Sustainable development has become a global goal and the utilization of bioresources is a key way to achieve this crucial goal. Glyoxylic acid-functionalized lignin (GA-lignin) is one of the novel lignin derivatives extracted from beech wood (hardwood) and has great potential to be an industrially important bioresource. In this thesis work, epoxies prepared by GA-lignin and polyethylene glycol diglycidyl ether (PEGDE) were studied, and the feasibility to prepare smart materials based on these epoxies was explored. Three smart properties, including self-healing properties, thermoelectric properties and piezoelectric properties, were successfully embedded in the GA-lignin-based materials. Many applications are envisioned based on the unique properties of GA-lignin and the value-added materials based on this lignin, including adhesives, hydrogels, flexible electronics, etc. In the first part of this thesis work, different pathways were performed to synthesize GA-lignin/PEGDE epoxies: solvent-free pathway, NaOH solution pathway, DMSO solvent pathway and 1,4-dioxane solvent pathway. The elastomeric epoxy with 50wt% lignin was synthesized following the solvent-free pathway showing mild self-healing properties. The introduction of NaOH solution was found to have the ability to enhance self-healing properties. The epoxy obtained following the dioxane solvent pathway had a similar structure to the original one without any medium, therefore dioxane was chosen to be the solvent for further fabrication of nanocomposites. In the second part, two kinds of GA-lignin-based nanocomposites were fabricated with dioxane as solvent. The first kind of nanocomposite was filled with reduced graphene oxide nanoparticles (rGO). 1wt%, 2wt% and 3wt% of rGO nanoparticles were dispersed into the 50wt% GA-lignin/PEGDE epoxy matrix. Power factor analysis was performed, and the potential of GA-lignin-based thermoelectric nanocomposite was verified. The second nanocomposite was filled with barium titanate nanoparticles (BaTiO3). 7.5wt% and 15wt% of BaTiO3 were dispersed into the epoxy matrix and the piezoelectric response test was performed to show the embedded piezoelectric properties. / Hållbar utveckling har blivit ett globalt mål och användningen av bioresurser är ett viktigt sätt att uppnå detta avgörande mål. Glyoxylsyra-funktionaliserad lignin (GA-lignin) är en av de nya ligninderivaten extraherade från bokträ (lövträ) och har stor potential att vara en industriellt viktig bioresurs. I detta examensarbete undersöktes epoxier framställda av GA-lignin och polyetylenglykol-diglycidyleter (PEGDE), och möjligheten att framställa smarta material baserade på dessa epoxier utforskades. Tre "smarta egenskaper" integrerades framgångsrikt i GA-lignin-baserade material, inklusive självläkande egenskaper, termoelektriska egenskaper och piezoelektriska egenskaper. Många tillämpningar förutspås baserat på de unika egenskaperna hos GA-lignin och de mervärdesmaterial som baseras på detta lignin, inklusive lim, hydrogeler, flexibel elektronik, osv.I den första delen av detta examensarbete genomfördes olika metoder för att syntetisera GA-lignin/PEGDE-epoxier: en metoden utan lösningsmedel, en metod med NaOH-lösning, en metod med DMSO-lösningsmedel och en metod med 1,4-dioxan som lösningsmedel. Den elastiska epoxin med 50 viktprocent lignin syntetiserades genom den lösningsmedelsfria metoden och uppvisade milda självläkningsegenskaper. Införandet av NaOH-lösningen visade sig kunna förbättra självläkningsegenskaperna. Epoxin som erhölls genom metoden med dioxan som lösningsmedel hade en liknande struktur som den ursprungliga epoxin utan något medium, därför valdes dioxan som lösningsmedel för vidare tillverkning av nanokompositer. I den andra delen tillverkades två typer av GA-lignin-baserade nanokompositer med dioxan som lösningsmedel. Den första typen av nanokomposit fylldes med reducerade grafenoxid-nanopartiklar (rGO). 1 viktprocent, 2 viktprocent och 3 viktprocent rGO-nanopartiklar disperserades i matrisen av 50 viktprocent GA-lignin/PEGDE-epoxi. En analys av effektfaktorn utfördes och potentialen hos GA-lignin-baserade termoelektriska nanokompositer verifierades. Den andra nanokompositen fylldes med bariumtitanat-nanopartiklar (BaTiO3). 7,5 viktprocent och 15 viktprocent BaTiO3 disperserades i epoximatrixen och en test för piezoelektrisk respons genomfördes för att visa de inbäddade piezoelektriska egenskaperna.

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Lignin is one of the most abundant natural polymers on Earth, and a valuable resource. Despite being widely available, only a small amount of the produced lignin is currently utilized to make high-value goods, with the majority being used for pulp mills to recover energy. However, the possibility to convert lignin into commercially viable products is presented by the rising need for sustainable and renewable resources. In the past, research has mostly concentrated on converting lignin into chemicals, materials, and biofuels; nevertheless, there has not been much advancement in practical applications. Lignin is difficult to depolymerize due to its intricate structure and resistance to degradation. To separate lignin from lignocellulosic biomass, a number of techniques have been developed, such as kraft and sulfite pulping. These techniques, though, result in lignin with various characteristics. As a result, improved lignin isolation methods are required in order to produce high-quality, pure lignin. Due to its capacity to solubilize lignocellulosic biomass and extract lignin, ionic liquid-based lignin isolation has attracted interest. Ionic liquids are environmentally friendly since they may be recycled and used again. There are still issues with toxicity, physicochemical data, and industrial-scale recovery, though. Lixea is a startup company that specializes in sustainable technology, especially lignin. They have created a novel method of fractionating lignocellulose known as Dendronic® that uses inexpensive ionic liquids to separate lignin and cellulose from biomass. Potentially, this process could result in renewable products, such as chemicals and biofuels on a large scale. Filtration of the lignin is one of the main bottlenecks operations at Lixea`s pilot plan. In this paper two different strategies; Maturing of the lignin suspension through temperature cycling and using previously isolated lignin filter cake as precipitation and filtration aid, have been tested out at the lab scale to improve the lignin filtration speed. Based on the observations in this work the heat treatment strategy is the most promising one, therefore it is recommended to test it the pilot plant to confirm the lab-scale experiments and improve the plant operation. Overall, further research and development are needed to unlock the full potential of lignin as a flexible and sustainable resource.

Functionalizable spherical colloidal lignin particles (CLPs) represent a valuable asset for the valorization of lignin side-streams from the pulp industry. The spherical structure allows for the circumvention of the heterogeneous and poorly dispersible structure of the biopolymer. However, organic solvents and alkaline media degrade the particle structure and dissolve the polymers due to their chemical nature and solubility. The solvents will alter the aggregated polymers into irregular shapes that would correspond to inconsistent physicochemical properties. Then, the material will become unusable for advanced material applications, namely wood adhesives. In this study, a replicable process to yield pH ca. 12 stable CLPs for wood adhesives or further functionalization for other advanced material applications was developed and optimized. Lignin was functionalized with cross-linkers, glyoxal or formaldehyde, and selfassembled into spherical structures in the micro emulsification of the organic solution. The formed colloids were partially rotary evaporated to retain organic solvents within the colloidal structures, and then be cured at 73-76 °C until pH stable and further functionalized for advanced material applications. The functionalization with glyoxal was pursued further for its possibly increased reactivity and the health concerns associated with formaldehyde. The process requires the addition of glyoxal to lignin in an acidic organi cmedia at ambient temperature, and the solution to react at 64 °C. Glyoxal is likely added to the polymer structure in its hydrated and dimerized form, and its attachment to lignin should be analyzed through the behavior of glyoxal in different media. The formed colloids were rotary evaporated to an organic solvent content of 60 wt. % of the spheres to allow the occurrence of the curing reaction. These materials were finally cured by thermosetting them at 73-76 °C until pH stable. The particles can be cured with base-catalysis through the controlled addition of the base NaOH(aq). However, the mode and rate of addition of the catalyst are critically important for a nondegradative infusion of a base into solvent present ot removed particles without morphological changes. Further procedural improvement and larger batches are necessary to conduct CLP adhesive experiments. / Funktionaliserbara sfäriska kolloidala ligninpartiklar (CLP) är en värdefull tillgång för valorisering av ligninsidoströmmar från massaindustrin. Den sfäriska strukturen reducerar effekten av den heterogena och dåligt dispergerbara biopolymeren. Organiska lösningsmedel och alkaliska medier försämrar emellertid partikelstrukturen och löser upp polymererna på grund av deras kemiska natur och löslighet. Lösningsmedel kommer att resultera i att de aggregerade polymererna antar oregelbundna former vilket skulle resultera i inkonsistenta fysikalisk-kemiska egenskaper. Därigenom blir materialet oanvändbart för avancerade materialapplikationer, såsom t ex trälim. I denna studie, utvecklades och optimerades en reproducerbar process för att ge pH ca. 12 stabila CLP för trälim eller ytterligare funktionalisering för andra avancerade materialapplikationer. Lignin funktionaliserades med tvärbindare, glyoxal eller formaldehyd och självorganiserades till sfäriskas trukturer genom mikroemulgering av organfasen. De bildade kolloiderna indunstades delvis roterande för att bibehålla det organiska lösningsmedlet i de kolloidala strukturerna och härdades sedan vid 73-76 ° C tills pH-stabilitet och funktionaliserades ytterligare för avancerade materialapplikationer. Funktionaliseringen med glyoxal utfördes också för att reaktiviteteten och begränsa de hälsoproblem som är förknippade med formaldehyd. Förfarandet kräver tillsats av glyoxal till lignin i ett surt organiskt medium vid rumstemperatur för att sedan reageras vid 64 ° C. Glyoxal i dess hydratiserade och dimeriserade form adderas sannolikt till polymeren, och dess kemiska inbindning till lignin kan analyseras genom att undersöka glyoxal uppförande i olika medier. De bildade kolloiderna indunstades till ett organiskt lösningsmedelsinnehåll av 60 viktprocent för att möjliggöra härdning. Dessa material härdades slutligen genom värmehärdning vid 73-76 ° C tills pH var stabilt. Partiklarna kan härdas med baskatalys genom kontrollerad tillsats av basen NaOH (aq). Emellerti där sättet och tillsatshastigheten för katalysatorn kritiskt viktigt. Ytterligare processförbättringar och större satser är nödvändiga för att genomföra CLP-limexperiment.

1. Investigations of styrene polymerized in wood using ionizing radiation as the chain initiator indicate that property improvements are of the same order as for thermally initiated polymerization. 2. Free radicals have been detected in irradiated cellulose, Dioxane lignin, Spruce Periodate lignin and Beaun’s “Isolated Native Lignin” as well as in wood subjected to radiation. Consequently, wood radical identification is not possible. 3. Analysis of radical concentrations and decay suggest the presence of one or more decaying radical species in irradiated wood. The persistent maximum in radical concentration found corresponds to one or two unique radical sites per molecule; possibly the terminal hydroxyl group. 4. Results suggest that in the grafting reaction the initiation is a direct radical-monomer couple and does not involve decomposing peroxides. / Thesis / Master of Engineering (ME)

The broader technical objective of this work is to develop a strategy for using the biopolymer lignin in a wide variety of surfactant applications through polymer grafting. These applications include emulsion stabilizers, dispersants and foaming agents. The scientific objective of the research performed within this thesis is to understand the effect of molecular architecture and polymer grafting on the interfacial activity at the air-liquid, liquid-liquid and solid-liquid interface. Research has focused on designing of these lignopolymers with controlled architecture using polyethylene glycol, poly(acrylic acid) and polyacrylamide grafts. The interfacial activity for all polymer grafts has been tested at all three interfaces using a broad range of techniques specific to the interface. Results have shown that the hydrophobicity of the lignin core is responsible for enhanced interfacial activity at the air-liquid and liquid-liquid interface. Conversely, improved hydrophilicity and “electrosteric” interactions are required for higher interfacial activity of the lignin at the liquid-solid interface. The high interfacial activity of the polymer-grafted lignin observed in the air-liquid and liquid-liquid interfaces not only resulted in viscosity reduction but also strength enhancement at the liquid-solid interface. The broader implication of this study is to be able to predict what chemical functionalities need to be adjusted to get the desired viscosity reduction.

As gramíneas são o mais importante grupo de plantas para em todo o mundo. Inúmeras são usadas para a alimentação dos animais, além de serem utilizadas para a produção de biocombustíveis, contribuindo para a redução do consumo de combustíveis fósseis e consequentemente da poluição ambiental. A biomassa vegetal é constituída basicamente por celulose, hemicelulose e lignina. Estudos na área de bioquímica e genética tem demonstrado a lignina como um dos principais compostos responsáveis pela recalcitrância da biomassa, sendo a resistência à digestão enzimática uma importante limitação do processo de produção de bioetanol. A lignina é um polímero vegetal resultantes da polimerização desidrogenativa de três monômeros de fenilpropanóides primários, os álcoois p-coumarilico (H), coniferilico (G) e sinapilico (S). A via metabólica dos fenilpropanóides envolve a participação de 11 enzimas, nas gramíneas, tais como PAL, C4H, 4CL, C3H, F5H, CCoAOMT, CSE, COMT, HCT, CCR e CAD. Até o momento, 28 genes de cana-de-açúcar foram identificados no SUCEST e explorados para identificar os possíveis bona fide. No entanto, com a disponibilização de bancos transcriptômicos (RNASeq) e ferramentas avançadas de bioinformática, o nosso grupo de pesquisa expandiu para 37 genes após o processo de identificação, anotação e classificação pelas análises filogenéticas. Diante disso, a presente proposta teve por objetivo realizar a análise de expressão destes transcritos anotados em uma variedade de cana-de-açúcar com a composição química da parede celular caracterizada. Para identificar quais genes estão envolvidos nesta via, o presente trabalho propôs correlacionar o perfil de expressão com os quatro estágios de desenvolvimento do entrenó, separando córtex e medula, os quais estão associados aos estágios de lignificação em maior e menor grau, respectivamente. Dentre as análises realizadas, 34 transcritos tiveram os primers padronizados , 26 foram expressos no colmo nas condições testadas, sendo 7 genes adicionais aos previamente descritos na literatura. Baseado nas análises de expressão gênica, PAL1.1/1.2, COMT1, CAD2/5/8, 4CL2, F5H1, CCoAMOT1.2/2.1 e CCR1 foram apontados como possíveis candidatos principais na via de biossíntese da lignina. / Sugarcane (Saccharum spp.) is a grass of great importance for the sustainable technological and agroindustrial development of Brazil. The cell wall of the grasses is basically composed of cellulose, hemicellulose, lignin and hydroxycinnamic acids. The study of the chemical composition of the cell wall of different sugarcane hybrids revealed that low lignin content, in particular for H89 (~ 16.8%), contribute to the low recalcitrance of the biomass. These studies obtained greater information when the regions of rind and pith of H89 were dissected, which present, respectively, 21.7% and 13.9% of total lignin. Lignin is a plant polymer resulting from the dehydrogenative polymerization of three primary phenylpropanoic monomers, the p-coumaril (H), coniferyl (G) and synapylic (S) alcohols. The metabolic pathway of the phenylpropanoids involves the participation of several enzymes, totalizing in the grasses 11 sets, such as PAL, C4H, 4CL, C3H, F5H, CCoAOMT, CSE, COMT, HCT, CCR and CAD. So far, 28 unigenes of sugarcane have been identified in SUCEST and explored to identify the possible bona fide. Recently, based on bioinformatics, phylogenetic and transcriptomic (RNA-Seq) analyzes of sugarcane and related grasses, our research group identified 37 transcripts possibly involved in monolignol biosynthesis. In the presence of detailed descriptions of the composition of lignin in H89 and of the large number of genes identified, the presente proposal aimed to perform the analysis of the expression of these transcripts annotated in H89. In order to amplify and reinforce which genes are involved in the monolignol pathway, the present work proposed to correlate the expression profile with four stages of the development of the enternode, exploring the regions of rind and pith. Among the analyzes performed, 34 genes were identified, 26 genes were expressed, being 7 additional genes to those previously described in the literature. In this context, PAL1.1 / 1.2, COMT1, CAD2 / 5/8, 4CL2, F5H1, CCoAMOT1.2 / 2.1 and CCR1 were identified as potential candidates in the lignin biosynthesis pathway.

Orientador: Dilermando Perecin / Coorientador: Michael dos Santos Brito / Coorientador: Silvana Aparecida Creste Dias de Souza / Banca: Elisson Antônio da Costa Romanel / Banca: Luciana Rossini Pinto / Resumo: A busca pela diversificação de fontes da matriz energética, priorizando fontes renováveis, acarreta no maior consumo de etanol de primeira geração, podendo este ser insuficiente em suprir a necessidade da frota brasileira. Dessa forma, o etanol de segunda geração (E2G) surge como uma alternativa para aumento da produção de combustíveis renováveis. Ele é produzido a partir da fermentação dos resíduos de glicose após a quebra da celulose presente na biomassa vegetal. Contudo, além da celulose, a biomassa vegetal é também composta pela lignina, composto considerado recalcitrante no processo de obtenção deste tipo de etanol. Para transpor este obstáculo, é necessário encontrar maneiras de diminuir a quantidade ou modificar a composição da lignina. Fatores de transcrição (FTs) são alvos altamente promissores para a modificação deste polímero, uma vez que estão envolvidos com a regulação de sua via de biossíntese, bem como, da formação de toda parede celular secundária (PCS). Plantas de arroz transformadas para a superexpressão de AtSHN2 de Arabdopsis, apresentaram uma diminuição na quantidade de lignina e mostraram uma modulação na via de celulose, enquanto que a superexpressão do outro gene SHN de Arabidopsis (AtSHN1) em Arabidopsis apresentou uma modificação na via de biossíntese de cera e cutina. Isto ressalta a necessidade de avaliar os FTs de maneira espécie-específica. Assim sendo, este trabalho vem com o objetivo de ajudar a elucidar os mecanismos de funcionamento do FT SHI... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The search for alternative sources of the energy, prioritizing renewable sources, increase the consumption of first generation ethanol, which could not be enough to supply the needs of the Brazilian flex fuel car fleet. In this scenario, second generation ethanol (E2G) appears as an alternative to increase production of renewable fuels. E2G it is produced from the fermentation of glucose residues after breaking the cellulose present in the plant biomass. However, adhered to the cellulose is lignin, a compound considered recalcitrant in the process of obtaining this type of ethanol. To overcome this obstacle, it is necessary to find ways to decrease the amount or modify the lignin composition. Transcription factors (TFs) are highly promising targets for the modification of this polymer, since they are involved in the regulation of its biosynthesis pathway, as well as the formation of the whole secondary cell wall (PCS). Rice plants transformed for the overexpression of AtSHN2 from Arabidopsis showed a decrease in the amount of lignin and a modulation of cellulose pathway whereas the overexpression of another gene of SHN (AtSHN1) in Arabidopsis showed a modification in the biosynthesis pathway of wax and cutin. This highlights the need to evaluate TFs in a species-specific manner. Basing on this, the present work has the objective of helping to elucidate the mode of action of TF SHINE (SHN), considered a potential regulator of PCS in grasses. Aiming to characterize SbSHN TF in ... (Complete abstract click electronic access below) / Mestre

Thesis (Sc.D.)--Massachusetts Institute of Technology, Dept. of Chemical Engineering, 1981. / MICROFICHE COPY AVAILABLE IN ARCHIVES AND SCIENCE / Includes bibliographical references. / by Michael Tully Klein. / Sc.D.