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Abstract: 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.
Keywords: model compounds, hydrodeoxygenation, organosolv lignin, depolymerisation, structural characteristics, kinetic modelling
Published in RUNG: 08.11.2024; Views: 145; Downloads: 0
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Abstract: The Cherenkov Telescope Array (CTA) is the next generation ground-based observatory for γ-ray astronomy at energies above 30 GeV. Thanks to its unique capabilities, CTA observations will address a plethora of open questions in astrophysics, ranging from the origin of cosmic messengers to the exploration of the frontiers of physics. In this note, we present a comprehensive sensitivity study to assess the potential of CTA to measure the γ-ray absorption on the extragalactic background light (EBL), to constrain or detect intergalactic magnetic fields (IGMFs), and probe physics beyond the standard model such as axion-like particles (ALPs) and Lorentz invariance violation (LIV), which could modify the γ-ray spectra features expected from EBL absorption. Our results suggest that CTA will have unprecedented sensitivity to detect IGMF signatures and will probe so-far unexplored regions of the LIV and ALP parameter space. Furthermore, an indirect measurement of the EBL and of its evolution will be performed with unrivaled precision.
Keywords: very-high-energy gamma rays, the Cherenkov Telescope Array (CTA) Observatory, extragalactic background light (EBL), intergalactic magnetic fields (IGMFs), axion-like particles (ALPs), Lorentz invariance violation (LIV)
Published in RUNG: 07.11.2024; Views: 179; Downloads: 4
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Abstract: We present optical and near-infrared observations of two Type Ibn supernovae (SNe), SN\,2018jmt and SN\,2019cj. Their light curves have rise times of about ten days, reaching an absolute peak magnitude of $M_g$(SN\,2018jmt) = $-$19.07 pm 0.37 and $M_V$(SN\,2019cj) = $-$18.94 pm 0.19 mag, respectively. The early-time spectra of SN\,2018jmt are dominated by a blue continuum, accompanied by narrow (600$-$1000 km $) He i lines with the P-Cygni profile. At later epochs, the spectra become more similar to those of the prototypical SN Ibn 2006jc. At early phases, the spectra of SN\,2019cj show flash ionisation emission lines of C iii N iii and He ii superposed on a blue continuum. These features disappear after a few days, and then the spectra of SN\,2019cj evolve similarly to those of SN\,2018jmt. The spectra indicate that the two SNe exploded within a He-rich circumstellar medium (CSM) lost by the progenitors a short time before the explosion. We modelled the light curves of the two SNe Ibn to constrain the progenitor and the explosion parameters. The ejecta masses are consistent with either what is expected for a canonical SN Ib (sim 2 odot $) or for a massive Wolf Rayet star ($>$ sim 4 M$_ odot $), with the kinetic energy on the order of $10^ $ erg. The lower limit on the ejecta mass ($>$ sim 2 M odot $) argues against a scenario involving a relatively low-mass progenitor (e.g. $M_ ZAMS $ sim 10 M$_ odot $). We set a conservative upper limit of sim 0.1 M$_ odot $ for the 56Ni masses in both SNe. From the light curve modelling, we determined a two-zone CSM distribution, with an inner, flat CSM component and an outer CSM with a steeper density profile. The physical properties of SN\,2018jmt and SN\,2019cj are consistent with those expected from the core collapse of relatively massive envelope-stripped stars.
Keywords: supernovae
Published in RUNG: 06.11.2024; Views: 171; Downloads: 3
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Keywords: diplomske naloge, kakovost, vhodna kontrola, reklamacije, certifikati, Futon, proizvodni proces, merilni pripomočki, tehnične risbe, informacijski sistem Infor
Published in RUNG: 05.11.2024; Views: 173; Downloads: 3
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Keywords: CDKL5, nanobodies, biopanning
Published in RUNG: 05.11.2024; Views: 151; Downloads: 0
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