sonication treatments.  A microfibril "cross section triangle scheme" was developed for the microfibril supramolecular modeling process and a 24-chain hexagonal/elliptical hybrid model was proposed as the most credible representation of the supramolecular arrangement for wood pulp-derived cellulose I" microfibril.  Comparative LCA of the fabrication of nanocellulose indicated that nanocellulose presented a significant environmental burden markup on its precursor, kraft pulp, and the environmental hotspot was attributed to the mechanical disintegration process.  Yet, overall nanocellulose still presented a prominent environmental advantage over other nanomaterials like single-walled carbon nanotubes, due to its relative low energy consumption. Overall, this research developed a facile approach to produce a new type of nanocellulose, the MT nanocellulose, provided new insights about the supramolecular structure of cellulose microfibrils, and evaluated the environmental aspects of the fabrication process of nanocellulose. / Ph. D.

No description available.

Self-assembled lipid tubules are particularly attractive for inorganic synthesis and drug delivery because they have hollow cylindrical shapes and relatively rigid mechanical properties. In this thesis work, we have synthesized lipid tubules of 1,2-bis(tricosa-10,12-dinoyl)-sn-glycero-3-phosphocholine (DC8,9PC) by self-assembly and polymerization in solutions. We demonstrate for the first time that both uniform and modulated molecular tilt orderings exist in the tubule walls, which have been predicted by current theories, and therefore provide valuable supporting evidences for self-assembly mechanisms of chiral molecules. Two novel methods are developed for studying the axial and radial deformations of DC8,9PC lipid tubules. Mechanical properties of DC8,9PC tubules are systematically studied in terms of persistence length, bending rigidity, strain energy, axial and radial elastic moduli, and critical force for collapse. Mechanisms of recovery and surface stiffening are discussed. Due to the high aspect ratio of lipid tubules, the hierarchical assembly of lipid tubules into ordered arrays and desired architectures is critical in developing their applications. Two efficient methods for fabricating ordered arrays of lipid tubules on solid substrates have been developed. Ordered arrays of hybrid silica-lipid tubes are synthesized by tubule array-templated sol-gel reactions. Ordered arrays of optical anisotropic fibers with tunable shapes and refractive indexes are fabricated. This thesis work provides a paradigm for molecularly engineered structures.

La thérapie génique est une forme de médecine moléculaire qui a des potentialités majeures dans le traitement d'un grand nombre de maladies héréditaires ou de cancers. Les acides nucléiques doivent pénétrer à l'intérieur des cellules et interagir avec la machinerie génétique présente. Une des plus grandes limitations dans l'application de ce type de traitement est le développement d'un vecteur sûr et efficace pour transporter ces molécules dans les cellules. Les vecteurs sont classifiés traditionnellement en deux grandes catégories : viral et non-viral. Les vecteurs de type viral sont les plus efficaces et utilisés dans la majorité des tests cliniques, cependant ils peuvent provoquer une forte réponse immunitaire et ils ont des coûts importants de production. Les vecteurs de type non viral peuvent être fabriqués facilement en grande quantité, ne sont pas immunogéniques et possèdent l'avantage de pouvoir être modulés en fonction des applications. Les lipides et les polymères cationiques sont les plus étudiés à cause de leurs propriétés de complexation avec les acides nucléiques. Cependant ces complexes chargés positivement peuvent être toxiques à cause de leur interaction non spécifique avec les membranes cellulaires, ce qui limite leur utilisation in vivo. Cela a conduit à la recherche de nouveaux vecteurs, neutres ou anioniques, pour diminuer les problèmes de cytotoxicité. Les nucléolipides (NL) sont des molécules hybrides bioinspirées amphiphiles formées d’une partie hydrophile nucléotidique et d’une partie hydrophobe lipidique. Ces molécules sont donc capables de s'autoassembler et de former des structures supramoléculaires avec des propriétés physico-chimiques principalement liées à la nature chimique de la tête polaire nucléotidique. L'interaction avec des acides nucléiques est alors possible grâce à des interactions de type Watson-Crick, cependant elles ne sont pas suffisamment élevées pour former un complexe stable pour être utilisées dans les conditions biologiques. La synthèse d’une nouvelle famille de molécules hybrides de type amino-nucléo-lipides (ANL) a été développée dans l'objectif d'améliorer les interactions et donc la complexation grâce à la présence d'un acide aminé sur la partie polaire de l’amphiphile. La synthèse chimique des ANLs avec différents acides aminés (glycine, phénylalanine) en position 5' du sucre et différentes lipides (dimiristoyl, dioleoyl) estérifié au phosphate présent en position 3' a été réalisée. Les études physico-chimiques réalisées par diffusion dynamique de la lumière (DLS), cryo-microscopie électronique (cryo-TEM) et diffusion des rayons X aux petits angles (SAXS) ont permis d'étudier la morphologie et l'organisation structurale des objets supramoléculaires formés par ces molécules. Ces études ont en particulier permis de mettre en évidence la relation entre la structure chimique et les propriétés physico-chimiques. Les NLs forment des vésicules unilamellaires et les ANLs, grâce à la présence de l'acide aminé sur la tête polaire, forment des vésicules de type multilamellaire. L'étude des interactions, réalisée par calorimétrie à titration isotherme (ITC), entre les vésicules et un acide nucléique modèle (poly A) montre qu'il existe une interaction entre les deux partenaires, mais que cette interaction n'est pas suffisamment forte pour envisager des applications biologiques. La stratégie d'utiliser un cation divalent, comme le calcium, pour ponter les charges négatives des nucléolipides et les charges négatives des acides nucléiques a été envisagé et les complexes ont été étudiés par SAXS. Enfin, des transitions de morphologies observées en fonction de la concentration ont été étudiées par DLS et cryo-TEM. Ces transitions de morphologies ont pu être corrélées à des effets de force ionique sur les propriétés de la tête polaire. / Gene therapy is a molecular medicine and a very powerful tool for the treatment of several diseases such as inherited disorder and cancer. Nucleic acids must penetrate into cells in order to interact with their genetic material. Currently the main limitation to the application of this treatment towards clinics is the lack of robust, safe and efficient gene delivery vectors. The two major classes of vectors are those based on recombinant viruses and those based on non-viral systems. Viral vectors are the most efficient and used in several clinical trials, however they can elicit a strong immune reaction and they possess high cost of production. Non-viral vectors are less immunogenic and can be easily produced on a large scale. A large variety of both cationic lipids and polymers have been developed due to their ability to interact spontaneously with negatively charged nucleic acids to form complexes. However these positively charged complexes can present some toxicity due their non-specific interaction with cell membranes and seric proteins. This is the main limitation for their clinical use. For this purpose, new vectors, neutral or anionic, have to be developed in order to diminish the cytotoxicity and increase the circulation time. Nucleotide-lipids (NLs) are bio-inspired amphiphilic hybrid molecules composed of a hydrophilic nucleotidic moiety and a hydrophobic lipophilic moiety. These molecules are able to self-assembly to form supramolecular structures which possess particular physico-chemical properties due to the chemistry of their polar head. These molecules can interact with a nucleic acid by Watson-Crick base pair interactions, however they are not sufficiently strong to form a stable complex that can be used for a biological application. A new chemical family of hybrid amphiphile, amino acid-nucleotide-lipids (ANLs), has been developed in order to increase the interactions and the stability of the complex thank to the presence of the amino acid on the polar head. Herein, we have synthesized novel amino acid-nucleotide-lipids, presenting phenylalanine (or glycine) and thymidine residues and saturated (dimiristoyl) or unsaturated (dioleoyl) diacyl glycerol lipid. The morphology and the structural organization of the supramolecular objects formed by these molecules was studied by dynamic light scattering (DLS), cryo-electron microscopy (cryo-TEM) and small angle X-ray scattering (SAXS). These studies allowed investigating the relation between the chemical structure and the physic-chemical properties. The amino acids, inserted at the 5′ position of the nucleotide-lipids, stabilize multilamellar systems, whereas unilamellar vesicles are formed preferentially in the case of nucleotide-lipids. Both NLs and ANLs exhibit weak interactions with complementary polyA RNA as revealed by isothermal titration calorimetry (ITC) investigations, however they are not sufficiently strong to form a stable complex that can be used for a biological application. The use of multivalent cations, such as Ca2+, which bridge the phosphate groups on the lipid polar heads with those of the backbone of nucleic acids, to form ternary complexes, has been investigated by SAXS. Finally, a structural study, by DLS and cryo-TEM of NLs aggregates in aqueous solutions as a function of ionic strength and surfactant concentration, has been conducted in order to investigate the different morphologies of the systems.