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Opis: Lignin, a complex aromatic polymer derived from lignocellulosic biomass, is a renewable resource for the production of aromatic-like chemicals and materials. However, its complex nature, depolymerisation and valorisation remain a major challenge for the bio-based community within biorefinery concepts. For this reason, lignin model compounds have been used to understand and design lignin depolymerisation, but insufficient attention has been paid to linking knowledge between simpler systems and applying it to a more complex problem. The objectives of this thesis were formulated accordingly to address the aforementioned gap in the literature. The objectives included a systematic approach correlating studies of lignin model compounds with lignin. Hydrodeoxygenation, cleavage of the β-O-4 bond and depolymerisation were investigated to evaluate the process- and structure-dependent correlations, effects on product distribution and kinetic parameters. The catalytic reactions were carried out in batch reactor and the conditions were applied and intensified according to the knowledge gained during the experimental work. The liquid samples for monomer yield evaluation were analysed by GC-MS, while the structural characteristics of lignin and oligomeric fragments, e.g. molecular weight, functionality/reactivity and structural features, were examined by SEC, quantitative 31P and 2D-HSQC NMR. Kinetic modelling was performed to determine the kinetic parameters (e.g. kinetic constants and activation energies) describing defunctionalisation, β-O-4 bond cleavage and depolymerisation. The study with monomeric lignin compounds contributed to the understanding of the key parameters leading to condensation during hydrotreatment. The unsaturated alkyl side-chain of eugenol and the reactive hydroxyl groups bound irreversibly and formed the carbonaceous species, while 4-propylphenol and 4-propylguaiacol provided important insights into the contribution of steric hindrances to a favourable reaction mechanism. An initial assessment of β-O-4 cleavage was performed with β-O-4-model compound, 2-phenoxy-1-phenylethanol, and linked to the lignin macromolecule by process- and structure-dependent correlations. Although the lignin model compound lacks the structural complexity of lignin, important insights into possible reaction processes were gained and accurate kinetic parameters were determined. Furthermore, lignin isolated in 50 vol% EtOH/H2O solutions was depolymerised and the optimal reaction conditions were defined at a temperature of 275 °C and a pressure of 1.5 MPa with regard to the product distribution and the changes in the structural characteristics of the corresponding oligomeric fragments. Depolymerisation of lignins isolated in different EtOH/H2O solutions showed the importance of the structural features, especially ethoxylation degree and the content of β-O-4 or α-ethoxylated β-O-4 bonds. A higher ethoxylation degree of lignin reduced its potential to depolymerise and achieve the theoretical monomer yield. Therefore, the structural characteristics of lignin play the main role in designing and prediction of lignin depolymerisation. The thesis represents a systematic approach of increasing the complexity of structures exposed to hydrodeoxygenation and depolymerisation. The approach contributed to incorporating the knowledge gained from less complex model compounds to real lignin samples by tailoring and designing lignin depolymerisation to exploit the potential of lignin for biorefinery concepts.
Ključne besede: model compounds, hydrodeoxygenation, organosolv lignin, depolymerisation, structural characteristics, kinetic modelling, dissertations
Objavljeno v RUNG: 08.11.2024; Ogledov: 1126; Prenosov: 15
Celotno besedilo (5,04 MB)

Opis: Copper is one of the most important pollutants in mine- contaminated soils. This study tests the response in a sensitive population vs a tolerant one of the model species Silene paradoxa in order to understand the general mechanisms of tolerance at the micromorphological and ultrastructural level. Two populations of Silene paradoxa were grown in hydroponics and exposed to different CuSO4 treatments. The roots were investigated with light, fluorescence and transmission electron microscope. Callose and lignin were spectrophotometrically determined. The tolerant population constitutively possessed a higher amount of mucilage and was able to reduce the length of the zone between the apex and the first lignified tracheids. Callose production decreased. It did not show remarkable copper-induced ultrastructural modifications, apart from the presence of precipitates in the tangential walls. The sensitive population showed huge nucleoli with a spongy periphery in the central cylinder together with the presence of electrondense granules in the mitochondria. Plastids were rarely observed and generally very electrondense and elongated. In the copper tolerant population of S. paradoxa some of the root traits concurring to generate metal-excluding roots were suggested to be mucilage and lignin production and the reduction of the subapical root zone.
Ključne besede: Root, Copper exclusion, Lignin, Callose, Tolerance to copper, Silene paradoxa
Objavljeno v RUNG: 20.04.2020; Ogledov: 4268; Prenosov: 0
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