Abstract: Chemically synthesized metal nanoparticles with morphological chiral features are known to exhibit strong circular dichroism. However, we still lack understanding of the correlation between morphological and chiroptical features of plasmonic nanoparticles. To shed light on that question, single nanoparticle experiments are required. We performed photothermal circular dichroism measurements of single chiral and achiral gold nanoparticles and correlated the chiroptical response to the 3D morphology of the same nanoparticles retrieved by electron tomography. In contrast to an ensemble measurement, we show that individual particles within the ensemble display a broad distribution of strength and handedness of circular dichroism signals. Whereas obvious structural chiral features, such as helical wrinkles, translate into chiroptical ones, nanoparticles with less obvious chiral morphological features can also display strong circular dichroism signals. Interestingly, we find that even seemingly achiral nanoparticles can display large g-factors. The origin of this circular dichroism signal is discussed in terms of plasmonics and other potentially relevant factors.

Abstract: Motivated by the potential of atomically thin magnets towards achieving tunable high-frequency magnonics, we detail the spin-wave dispersion of bilayer CrI3. We demonstrate that the magnonic behavior of the bilayer strongly depends on its stacking configuration and the interlayer magnetic ordering, where a topological band gap opens in the dispersion caused by the Dzyaloshinskii-Moriya and Kitaev interactions, classifying bilayer CrI3 as a topological magnon insulator. We further reveal that both the size and the topology of the band gap in a CrI3 bilayer with an antiferromagnetic interlayer ordering are tunable by an external magnetic field.

Abstract: When using hexagonal boron-nitride (hBN) as a substrate for graphene, the resulting moire pattern creates secondary Dirac points. By encapsulating a multilayer graphene within aligned hBN sheets the controlled moire stacking may offer even richer benefits. Using advanced tight-binding simulations on atomistically-relaxed heterostructures, here we show that the gap at the secondary Dirac point can be opened in selected moire-stacking configurations, and is independent of any additional vertical gating of the heterostructure. On the other hand, gating can broadly tune the gap at the principal Dirac point, and may thereby strongly compress the first moire mini-band in width against the moire-induced gap at the secondary Dirac point. We reveal that in hBN-encapsulated bilayer graphene this novel mechanism can lead to isolated bands flatter than 10 meV under moderate gating, hence presenting a convenient pathway towards electronically-controlled strongly-correlated states on demand.

Abstract: Micro-and nanoscopic X-ray techniques were used to investigate the relationship between uranium (U) tissue distributions and adverse effects to the digestive tract of aquatic model organism Daphnia magna following uranium nanoparticle (UNP) exposure. X-ray absorption computed tomography measure-ments of intact daphnids exposed to sublethal concentrations of UNPs or a U reference solution (URef) showed adverse morphological changes to the midgut and the hepatic ceca. Histological analyses of exposed organisms revealed a high proportion of abnormal and irregularly shaped intestinal epithelial cells. Disruption of the hepatic ceca and midgut epithelial tissues implied digestive functions and intestinal barriers were compro-mised. Synchrotron-based micro X-ray fluorescence (XRF) elemental mapping identified U co-localized with morphological changes, with substantial accumulation of U in the lumen as well as in the epithelial tissues. Utilizing high-resolution nano-XRF, 400-1000 nm sized U particulates could be identified throughout the midgut and within hepatic ceca cells, coinciding with tissue damages. The results highlight disruption of intestinal function as an important mode of action of acute U toxicity in D. magna and that midgut epithelial cells as well as the hepatic ceca are key target organs.

Abstract: Circularly polarized luminescent (CPL) films with high dissymmetry factors hold great potential for optoelectronic applications. Herei n , we propose a strategy for achieving strongly dissymetric CPL in nanocomposite films based on chira l i t y induction and energy transfer to semiconductor nanocrystals. First, focusing on a purely organic system, aggregation-induced emission (AIE) and CPL activity of organic liquid crystals (LCs) forming helical nanofilaments was detected, featuring green emission with high dissymmetry factors g(lum) similar to 10(-2). The handedness of helical filaments, and thus the sign of CPL, was controlled via minute amounts of a small chiral organic dopant. Second, nanocomposite films were fabricated by incorporating InP/ZnS semi-conductor quantum dots (QDs) into the LC matri x , which induced the chiral assembly of QDs and endowed them with chiroptical properties. Due to the spectral matching of the components, energy transfer (ET) from LC to QDs was possible enabling a convenient way of tuning CPL wavelengths by varying the LC/QD ratio. As obtained, composite films exhibited absolute glum values up to similar to 10(-2) and thermally on/off switchable luminescence. Overall, we demonstrate the induction of chiroptical properties by the assembly of nonchiral building QDs on the chiral organic template and energy transfer from organic films to QDs, representing a simple and versatile approach to tune the CPL activity of organic materials.

Abstract: Co-digestion of organic waste and wastewater is receiving increased attention as a plausible waste management approach toward energy recovery. However, traditional anaerobic processes for co-digestion are particularly susceptible to severe organic loading rates (OLRs) under long-term treatment. To enhance technological feasi-bility, this work presented a two-stage Anaerobic Membrane Bioreactor (2 S-AnMBR) composed of a hydrolysis reactor (HR) followed by an anaerobic membrane bioreactor (AnMBR) for long-term co-digestion of food waste and kitchen wastewater. The OLRs were expanded from 4.5, 5.6, and 6.9 kg COD m- 3 d-1 to optimize biogas yield, nitrogen recovery, and membrane fouling at ambient temperatures of 25-32 degrees C. Results showed that specific methane production of UASB was 249 +/- 7 L CH4 kg-1 CODremoved at the OLR of 6.9 kg TCOD m- 3 d-1. Total Chemical Oxygen Demand (TCOD) loss by hydrolysis was 21.6% of the input TCOD load at the hydraulic retention time (HRT) of 2 days. However, low total volatile fatty acid concentrations were found in the AnMBR, indicating that a sufficiently high hydrolysis efficiency could be accomplished with a short HRT. Furthermore, using AnMBR structure consisting of an Upflow Anaerobic Sludge Blanket Reactor (UASB) followed by a side -stream ultrafiltration membrane alleviated cake membrane fouling. The wasted digestate from the AnMBR comprised 42-47% Total Kjeldahl Nitrogen (TKN) and 57-68% total phosphorous loading, making it suitable for use in soil amendments or fertilizers. Finally, the predominance of fine particles (D10 = 0.8 mu m) in the ultra -filtration membrane housing (UFMH) could lead to a faster increase in trans-membrane pressure during the filtration process.

Abstract: Transmission electron microscopy (TEM) is a powerful tool for unveiling the structural, compositional, and electronic properties of organic-inorganic hybrid perovskites (OIHPs) at the atomic to micrometer length scales. However, the structural and compositional instability of OIHPs under electron beam radiation results in misunderstandings of the microscopic structure-property-performance relationship in OIHP devices. Here, ultralow dose TEM is utilized to identify the mechanism of the electron-beam-induced changes in OHIPs and clarify the cumulative electron dose thresholds (critical dose) of different commercially interesting state-of-the-art OIHPs, including methylammonium lead iodide (MAPbI(3)), formamidinium lead iodide (FAPbI(3)), FA(0.83)Cs(0.17)PbI(3), FA(0.15)Cs(0.85)PbI(3), and MAPb(0.5)Sn(0.5)I(3). The critical dose is related to the composition of the OIHPs, with FA(0.15)Cs(0.85)PbI(3) having the highest critical dose of approximate to 84 e angstrom(-2) and FA(0.83)Cs(0.17)PbI(3) having the lowest critical dose of approximate to 4.2 e angstrom(-2). The electron beam irradiation results in the formation of a superstructure with ordered I and FA vacancies along (c), as identified from the three major crystal axes in cubic FAPbI(3), (c), (c), and (c). The intragrain planar defects in FAPbI(3) are stable, while an obvious modification is observed in FA(0.83)Cs(0.17)PbI(3) under continuous electron beam exposure. This information can serve as a guide for ensuring a reliable understanding of the microstructure of OIHP optoelectronic devices by TEM.

Abstract: Dynamics of electron wave-packets is studied using the continuum Dirac model in a graphene geometric diode where the propagation of the wave packet is favored in certain direction due to the presence of geometric constraints. Clear rectification is obtained in the THz frequency range with the maximum rectification level of 3.25, which is in good agreement with recent experiments on graphene ballistic diodes. The rectification levels are considerably higher for systems with narrower channels. In this case, the wave packet transmission probabilities and rectification rate also strongly depend on the energy of the incident wave packet, as a result of the quantum nature of energy levels along such channels. These findings can be useful for fundamental understanding of the charge carrier dynamics in graphene geometry diodes.

Abstract: One of the most basic criteria in documenting rangeland use prospects is the recognition of byproducts and their economic appraisal. The current study was conducted to assess the economic indices of exploiting byproduct production in Shahindej, Northwest Iran. For this purpose, 24 by-product-generating species were selected in 114 locations that belong to 49 rangeland units. The total expected value of 24 by-product generating species yield and forage production was calculated at 44.22 USD ha(-1). The results of this study showed that the sustainability of natural resources depends on the effective participation and empowerment of local communities. Furthermore, by-product exploitation contributes significantly to the local economy and employment while also reducing grazing intensity. Overall, the findings of this study show that by-product earnings should be considered in range management schemes and comprehensive natural-area management.

Abstract: This study explores consumers' visual sustainability impressions of paper-based packaging that has incorporated obvious waste content. Two research questions were addressed concerning (i) the environmental sustainability perception of noticeable waste content in packaging and (ii) the impact of the presentation format (i.e., online versus in-person surveys) when studying these perceptions. Best-worst scaling experiments were conducted, which made respondents choose the 'most' and 'least' environmentally friendly package. Packages were designed using paperboard substrates blending either brown linerboard or white hardwood pulp with different recovered waste materials. The results showed that consumers perceive obvious waste-containing packaging as more environmentally friendly than classical packaging (with no visual waste). Samples with a brown base and agricultural waste were perceived as more sustainable compared to white packaging and the use of paper waste. In addition, the presentation format changed respondents' perception, and should therefore be carefully considered when designing surveys.

Abstract: The Ricardian model is a widely used approach based on cross-sectional regression analysis to estimate climate change impacts on agricultural productivity. Up until now, researchers have focused on the impacts of gradual changes in temperature and precipitation, even though climate change is known to encompass also changes in the severity and frequency of extreme weather events. This research investigates the impact of heatwaves on European agriculture, additional to the impact of average climate change. Using a dataset of more than 60,000 European farms, the study examines whether adding a measure for heatwaves to the Ricardian model influences its results. We find that heatwaves have a minor impact on agricultural productivity and that this impact is moderated by average temperature. In colder regions, farm productivity increases with the number of heatwave days. For warmer regions, land values decrease with heatwave frequency. Despite the moderating effect, the marginal effect of heatwave frequency, i.e. the percentage change in agricultural land values caused by one more heatwave day per year, is small in comparison to the effect of average temperature increases. Non-marginal effects are found to be relevant, but only in the case of increased heatwave frequency. According to our results, farms are not expected to suffer more from extreme weather than from mean climate change, as was claimed by several previous studies.

Abstract: The rise in plastic packaging production and disposal has encouraged the progress of recycling technologies and aroused policy discussion on how to increase recycling rates. However, the effect that these policy instruments will have on the development of the different recycling technologies has not been studied holistically yet. This dissertation explores how new and existing technologies will behave under the market and policy conditions observed at present and after the implementation of the policy instruments that are under discussion. The technologies that are analyzed in this thesis are mechanical recycling and thermochemical recycling of post-consumer polyolefin waste. Using a techno-economic assessment that takes into account the physical properties of the different plastic fractions and their contamination level, the study shows that both mechanical and thermochemical recycling can be profitable if oil prices remain steady or increase. Specifically, mechanical recycling will show better results than thermochemical recycling for plastic fractions with low contamination levels. On the contrary, thermochemical recycling is more profitable for fractions with a higher contamination level from which high-quality products cannot be obtained with mechanical recycling, such as PE films. Moreover, it demonstrates that besides the oil prices and sorted waste prices, waste purity and the plant capacity are the variables that influence more the net present value of thermochemical recycling and the labor cost and waste purity the ones of mechanical recycling. The thesis explores the dynamics between the stakeholders of the circular value chain and predicts the recycling rates under the implementation of several policy instruments. This is done with a supply chain equilibrium model, based on the extended producer responsibility scheme implemented in Flanders, that uses as an input the cost structures of mechanical and thermochemical recycling obtained from the techno-economic assessments. Direct interventions like recycled content standards, can decouple the recycling industry from the oil market, but in the long term, they may not present incentives to achieve recycling levels beyond the targeted amounts and thus limit technological innovation. On the contrary, economic interventions such as taxes, create economic incentives for recycling and allow fund collection from the government but leave the recycled levels dependent on external markets. Results also show that higher recycling rates does not necessarily mean better environmental performance. Therefore, when designing circular economy policies, policymakers should carefully analyze whether the intention is to increase circularity or improve the sustainability of the value chains.

Abstract: Novel emerging biorefinery technologies have gained interest and have the potential to tackle several sustainability challenges in our society. A lignin-first biorefinery process – reductive catalytic fractionation (RCF) – is currently under development with the aim to process wood into high-value end-products that replace highly polluting fossil oil-based products. However, such emerging technologies are not matured yet, holding a certain degree of technological, economic, and environmental uncertainty. Hence, an appropriate assessment method is required to assess techno-economic feasibility and environmental impacts of emerging uncertain technologies (e.g lignin-first RCF process). This dissertation aims to develop an integrated techno-environmental economic assessment framework to assess emerging technologies dynamically and prospectively from economic and environmental points of view. First, a techno-economic assessment (TEA) is performed to assess the economic feasibility and the most influential economic and technological parameters of the lignin-first RCF biorefinery taking the whole wood value chain into account. By making the relations across the wood value chain, the scale of the biorefinery, wood species, and output prices highly determine the economic feasibility. The economic feasibility can be reached by a sufficient capacity level which depends on wood species-specific conditions. Also, waste wood proves to be the most profitable feedstock in comparison to virgin wood. Second, an analytical real options analysis (ROA) is performed taking two correlated market uncertainties and the value of flexibility into account to identify the optimal investment decision in an RCF biorefinery. Two different investment options, separated and united investments in harvesting equipment and RCF biorefinery, are analyzed. In both scenarios, market uncertainty postpones the investment. When both investment decisions are united, the probability of investment increases in comparison to separated investments. The study reveals that RCF has the potential to stimulate investments within the wood value chain. Third, a consequential life cycle assessment (LCA) is performed to assess the carbon emissions and the environmental consequences of the lignin-first RCF process and its products. The study reveals that at the current stage RCF products have higher carbon emissions than their alternative counterparts. Several options to improve the environmental performance are discussed such as different RCF technology configurations, targeting different RCF products with the ability to replace higher polluting alternative counterparts on the markets. Other discussion points such as transportation type and the distance, (in-)direct land-use change, the use stage and disposal stages implications, and a more comprehensive environmental view of the RCF products, show the potential to improve the environmental performance of the RCF technology. Overall, the study shows that the RCF process can be environmentally desirable if the appropriate RCF configuration and products are chosen. Finally, the above-mentioned methods – techno-economic assessment, analytical real options analysis, and consequential life cycle assessment – are uniquely integrated within the newly developed integrated assessment framework. The framework has the aim to complement the shortcomings and combine the advantages of all three methods. The framework assesses emerging technologies to give predictive insights about the time-specific economic and environmental performance under the newly developed three threshold conditions: technological readiness, economic feasibility, and environmental desirability. The developed integrated assessment framework assesses dynamically and prospectively the RCF biorefinery implementation under Belgian conditions. It reveals that the economic feasibility increases and carbon emissions decrease over time. The RCF biorefinery fulfills all three threshold conditions – technological readiness, economic feasibility, and environmental desirability – consecutively. The newly developed integrated assessment framework offers decision support to several stakeholders of emerging technologies starting from low technology readiness level (TRL). Practitioners such as the technology developers, researchers, and policymakers can use the framework to evaluate emerging technologies that deal with high levels of technological, economic, and environmental uncertainties. The framework assesses emerging technologies on a detailed level to give decision-makers in-depth insights into the intertwined nature of the technological, economic, and environmental dimensions. It offers insights into the expected time-specific economic and environmental performances, potential, and challenges of the emerging technology to further improve the technology and direct R&Ds along the right path.

Abstract: The development of biomass pretreatment approaches that, next to (hemi)cellulose valorization, aim at the conversion of lignin to chemicals is essential for the long-term success of a biorefinery. Herein, we discuss a dithionite-assisted organosolv fractionation (DAOF) of lignocellulose in n-butanol and water to produce cellulosic pulp and mono-/oligo-aromatics. The study frames the technicalities of this biorefinery process and relates them to the features of the obtained product streams. We comprehensively identify and quantify all products of interest: solid pulp (acid hydrolysis-HPLC, ATR-FTIR, XRD, SEM, enzymatic hydrolysis-HPLC), lignin derivatives (GPC, GC-MS/FID, 1H-13C HSQC NMR, ICP-AES), and carbohydrate derivatives (HPLC). These results were used for inspecting the economic feasibility of DAOF. In the best process configuration, a high yield of monophenolics was reached (~20%, based on acid insoluble lignin in birch sawdust). Various other lignocellulosic feedstocks were also explored, showing that DAOF is particularly effective on hardwood and herbaceous biomass. Overall, this study demonstrates that DAOF is a viable fractionation method for the sustainable upgrading of lignocellulosic biomass.

Abstract: The first covalently linked conjugate of metal phthalocyaninate and chlorin e(6) derivative has been obtained by transesterification of alpha-ketomethyl ester in methylpheophorbide a with zinc(II) 2-(2-hydroxymethylbenzyloxy)-9(10),16(17),23(24)-tri-tert-butylphthalocyaninate under mild conditions. The dyad exhibits a panchromatic nature revealing both the phthalocyanine and pheophorbide derived bands in the UV-Vis absorption spectrum. The H-1 NMR spectroscopy data combined with theoretical calculations indicate the presence of spatial intramolecular interactions between the phthalocyanine, pheophorbide and spacer fragments of the dyad allowing to forecast its enhanced nonlinear optical properties, as well as the characteristic energy transfer from the excited pheophorbide subunit to the phthalocyanine core. Indeed, when excited in the UV-Vis range, the conjugate shows red fluorescence with the spectral maximum at 686 nm, which is close to the one of the initial zinc phthalocyaninate. Furthermore, the dyad effectively generates singlet oxygen and, in the presence of polyvinylpyrrolidone (PVP) as biocompatible solubilizer, forms stable micellar saline solutions with the particles ranged in size between 40 and 100 nm. These nanoparticles represent promising third-generation photosensitizing systems for application in theranostics.