Abstract: This study introduces solid-state tuning of a mesostructured cellular foam (MCF) to enhance hydrogen (H-2) storage in clathrate hydrates. Grafting of promoter-like molecules (e.g., tetrahydrofuran) at the internal surface of the MCF resulted in a substantial improvement in the kinetics of formation of binary H-2-THF clathrate hydrate. Identification of the confined hydrate as sII clathrate hydrate and enclathration of H-2 in its small cages was performed using XRD and high-pressure H-1 NMR spectroscopy respectively. Experimental findings show that modified MCF materials exhibit a similar to 1.3 times higher H-2 storage capacity as compared to non-modified MCF under the same conditions (7 MPa, 265 K, 100% pore volume saturation with a 5.56 mol% THF solution). The enhancement in H-2 storage is attributed to the hydrophobicity originating from grafting organic molecules onto pristine MCF, thereby influencing water interactions and fostering an environment conducive to H-2 enclathration. Gas uptake curves indicate an optimal tuning point for higher H-2 storage, favoring a lower density of carbon per nm(2). Furthermore, a direct correlation emerges between higher driving forces and increased H-2 storage capacity, culminating at 0.52 wt% (46.77 mmoles of H-2 per mole of H2O and 39.78% water-to-hydrate conversions) at 262 K for the modified MCF material with fewer carbons per nm(2). Notably, the substantial H-2 storage capacity achieved without energy-intensive processes underscores solid-state tuning's potential for H-2 storage in the synthesized hydrates. This study evaluated two distinct kinetic models to describe hydrate growth in MCF. The multistage kinetic model showed better predictive capabilities for experimental data and maintained a low average absolute deviation. This research provides valuable insights into augmenting H-2 storage capabilities and holds promising implications for future advancements.

Abstract: The emerging reductive catalytic fractionation biorefinery which is currently under development aims to convert woody biomass efficiently into high-value products. Despite its potential, the environmental consequences of its implementation are not well known. Therefore, a forward-looking consequential life cycle assessment examines greenhouse gas emissions associated with its products (pulp, phenolic monomers, and oligomers) compared to alternative market options. Findings indicate that current greenhouse gas emissions exceed those of the existing alternatives, with by-products and the gaseous waste stream as major contributors. Process adaption to (i) produce higher-valued products (bleached pulps, phenols, and propylene) and (ii) incinerate gaseous waste stream for energy are proposed, potentially reducing emissions by up to 50 %, outperforming alternative options. Compared to land-based transportation, waterways can increase feedstock availability by up to 1000 km without an increase in emissions. In conclusion, the consequential approach provides valuable insights for enhancing and optimizing the environmental performance of the process.

Abstract: In 2023, the European Union will vote on the reauthorization of glyphosate use, renewed in 2017 despite concern on impacts on the environment and public health. A ban is supported by several Member States but rejected by most farmers. What are citizens’ preferences to phase out glyphosate? To assess whether taxation could be an alternative to a ban, we conducted a discrete choice experiment in five European countries. Our results reveal that the general public is strongly willing to pay for a reduction in glyphosate use. However, while 75.5% of respondents stated to support a ban in the pre-experimental survey, experimental results reveal that in 73.35% of cases, earmarked taxation schemes are preferred when they lead to a strong reduction in glyphosate use for an increase in food price lower than that induced by a ban. When glyphosate reduction is balanced against its costs, a tax may be preferred.

Abstract: Appropriate use of agricultural technologies and diversifying the farming activities is critical to addressing food security problems in Africa, including Ethiopia. The country is experimenting with the new Agricultural Innovation System (AIS) approach alongside the well-established Transfer of Technology (ToT) approach. This paper analyzes the gaps between policy discourses (as reflected in policy documents and strategic orientation documents) and extension practices (as reflected in the daily exchanges between farmers and the frontline staff of the Ethiopian extension system). It provides insights into the challenges faced and emphasizes the need for better coordination between policy formulation and implementation to enhance extension services. Policymakers, practitioners, and researchers can benefit from the valuable perspectives the findings offer. The study contributes to understanding the relationship between policy discourses and extension practices, and its implications can inform policy design and implementation in similar contexts. A qualitative research approach was deployed to analyze policy discourse and practice. Data were collected in Fogera, a district in Northwest Ethiopia, between August 2018 and February 2019. The data for the paper were obtained from 23 Focus Group Discussions conducted with men and women. 13 Informant Interviews (KIIs) were also carried out with personnel at different levels of government agricultural services and departments. Transcripts of recordings of the Focus Group Discussions (FGDs) and Key Informant Interviews (KIIs) were analyzed using a deductive approach. The study focuses on rice crops in the Fogera district, which are crucial for food security and reducing poverty. Although the geographic area is limited, the results can be used to improve the extension system in other areas facing similar challenges. Specifically, the study suggests switching from the traditional transfer of technology approach to the agricultural innovation system approach. Furthermore, the study's techniques, such as qualitative interviews, may have limitations and not fully capture the intricacies of policy and extension practices. The findings demonstrate that, although the policy documents strongly adhere to agricultural innovation system principles, top-down transfer of technology approaches continues to dominate in practice. Moreover, we have found potential discrepancies between the training content delivered and the specific needs of smallholder farmers. Practically, prescriptive systems are still used because agricultural innovation system approaches are not well understood by the Extension Agents. To realize a genuine agricultural innovation system, Ethiopia's extension apparatus should move forward with building committed and robust relationships between farmers, extension agents, researchers, private sectors, and non-governmental organizations. To this end, more research, enhanced training, and improved institutions are needed on what genuine agricultural innovation system could look like at the grass-roots level. This also includes understanding the roles that different actors within Ethiopia's development army should assume how a multi-actor policy dialogue can be organized.

Abstract: Climate change is causing alterations in precipitation patterns, leading to adverse ecological consequences in many ecosystems. Recently, an increasingly persistent weather pattern has emerged, characterized by lengthening the duration of alternating dry and wet periods, which is more complex than exclusively drought or increasing precipitation. It is currently unclear how soil microbial communities respond to these new regimes in relation to their interactions with plants, especially in precipitation-sensitive ecosystems, such as tropical rainforests and grasslands. In this thesis, we explored responses of soil bacterial and fungal communities to increasing weather persistence in rainforests and grasslands, using high throughput sequencing technology. We firstly investigated the resistance and resilience of microbial communities to prolonged drought in a mature seasonal tropical rainforest which experiences unusually intensive dry seasons in the current century. Through excluding rainfall during and after the dry season, a simulated prolongation of the dry season by five months was compared to the control. Our results indicate that as rain exclusion progressed, the microbial communities increasingly diverged from the control, indicating a moderate resistance to prolonged drought. However, when the drought ceased, the composition and co-occurrence patterns of soil microbial communities immediately recovered to that in the control, implying a high resilience. To further investigate the ecological roles of soil microbial communities in response to increasing weather persistence, we set up grassland mesocosm experiments. In these experiments, precipitation frequency was adjusted along a series, ranging from 1 to 60 consecutive days alternating of dry and wet periods, while keeping the total precipitation constant. Our results show that microbial community assembly tended to be more stochastic processes at intermediate persistence of dry and wet alternations while more deterministic processes dominated at low and high persistence within 120 days regime exposure. Moreover, more persistent precipitation reduced the fungal diversity and network connectivity but barely impacted that of bacterial communities. The prior experiences of persistent weather events for one year caused legacy effects. The soil microbial legacy induced by soil microbial communities subjected to prior persistent weather events was more enduring in subsequent fungal communities than bacterial communities, likely due to slower growth of fungi compared to bacteria. However, a minor effect of soil microbial legacy  was observed on plant performance. In addition, we kept the grassland mesocosm experiment for two growing seasons. The effects of precipitation persistence on soil microbial communities increased in the second year. The dissimilarities of microbial communities between the first and second year were less with more persistent precipitation, potentially resulting in more vulnerable microbial communities, due to some taxa disappearing and a reduction in functional redundancy under more persistent weather. To conclude, our findings provide a comprehensive theoretical understanding of soil microbial communities in response to the current and future climate change, drawing from both natural and experimental systems. It helps in predicting and managing the impacts of future climate change on ecosystems mediated by microbial communities. Additionally, the findings of microbe-mediated legacy effects on grassland ecosystems can provide practical guidance for their application in agriculture, specifically for using an inoculum to mitigate the impacts of climate change.

Abstract: Aside from potential environmental benefits, the implementation of circular economy principles in businesses can have merits for the labour market. The current unemployment in several regions of Europe and the qualitative mismatch between supply and demand could be countered by reskilling the labour force to adjust supply and demand to one another for increased reuse, repair, or recycling, among others. This study uses interviews to increase the focus of the research question and uses survey data to perform an ordered probit regression analysis to sketch the current and future landscape of startups’ skills in Flanders (Belgium), and to analyse the relationship between circular strategies and different types of skills. The results show that design to lower material use increases the need for transport and logistics skills, digitalisation increases the need for R&D and IT skills, and the recuperation of waste requires technical knowledge. Furthermore, gender, age, and experience of the entrepreneur influence the needed skills. The paper probed for policy recommendations for the uptake of circular strategies and recommendations for future research. The most asked policy measures by the respondents are innovation and collaboration support (subsidies), fiscal measures that support circular goods and services, and public procurement for circular goods and services. This research is of relevance for several stakeholders, such as startup ecosystems, sector organisations, policy makers in innovation policy and labour market policy, and educational institutions.

Abstract: Photoelectrochemical detection of nucleic acid-based cancer biomarkers offers opportunities for highly sensitive, selective, and fast quantitative detection using low-cost measurement instruments. In order to establish itself as a standard method for identifying and quantifying nucleic acids, we have developed a multiplexing strategy using LED technology for photoelectrochemical detection in 96 samples simultaneously. A dedicated setup based on the 96-well plate configuration with a custom-made 96-well LED array was developed. Subsequently, a proof-of-concept study was performed for three miRNAs that are associated with prostate cancer, i.e., miRNA-141, miRNA-145, and miRNA-375. First, measurements with photosensitizer chlorin e6 and redox reporter hydroquinone free in solution proved the proper functioning of the multiplexed detection. Second, the photoelectrochemical detection of the three miRNAs at 24 nM levels was successfully demonstrated. Thereafter, linear calibration curves (R2 > 0.9 for all analytes) were made with plasma spiked with 8–500 pM miRNA. This work presents the first system for multiplexed high-throughput photoelectrochemical detection, allowing it potentially to become a cost-effective and faster alternative to RT-qPCR and gene sequencing techniques in the future.

Abstract: Searching for sustainable polymers requires access to biomass-based monomers. In that sense, glucose-derived cis,cis-muconic acid stands as a high-potential intermediate. However, to unlock its potential, an isomerization to the value-added trans,trans-isomer, trans,trans-muconic acid, is required. Here we develop atomically dispersed low-loaded Ru on beta zeolite catalysts that produce trans,trans-muconate in ethanol with total conversion (to equilibrium) and a selectivity of >95%. We reach very high turnovers per Ru and productivity rates of 427 mM h(-1) (similar to 85 g l(-1) h(-1)), surpassing the bio-based cis,cis-muconic acid production rates by an order of magnitude. By coupling isomerization to Diels-Alder cycloaddition, terephthalate intermediates are produced in around 90% yields, circumventing the isomer equilibrium. Isomerization is promoted by Ru hydride species where the hydrides are generated from the alcohol solvent, as evidenced by Fourier transform infrared spectroscopy. Beyond isomerization, the Ru-zeolite and its hydride-forming capacity could be of use as a heterogeneous catalyst for other hydride chemistries, demonstrated by a successful hydride transfer hydrogenation.

Abstract: Two-dimensional (2D)egg-shape equa-tions are potent mathematical tools, facilitating the description of avian egg geometries in their applied mathematical modelling and poultry science implementations. In the present study, 2 distinct polar equations,namely the Carter-Morley-Jones equation (CMJE) and simplified Gielis equation(SGE), were used to fit the profile geometries of 415 domestic pigeon (Columba livia domestica) eggs based on nonlinear least squares regression methods.

Abstract: The voltage decay of Li -rich layered oxide cathode materials results in the deterioration of cycling performance and continuous energy loss, which seriously hinders their application in the high-energy – density lithium -ion battery (LIB) market. However, the origin of the voltage decay mechanism remains controversial due to the complex influences of transition metal (TM) migration, oxygen release, indistinguishable surface/bulk reactions and the easy intra/inter-crystalline cracking during cycling. We investigated the direct cause of voltage decay in micrometer -scale single -crystal Li 1.2 Mn 0.54 Ni 0.13 Co 0.13 O 2 (SC-LNCM) cathode materials by regulating the cut-off voltage. The redox of TM and O 2- ions can be precisely controlled by setting different voltage windows, while the cracking can be restrained, and surface/bulk structural evaluation can be monitored because of the large single crystal size. The results show that the voltage decay of SC-LNCM is related to the combined effect of cation rearrangement and oxygen release. Maintaining the discharge cutoff voltage at 3 V or the charging cutoff voltage at 4.5 V effectively mitigates the voltage decay, which provides a solution for suppressing the voltage decay of Lirich and Mn-based layered oxide cathode materials. Our work provides significant insights into the origin of the voltage decay mechanism and an easily achievable strategy to restrain the voltage decay for Li -rich and Mn-based cathode materials.

Abstract: This dataset contains 30 STL files of different geometries of microneedles (face angle, inner diameter, outer diameter, wall thickness) which are 3D printable using mSLA printers.

Abstract: The growing non-medical use of benzodiazepines (BZs) has led to the emergence of counterfeit BZ pills and new psycho-active substances (NPS) in the BZ class on the illicit market. Comprehensive analytical methods for BZ identification are required to allow law enforcement, first aid responders and drug-checking services to analyze a variety of sample types and contents to make timely decisions on the spot. In this work, the electrochemical behavior of diazepam (DZ), clonazepam (CZ) and alprazolam (AP) is studied on graphite screen-printed electrodes, both with and without dissolved oxygen in the solution, to link their redox signals to their chemical structure. After elucidation of their reduction mechanisms using liquid chromatography coupled to highresolution mass spectrometry, three structural classes (Class 1, Class 2 and Class 3) were defined, each with different redox centers and electrochemical behavior. Subsequently, 22 confiscated pills containing 14 different BZs were correctly assigned to these three structural classes, with the deoxygenated conditions displaying the highest class selectivity. Finally, the three classes were successfully detected after being spiked into five alcoholic beverages in the context of drug-facilitated sexual assault. For analysis in red wine, which complicated the analysis by interfering with Class 1, a dual test strategy in pH 2 and pH 7 was proposed for accurate detection. Its rapid measurements, broad scope and lack of interference from diluents or colors makes this method a promising approach for aiding various services in combating problematic BZ use.

Abstract: Lead based bulk piezoelectric materials, e.g., PbZrxTi1-xO3 (PZT), are widely used in electromechanical applications, sensors, and transducers, for which optimally performing thin films are needed. The results of a multi-domain Landau-Ginzberg-Devonshire model applicable to clamped ferroelectric thin films are used to predict the lattice symmetry and properties of clamped PZT thin films on different substrates. Guided by the thermal strain phase diagrams that are produced by this model, experimentally structural transitions are observed. These can be related to changes of the piezoelectric properties in PZT(x = 0.6) thin films that are grown on CaF2, SrTiO3 (STO) and 70% PbMg1/3Nb2/3O3-30% PbTiO3 (PMN-PT) substrates by pulsed laser deposition. Through temperature en field dependent in situ X-ray reciprocal space mapping (RSMs) and piezoelectric force microscopy (PFM), the low symmetry monoclinic phase and polarization rotation are observed in the film on STO and can be linked to the measured enhanced properties. The study identifies a monoclinic -rhombohedral M-C-M-A-R crystal symmetry path as the polarization rotation mechanism. The films on CaF2 and PMN-PT remain in the same symmetry phase up to the ferroelectric-paraelectric phase transition, as predicted. These results support the validity of the multi-domain model which provides the possibility to predict the behavior of clamped, piezoelectric PZT thin films, and design films with enhanced properties.

Abstract: Transmission electron microscopy is an important technique in the exploration of materials’ structures. This is especially true since the development of electron optical aberration correctors greatly facilitated atomic resolution imaging. We are currently experiencing an ongoing revolution in electron microscopy with the widespread adoption of direct electron detectors. Scientists have reported a lot of key scientific findings facilitated by direct electron detectors. One particular research domain is electron ptychography, which holds promise for unraveling the intricate structures of highly beam-sensitive materials like bio samples and achieving super-resolution without the limitation of aperture in the condenser lens system. Nevertheless, challenges persist both in experimental setups and algorithmic processes. Issues such as the comparatively sluggish scanning speed of cameras and contrast reversals of the reconstructed phase for relatively thick specimens, disrupting phase or weak phase approximations, remain noteworthy limitations. This thesis addresses these challenges by the event-driven Timepix3 detector, presenting a viable solution to the speed bottleneck. Moreover, innovative approaches for applying electron ptychography to relatively thick samples, employing a middle focusing strategy, are proposed. This research aims to push the boundaries of electron microscopy, offering solutions to existing limitations and advancing the field towards more efficient and accurate imaging techniques.