L’objectif principal de cette thèse a été de développer de nouveaux systèmes catalytiques efficaces pour la dépolymérisation de la biomasse et des plastiques. La stratégie choisie pour favoriser cette transformation a été l’hydrosilylation de liaisons C-O. Le catalyseur d’iridium(III) de Brookhart s'est révélé particulièrement efficace pour l’hydrosilylation la lignine conduisant à des produits aromatiques purs avec des rendements très élevés. Il a également été utilisé pour la dépolymérisation réductrice de plastiques oxygénés qui ont permis d’isoler les monomères et des composés de haute valeur ajoutée.Dans un second temps, une dépolymérisation plus « verte » de polycarbonates et de polyesters a été mise en œuvre. Celle-ci ne fait intervenir ni métaux ni solvant grâce à l’utilisation du fluorure de tetra-n-butyle amonium comme catalyseur. Enfin, l’uranium appauvri, considéré comme un déchet de l’industrie nucléaire, a été valorisé comme catalyseur pour la réduction des liaisons C-O. Il a été découvert qu’un complexe de triflate d'uranyle favorisait efficacement le couplage réducteur de l'aldéhyde en présence d'hydrosilanes conduisant à l'éther symétrique. / The main objective of this thesis is the development of new efficient catalytic systems for the depolymerization of biomass and plastics. The chosen strategy to promote such transformations was the hydrosilylation of C-O bonds. Brookhart's iridium(III) catalyst was found to be very effective for hydrosilylation of lignin leading to pure aromatic products isolated in very high yields. It was also used for the reductive depolymerization of oxygenated plastics, allowing the isolation of monomers and valuable chemicals.In a second step, a "greener" depolymerization of polycarbonates and polyesters was implemented. This does not involve metals or solvents through the use of tetra-n-butyl amonium fluoride as a catalyst for hydrosilylation. Finally, depleted uranium, considered as a waste product of the nuclear industry, was valorized as a catalyst for the reduction of C-O bonds. It has been discovered that a uranyl(VI) triflate complex efficiently promotes reductive coupling of the aldehyde in the presence of hydrosilanes leading to symmetric ethers.

Due to its large flexibility, low-price, large availability, and properties lignin is seen as an important compound with a wide range of applications. The increasing demand of fossil-based rubber materials is causing a serious threat to the environment and it is contributing to plastic- and marine pollution, ozone depletion and carbon dioxide emission (CO2) [1,2]. Numerous toxicological researches highlight that Carbon black may act as a universal carrier of wide variety of chemicals of varying toxicity to the human body [3,4]. Consequently, researcher endeavours in finding sustainable and eco-friendlier alternatives. The aim of this thesis was to further investigate the possibilities of replacing carbon black with modified lignin in rubber elastomeric materials- for the development of sustainable tyre technology. The research questions for this thesis were divided in four parts:   How does lignin (unmodified and modified) structure affect the mechanical properties of the rubber compound? How does lignin affect the cross-link and vulcanisation of the rubber compound? How does lignin affect the dispersion of the rubber compound? Which modification of lignin is more compatible with the rubber compound? Lignin is the second most abundant biopolymer on earth (after cellulose) and is mainly extracted from black liquor, which is obtained as a by-product from the pulp- and paper. In this study, pure lignin was obtained from Lignoboost process (Lignocity) and underwent an esterification process of aldehydes (1. Protonic, 2. Butyric, 3. Isobutyric 4. Methacrylic and 5. Crotonic). LignoCity 2.0 is a project focusing on the development of sustainable products and processes connected to lignin. The structure of the modified lignin was characterized using a FTIR-spectra. Furthermore, seven different rubber compounds were produced at Anva Poly Tech, which is a company that manufactures rubber materials in Sunne, Sweden. The mechanical testing involved: Tensile strength, IRHD, Hardness, Rebound Resilience and Rheometer curve. It was observable that the addition of lignin in rubber compounds did not significantly improve the mechanical properties compared to conventional carbon black. However, the rheometer curves of the lignin samples clearly indicate an increase in scorch time and that lignin takes part in the vulcanization process, thus the delay in crosslinking phase.  In addition, it was visible that the fully replacement of carbon black with lignin (unmodified and modified) increased the elongation at break. Furthermore, the FTIR spectra indicated a complete and successful modification of lignin. In addition, compared to unmodified lignin, it was visible that the modified lignin significantly improved the mechanical properties. Therefore, it was possible to conclude that the configuration and double bonds of the aldehydes had an impact on the vulcanization process. Butyric and isobutyric lignin were the better choices compared to the other lignin samples. / De rådande miljöproblemen som: plast- och gummiutsläpp i havet, växthusgasutsläppet och den ekologiska utarmningen i kombination med den ökande efterfrågan av fossilbaserade material har lett till en ökad satsning på att hitta mer hållbara och miljövänligare alternativ [1, 2]. Kimrök i gummimaterial utgör en del hälsorisker och samtidigt har negativ påverkan på miljön. Flertals studier visar att långtidsexponering av kimrök kan ge allvarliga lungproblem och även cancer [3,4]. På grund av dess stora tillgänglighet, låga kostnad och unika egenskaper anses lignin vara en möjlig och intressant framtidskandidat för ersättande av fossila produkter. Syftet med denna studie var att undersöka möjligheterna om att ersätta kimrök med modifierad lignin i gummimaterial för utvecklandet av ’grönare däckteknologi’. Frågeställningarna i detta arbete var uppställda i fyra i olika delar: Hur påverkar tillsättningen av lignin (omodifierad och modifierad) gummiblandningens mekaniska egenskaper? Hur påverkar tillsättningen av lignin tvärbindningarna och vulkningen i gummiblandningen? Hur påverkas tillsättningen av lignin gummiblandningars dispersion? Vilken modifikation av lignin är mest kompatibel med gummimaterialet? Lignin är en organisk biopolymer som är den näst mest (efter cellulosa) förekommande biomassan i naturen och produceras som en biprodukt från pappers- och massa industrin. Ren lignin erhålls genom extraktion från svartlut med diverse isolations metoder. I detta arbete erhölls lignin genom Lignoboost processen från Lignocity.  Lignocity 2.0 är ett projekt som syftar till att utveckla, kommersiella och effektivisera hållbara processer och produkter med fokus på lignin. I detta arbete modifierades ligninet genom en s.k. esterfierings process av fem olika aldehyder 1.Propionic, 2. Butyric, 3. Isobutyric, 4. Methacrylic och 5. Crotonic som sedan undersöktes i en FTIR-spektra. Sju olika gummiblandningar skapades (inklusive ett gummi som endast innehöll kimrök och ett gummi som ej innehöll kimrök eller lignin). Gummiblandningarnas mekaniska egenskaper undersöktes på följande sätt: Dragstyrka, IRHD (Hårdhet), Hårdhet, studselasticiteten och reometrisk karaktärisering De ligninbaserade gummiblandningarna gav ingen signifikant förbättring i de mekaniska egenskaperna. Dock visade den reometriska kurvan att tillsättning av lignin gav en ökning i bränntid samt att ligninet gav en förskjutning i tvärbindningsfasen. Vidare gav den reometriska kurvan en indikation på att ligninet deltog i vulkaniseringsprocessen. Isobutyric lignin hade den högsta bränntiden. Det var även bevisat att tillsättningen av lignin gav en ökning i töjning. Modifieringen av lignin gav en signifikant förbättring av de mekaniska egenskaperna jämfört med omodifierad lignin. FTIR-spektrumet av ligninproven indikerade på en lyckad modifiering och koppling av aldehydgrupperna. Trots att de ligninbaserade gummiblandningarna inte förbättrade de mekaniska egenskaperna så kunde intressanta kopplingar mellan aldehydens konfigurationer, dubbelbindningar och vulkaniserings processen göras. Butyric och isobutyric visade bäst resultat jämfört de andra ligninproven.

Med rapsfrön som en eftertraktad produkt från raps kvarstår rapshalm, vilket anses vara en avfallsprodukt. Dock är rapshalmen en god källa till biopolymerer och kan spela en potentiell roll som råvara till materialframställning. Det övergripande målet med detta examensarbete var att fullständigt separera lignin och cellulosa från varandra i den halmrest som återstår efter hydrotermisk extraktion av rapshalm vilket delprojekt 1 har behandlat. Den huvudmetod som har tillämpats under projektet var alkalisk delignifiering, med bestämd tid, temperatur och koncentrationen NaOH. Två prover av halmrester valdes för behandling i detta projekt varav den första har extraherats med närvaro av bikarbonat som buffertlösning medan den andra har extraherats vid en högre temperatur. Ytterligare metoder för att erhålla lignin och cellulosa var ligninfällning och defibrering. Av den erhållna cellulosamassan framställdes papper. De erhållna produkterna med kolhydratanalys (IC), askhalt (TGA), och bestämning av funktionella grupper (FTIR). Cellulosamassan analyserades med SEM och ljusmikroskopi. De framställda pappersarken analyserades med dragprovning för bestämning av mekaniska egenskaper. Det totala utbytet av lignin inte så högt, en tredjedel av ligninmängden i rapshalm. Det första provet gav ett högre utbyte än det andra, däremot gav det andra ett mer ligninrikt utbyte. Fibermassan från det andra provet hade en högre halt cellulosa. Mikroskopianalyser visade att fibrerna inte frilagts fullständigt från varandra, med kvarvarande biomassa som bibehåller sin originalstruktur. Mängden frilagda fibrer var högre i det första provet samt fiberstrukturen på de spiralformade fibrerna höll kvar sin primära form. Enligt resultaten från dragprovningsanalysen hade papperet från det första provet en signifikant högre brottgräns och E-modul än det andra. / The oil rich seeds from the rapeseed are products of interest, which leaves the straws as a waste product. Rapeseed straw is a good source of biopolymers which have potential as material resources. The overall aim of this degree project was to fully separate lignin from cellulose in pretreated straws. The main method applied was delignification with alkali under specified conditions including time, temperature, and the concentration of sodium hydroxide. Two samples of preextracted straw were chosen. The first sample was extracted in the presence of a buffer while the second was extracted at a higher temperature. Other methods were also used, such as kraft lignin precipitation for a better yield of lignin, and defibration of the cellulosic fibre mass. Paper sheets were made from the obtained fibre mass. The products were analyzed with a variety of analytic methods, including IC, TGA, and FTIR. The straws and the cellulosic mass were further analyzed with SEM and optical microscopy. The obtained paper materials were analyzed mechanically by tensile testing. The total yield of lignin was not so high, about a third of the total lignin content in the rapeseed straw. The first sample gave a higher than the second sample, however the second sample gave a more lignin rich yield. The obtained fibre mass in the second sample had a considerably higher content of cellulose. Microscopy analyses showed that the fibres did not fully separate, and there were remains of biomass in their current structure. The amount of separated fibres were higher in the first sample as well as the spiral-shaped fibres maintained their structure. The results from the tensile test showed that the paper prepared from the first sample had a significantly higher tensile strength than the paper obtained from the second sample.

This dissertation is composed of two research projects. The first research project is aimed at using synthetic fluorogenic probes to study the possible or dominant linkages in biomass. These probes that mimic the linkages found in lignin-cellulosic biomass are designed to select the optimal fungi from direct evaluation process or could be tested against other microbials to screen candidates which can break ligno-hemicellulose bonds. For the first stage, these probes would be tested against white rot fungi extract. The white rot fungi are used for the first stage to see if releasing or degrading carbohydrates while keeping lignin largely intact is possible or not. These probes can help to answer fundamental questions, such as what could be the dominant linkages between lignin and hemicellulose, and what are the possible mechanisms for the cleavage of carbohydrates in biomasses. Understanding the linkages in these biomass will enable high efficient degradation or release of carbohydrates, primarily hemicelluloses, from biomass. The second project is focused on synthesizing new aminoglycoside analogs and exploring the potential to revive traditional antibacterial kanamycin as new types of antifungal agents. Aminoglycosides are widely used broad spectrum antibiotics. Although mainly used as antibacterial agents, there have been studies to show amphiphilic aminoglycoside derivatives could be possibly employed as antifungal agents. A concise and novel method for site-selective alkylation of tetra-azidokanamycin has been developed that leads to the divergent synthesis of three classes of kanamycin derivatives. These new amphiphilic kanamycin derivatives bearing alkyl chains length of 4, 6, 7, 8, 9, 10, 12, 14，16 have been synthesized and tested against bacteria and fungi. Surprisingly, the antibacterial effect of the synthesized kanamycin derivatives decline or disappear compared with the original kanamycin A, but some of the compounds show very strong activity as antifungal agents.

京都大学 / 0048 / 新制・課程博士 / 博士(農学) / 甲第19036号 / 農博第2114号 / 新制||農||1031(附属図書館) / 学位論文||H27||N4918(農学部図書室) / 31987 / 京都大学大学院農学研究科森林科学専攻 / (主査)教授 髙部 圭司, 教授 髙野 俊幸, 教授 矢﨑 一史 / 学位規則第4条第1項該当 / Doctor of Agricultural Science / Kyoto University / DGAM

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第20395号 / 工博第4332号 / 新制||工||1671(附属図書館) / 京都大学大学院工学研究科物質エネルギー化学専攻 / (主査)教授 中村 正治, 教授 大江 浩一, 教授 村田 靖次郎 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

京都大学 / 0048 / 新制・課程博士 / 博士(エネルギー科学) / 甲第20477号 / エネ博第346号 / 新制||エネ||69(附属図書館) / 京都大学大学院エネルギー科学研究科エネルギー社会・環境科学専攻 / (主査)教授 坂 志朗, 教授 髙部 圭司, 准教授 河本 晴雄 / 学位規則第4条第1項該当 / Doctor of Energy Science / Kyoto University / DGAM

京都大学 / 0048 / 新制・課程博士 / 博士(エネルギー科学) / 甲第21386号 / エネ博第374号 / 新制||エネ||73(附属図書館) / 京都大学大学院エネルギー科学研究科エネルギー基礎科学専攻 / (主査)教授 片平 正人, 教授 森井 孝, 准教授 小瀧 努 / 学位規則第4条第1項該当 / Doctor of Energy Science / Kyoto University / DFAM

Lignin is one of the most common biopolymers in the world. Together with cellulose andhemicellulose it constitutes the fibers in the wood. It has a high molecular weight due to its complexstructure consisting of crossed-linked phenolic monomers and is concatenated with different types ofcarbon and ether bonds.In pulping processes, lignin is extracted in large quantities and used on site to produce energy for milloperations but is also removed as a waste product. This enables a product with high resources andaccessibility due to lignin's diverse properties. Therefore, lignin has the potential to be utilized inhigher value applications such as polymer materials, as well as a source of platform chemicals. Atpresent, the value applications of lignin are promising as additives for different kinds of productssuch as emulsifiers and especially as biofuel due to lignin's high carbon content.New technologies for development for utilization lignin are emerging for different kinds ofapplications due to lignin’s biocompatibility. The possibilities of lignin combined with existingresearch of nanotechnology gives opportunities to improve biomedical applications. By designinglignin derived nanoparticles with incorporated magnetic materials, the NPs obtainsuperparamagnetic properties which can be utilized for target drug delivery. This could be promisingagainst intractable cancer such as pancreatic cancer.This report presents a protocol for developing magnetic lignin nanoparticles from the lowestmolecular weight kraft lignin fractions of eucalyptus (hardwood) and spruce (softwood). By a methodof self-assembly, particles with a doughnut and core-shell morphology, as indicated by SEM and TEM,were yielded with a 10-50μL content of water-stabilized magnetite. The particle size distribution andzeta potential were determined by DLS and the possibility of the particles being suitable forbiomedical applications was discussed.

Phenolic adhesives are widely used in the production of engineered wood products due to their exceptional moisture and thermal resistance, chemical stability, and bonding strength. The phenolic adhesive is currently produced through condensation polymerization of two fossil fuel-derived compounds: phenol and formaldehyde. However, due to fluctuations in the price of phenol and formaldehyde with the price of oil, environmental and health issues associated with using these compounds, there is a strong interest in finding alternative renewables feedstocks. Lignin is a natural polyphenolic compound with excellent potential to substitute phenol in phenolic adhesive formulations. Lignin is produced as byproducts during pulp and bioethanol processes. On the other hand, biobased aldehydes such as glyoxal have recently gained a lot of attention for replacing the toxic formaldehyde in production of environmentally friendly wood products. In this study, a wide range of lignin samples from different resources (hardwood, softwood, wheat straw, and corn stover), and isolated via various processes (kraft, organosolv, soda, sulfite, and enzymatic hydrolysis), were used to formulate 100% lignin-based phenolic adhesives. In a separate work, formaldehyderee phenolic adhesives were also developed using either glyoxal or gossypol (a dialdehyde from cotton seed) in combination with phenol. Chemical, physical, and thermal properties of lignin samples and developed phenolic resins and adhesive were measured using advanced analytical techniques and appropriate ASTM standard test methods. Based on two-way ANOVA analysis results of shear strength data, a biorefinery corn stover lignin that had the highest p-hydroxyphenyl and p-coumaric acid content was the most suitable lignin for replacing 100% of phenol in phenolic adhesive formulation. In addition, the developed lignin-based adhesive (formulated with biorefinery corn stover lignin) showed similar dry and wet adhesion strengths as that of commercially formulated phenol resorcinol formaldehyde (PRF) adhesive. On weight basis, the formaldehyde consumption in the developed lignin-based adhesive was 50% lower than the formaldehyde used in phenol formaldehyde (PF) resin. Moreover, two formaldehyderee formulated adhesives using glyoxal and gossypol (renewable feedstocks) had very similar physico-chemical properties to phenol formaldehyde adhesive.