Abstract: Gian Giacomo Inchiocchio (1604-1656), better known as Barbelli, was one of the main exponents of Lombard painting of the seventeenth century. A large body of work is attributed to him, encompassing a wide range of drawings, murals, and oil paintings. However, despite his broad production, there are still many open questions regarding his painting techniques and materials. In this paper, a multi-analytical study of the cycle Stories of the life of Saint George that originally decorated the presbytery of the parish church of Casaletto Vaprio (Cremona, Italy) was performed, combining non-invasive techniques with the characterisation of selected micro samples. Results show that Barbelli used a very limited number of inorganic pigments, often mixing them together to create different colours and shades. Remains of caseinate and degradation products (i.e. weddellite and whewellite) related to the strappo intervention were also highlighted. The study helped to decipher the materials and technique of this painting, providing data that can be used as a reference to study his extensive production.

Abstract: This paper brings the comparison of performances of CO2 conversion by plasma and plasma-assisted catalysis based on the data collected from literature in this field, organised in an open access online data-base. This tool is open to all users to carry out their own analyses, but also to contributors who wish to add their data to the database in order to improve the relevance of the comparisons made, and ultimately to improve the efficiency of CO2 conversion by plasma-catalysis. The creation of this database and data-base user interface is motivated by the fact that plasma-catalysis is a fast-growing field for all CO2 con-version processes, be it methanation, dry reforming of methane, methanolisation, or others. As a result of this rapid increase, there is a need for a set of standard procedures to rigorously compare performances of different systems. However, this is currently not possible because the fundamental mechanisms of plasma-catalysis are still too poorly understood to define these standard procedures. Fortunately how-ever, the accumulated data within the CO2 plasma-catalysis community has become large enough to war-rant so-called “big data” studies more familiar in the fields of medicine and the social sciences. To enable comparisons between multiple data sets and make future research more effective, this work proposes the first database on CO2 conversion performances by plasma-catalysis open to the whole community. This database has been initiated in the framework of a H2020 European project and is called the “PIONEER DataBase”. The database gathers a large amount of CO2 conversion performance data such as conversion rate, energy efficiency, and selectivity for numerous plasma sources coupled with or without a catalyst. Each data set is associated with metadata describing the gas mixture, the plasma source, the nature of the catalyst, and the form of coupling with the plasma. Beyond the database itself, a data extraction tool with direct visualisation features or advanced filtering functionalities has been developed and is available online to the public. The simple and fast visualisation of the state of the art puts new results into context, identifies literal gaps in data, and consequently points towards promising research routes. More advanced data extraction illustrates the impact that the database can have in the understanding of plasma-catalyst coupling. Lessons learned from the review of a large amount of literature during the setup of the database lead to best practice advice to increase comparability between future CO2 plasma-catalytic studies. Finally, the community is strongly encouraged to contribute to the database not only to increase the visibility of their data but also the relevance of the comparisons allowed by this tool. (c) 2023 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by ELSEVIER B.V. and Science Press. This is an open access article under the CC BY license (http://creati- vecommons.org/licenses/by/4.0/).

Abstract: Two-dimensional (2D) ultra-thin materials are more crucial than their bulk counterparts for the covalent functionalization of their surface owing to atomic thinness, large surface-to-volume ratio, and high reactivity of surface atoms having unoccupied orbitals. Since the surface of a 2D material is composed of atoms having unoccupied orbitals, covalent functionalization enables one to improve or precisely modify the properties of the ultra-thin materials. Chemical functionalization of 2D materials not only modifies their intrinsic properties but also makes them adapted for nanotechnology applications. Such engineered materials have been used in many different applications with their improved properties. In the present Perspective, we begin with a brief history of functionalization followed by the introduction of functionalized 2D materials. Our Perspective is composed of the following sections: the applications areas of 2D graphene and graphene oxide crystals, transition metal dichalcogenides, and in-plane anisotropic black phosphorus, all of which have been widely used in different nanotechnology applications. Finally, our Perspectives on the future directions of applications of functionalized 2D materials are given. The present Perspective sheds light on the current progress in nanotechnological applications of engineered 2D materials through surface functionalization.

Abstract: Environmental circumstances shaping soil microbial communities have been studied extensively. However, due to disparate study designs, it has been difficult to resolve whether a globally consistent set of predictors exists, or context‐dependency prevails. Here, we used a network of 18 grassland sites (11 of those containing regional plant productivity gradients) to examine (i) if similar abiotic or biotic factors predict both large‐scale (across sites) and regional‐scale (within sites) patterns in bacterial and fungal community composition, and (ii) if microbial community composition differs consistently at two levels of regional plant productivity (low vs. high). Our results revealed that bacteria were associated with particular soil properties (such as base saturation) and both bacteria and fungi were associated with plant community composition across sites and within the majority of sites. Moreover, a discernible microbial community signal emerged, clearly distinguishing high and low‐productivity soils across different grasslands independent of their location in the world. Hence, regional productivity differences may be typified by characteristic soil microbial communities across the grassland biome. These results could encourage future research aiming to predict the general effects of global changes on soil microbial community composition in grasslands and to discriminate fertile from infertile systems using generally applicable microbial indicators.

Abstract: Long-term human space exploration missions require environmental control and closed Life Support Systems (LSS) capable of producing and recycling resources, thus fulfilling all the essential metabolic needs for human survival in harsh space environments, both during travel and on orbital/planetary stations. This will become increasingly necessary as missions reach farther away from Earth, thereby limiting the technical and economic feasibility of resupplying resources from Earth. Further incorporation of biological elements into state-of-the-art (mostly abiotic) LSS, leading to bioregenerative LSS (BLSS), is needed for additional resource recovery, food production, and waste treatment solutions, and to enable more self-sustainable missions to the Moon and Mars. There is a whole suite of functions crucial to sustain human presence in Low Earth Orbit (LEO) and successful settlement on Moon or Mars such as environmental control, air regeneration, waste management, water supply, food production, cabin/habitat pressurization, radiation protection, energy supply, and means for transportation, communication, and recreation. In this paper, we focus on air, water and food production, and waste management, and address some aspects of radiation protection and recreation. We briefly discuss existing knowledge, highlight open gaps, and propose possible future experiments in the short-, medium-, and long-term to achieve the targets of crewed space exploration also leading to possible benefits on Earth.

Abstract: The highly tunable band structure of the zero-energy Landau level (zLL) of bilayer graphene makes it an ideal platform for engineering novel quantum states. However, the zero-energy Landau level at high electric fields has remained largely unexplored. Here we present magnetotransport measurements of bilayer graphene in high transverse electric fields. We observe previously undetected Landau level crossings at filling factors nu = -2, 1, and 3 at high electric fields. These crossings provide constraints for theoretical models of the zero-energy Landau level and show that the orbital, valley, and spin character of the quantum Hall states at high electric fields is very different from low electric fields. At high E, new transitions between states at nu = -2 with different orbital and spin polarization can be controlled by the gate bias, while the transitions between nu = 0 -> 1 and nu = 2 -> 3 show anomalous behavior.

Abstract: Energy-lean nitrogen removal technologies, such as partial nitritation/anammox, often encounter effluent issues due to elevated nitrate and ammonium levels. This study proposed a novel autotrophic polishing strategy coupling sulfur-driven denitratation with anammox. To explore the denitratation potential in obtaining stable and sufficient nitrite accumulation, the effects of pH, residual nitrate level, and biomass-specific nitrate loading rate (BSNLR) were investigated in an S0-packed bed reactor at low hydraulic retention time (i.e., 0.2 h). Implementing pH and residual nitrate control strategies would be easier in practice than BSNLR control to polish secondary effluent. Alkaline pH values could realize successful nitrite accumulation without residual nitrate, and further intensify the accumulation under increased residual nitrate levels. The nitrate level was positively correlated with the nitrite accumulation efficiency. At pH 8.5 and nitrate concentration of 1.0 ± 0.8 mg N L−1, sulfur-driven denitratation could successfully maintain nitrite accumulation of 6.4 ± 1.0 mg NO2−-N L−1, ideally for the downstream anammox in case of residual ammonium levels of around 5 mg N L−1. Since Thiobacillus members play a key role in managing nitrite accumulation, their abundance should be guaranteed in the practical application.

Abstract: The understanding of catalyst active sites is a fundamental challenge for the future rational design of optimized and bespoke catalysts. For instance, the partial reduction of Ce4+ surface sites to Ce3+ and the formation of oxygen vacancies are critical for CO2 hydrogenation, CO oxidation, and the water gas shift reaction. Furthermore, metal nanoparticles, the reducible support, and metal support interactions are prone to evolve under reaction conditions; therefore a catalyst structure must be characterized under operando conditions to identify active states and deduce structure-activity relationships. In the present work, temperature-induced morphological and chemical changes in Ni nanoparticle-decorated mesoporous CeO2 by means of in situ quantitative multimode electron tomography and in situ heating electron energy loss spectroscopy, respectively, are investigated. Moreover, operando electron energy loss spectroscopy is employed using a windowed gas cell and reveals the role of Ni-induced hydrogen spillover on active Ce3+ site formation and enhancement of the overall catalytic performance.

Abstract: Hydrogen (H2) storage, in the form of clathrate hydrates, has emerged as an attractive alternative to classical storage methods like compression or liquefaction. Nevertheless, the sluggish enclathration kinetics along with low gas storage capacities in bulk systems is currently impeding the progress of this technology. To this end, unstirred systems coupled with porous materials have been shown to tackle the aforementioned drawbacks. In line with this approach, the present study explores the use of hydrophobic periodic organosilica nanoparticles, later denoted as hollow ring-PMO (HRPMO), for H2 storage as clathrate hydrates under mild operating conditions (5.56 mol% THF, 7 MPa, and 265–273 K). The surface of the HRPMO nanoparticles was carefully decorated/functionalized with THF-like moieties, which are well-known promoter agents in clathrate formation when applied in classical, homogeneous systems. The study showed that, while the non-functionalized HRPMO can facilitate the formation of binary H2-THF clathrates, the incorporation of surface-bound promotor structures enhances this process. More intriguingly, tuning the concentration of these surface-bound promotor agents on the HRPMO led to a notable effect on solid-state H2 storage capacities. An increase of 3% in H2 storage capacity, equivalent to 0.26 wt%, along with a substantial increase of up to 28% in clathrate growth kinetics, was observed when an optimal loading of 0.14 mmol g−1 of promoter agent was integrated into the HRPMO framework. Overall, the findings from this study highlight that such tuning effects in the solid-state have the potential to significantly boost hydrate formation/growth kinetics and H2 storage capacities, thereby opening new avenues for the ongoing development of H2 clathrates in industrial applications.

Abstract: Wearable devices based on microneedle (MN) technology have recently emerged as tools for in situ transdermal sensing or delivery in interstitial fluid (ISF). Particularly, MN-based electrochemical sensors allow the continuous monitoring of analytes in a minimally invasive manner through ISF. Exogenous small molecules found in ISF such as therapeutic drugs are ideal candidates for MN sensors due to their correlation with blood levels and their relevance for the optimal management of personalized therapies. Herein, a hollow MN array patch is modified with conductive pastes and functionalized with cross-linked chitosan to develop an MN-based voltammetric sensor for continuous monitoring of methotrexate (MTX). Interestingly, the chitosan coating avoids biofouling while enabling the adsorption of MTX at the electrode’s surface for sensitive analysis. The MN sensor exhibits excellent analytical performance in vitro with protein-enriched artificial ISF and ex vivo under a Franz diffusion cell configuration. The MN sensor shows a linear range from 25 to 400 μM, which fits within the therapeutic range of high-dose MTX treatment for cancer patients and an excellent continuous operation for more than two days. Moreover, an iontophoretic hollow MN array patch is developed with the integration of both the anode and cathode in the single MN array patch. The ex vivo characterization demonstrates the transdermal on-demand drug delivery of MTX. Overall, the combination of both MN patches represents impactful progress in closed-loop systems for therapeutic drug management in disorders such as cancer, rheumatoid arthritis, or psoriasis.

Abstract: Solid carbon deposition is a persistent challenge in dry reforming of methane (DRM), affecting both classical and plasma-based processes. In this work, we use a microwave plasma in reverse vortex flow configuration to overcome this issue in CO₂/CH₄plasmas. Indeed, this configuration efficiently mitigates carbon deposition, enabling operation even with pure CH₄feed gas, in contrast to other configurations. At the same time, high reactor performance is achieved, with CO₂and CH₄conversions reaching 33% and 44% respectively, at an energy cost of 14 kJ L⁻¹for a CO₂ : CH₄ratio of 1 : 1. Laser scattering and optical emission imaging demonstrate that the shorter residence time in reverse vortex flow lowers the gas temperature in the discharge, facilitating a shift from full to partial CH₄pyrolysis. This underscores the pivotal role of flow configuration in directing process selectivity, a crucial factor in complex chemistries like CO₂/CH₄mixtures and very important for industrial applications.

Abstract: CsPbI3 is a promising perovskite material for photovoltaic applications in its photoactive perovskite or black phase. However, the material degrades to a photovoltaically inactive or yellow phase at room temperature. Various mitigation strategies are currently being developed to increase the lifetime of the black phase, many of which rely on inducing strains in the material that hinder the black-to-yellow phase transition. Physical insight into how these strategies exactly induce strain as well as knowledge of the spatial extent over which these strains impact the material is crucial to optimize these approaches but is still lacking. Herein, we combine machine learning potential-based molecular dynamics simulations with our in silico strain engineering approach to accurately quantify strained large-scale atomic structures on a nanosecond time scale. To this end, we first model the strain fields introduced by atomic substitutions as they form the most elementary strain sources. We demonstrate that the magnitude of the induced strain fields decays exponentially with the distance from the strain source, following a decay rate that is largely independent of the specific substitution. Second, we show that the total strain field induced by multiple strain sources can be predicted to an excellent approximation by summing the strain fields of each individual source. Finally, through a case study, we illustrate how this additive character allows us to explain how complex strain fields, induced by spatially extended strain sources, can be predicted by adequately combining the strain fields caused by local strain sources. Hence, the strain additivity proposed here can be adopted to further our insight into the complex strain behavior in perovskites and to design strain from the atomic level onward to enhance their sought-after phase stability.

Abstract: Pancreatic ductal adenocarcinoma (PDAC) is one of the most lethal diseases, characterized by a treatment-resistant and invasive nature. In line with these inherent aggressive characteristics, only a subset of patients shows a clinical response to the standard of care therapies, thereby highlighting the need for a more personalized treatment approach. In this study, we comprehensively unraveled the intra-patient response heterogeneity and intrinsic aggressive nature of PDAC on bulk and single-organoid resolution. We leveraged a fully characterized PDAC organoid panel ( N  = 8) and matched our artificial intelligence-driven, live-cell organoid image analysis with retrospective clinical patient response. In line with the clinical outcomes, we identified patient-specific sensitivities to the standard of care therapies (gemcitabine-paclitaxel and FOLFIRINOX) using a growth rate-based and normalized drug response metric. Moreover, the single-organoid analysis was able to detect resistant as well as invasive PDAC organoid clones, which was orchestrates on a patient, therapy, drug, concentration and time-specific level. Furthermore, our in vitro organoid analysis indicated a correlation with the matched patient progression-free survival (PFS) compared to the current, conventional drug response readouts. This work not only provides valuable insights on the response complexity in PDAC, but it also highlights the potential applications (extendable to other tumor types) and clinical translatability of our approach in drug discovery and the emerging era of personalized medicine.

Abstract: Herein, the efficacy of WOx-promoted CeO2-SiO2 and CeO2-ZrO2 mixed oxide catalysts in the solvent-free selective oxidation of benzyl alcohol to benzaldehyde using molecular oxygen as an oxidant is reported. We evaluated the effects of the oxidant and catalyst concentration, reaction duration, and temperature on the reaction with an aim to optimize the reaction conditions. The as-prepared CeO2, CeO2-ZrO2, CeO2-SiO2, WOx/CeO2, WOx/CeO2-ZrO2, and WOx/CeO2-SiO2 catalysts were characterized by X-ray diffraction (XRD), N-2 adsorption-desorption, Raman spectroscopy, temperature-programmed desorption of ammonia (TPD-NH3), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). These characterisation results indicated that the WOx/CeO2-SiO2 catalyst possessed improved physicochemical (i.e., structural, textural, and acidic) properties owing to the strong interactivity between WOx and CeO2-SiO2. A higher number of Ce3+ ions (I-u '''/I-Total) were created with the WOx/CeO2-SiO2 catalyst than those with the other catalysts in this work, indicating the generation of a high number of oxygen vacancies. The WOx/CeO2-SiO2 catalyst exhibited a high conversion of benzyl alcohol (>99%) and a high selectivity (100%) toward benzaldehyde compared to the other promoted catalysts (i.e., WOx/CeO2 and WOx/CeO2-ZrO2), which is attributed to the smaller particle size of the WOx and CeO2 and their high specific surface area, more significant number of acidic sites, and superior number of oxygen vacancies. The WOx/CeO2-SiO2 catalyst could be quickly recovered and utilized at least five times without suffering any appreciable activity loss.

Abstract: Extension professionals are expected to help disseminate agricultural technologies, information, knowledge and skills to farmers. In order to develop valuable and long-lasting extension services, it is essential to understand the methods of extension that farmers find most beneficial. This understanding helps adopt improved practices, overcome barriers, provide targeted interventions and continuously improve agricultural extension programs. Thus, assessing factors affecting farmers' choice of agricultural extension methods is essential for developing extension methods that comply with farmers' needs and socio-economic conditions. Therefore, we analyzed the factors affecting farmers' preferences in extension methods, using cross-sectional data collected from 300 households in two sample districts and 16 Kebelles in Ethiopia between September 2019 and March 2020. Four extension methods, including training, demonstration, office visits and phone calls were considered as outcome variables. We fitted a multivariate probit model to estimate the factors that influence farmers' choice of extension methods. The results of the study showed that the number of dependents in the household head, formal education and membership of Idir (an informal insurance program a community or group runs to meet emergencies) were negatively associated with farmers' choices to participate in different extension methods compared to no extension. On the other hand, the sex of the household head, farm experience, participation in non-farm activities, monetary loan access, owning a mobile phone, radio access and membership of cooperatives were found to have a statistically significant positive impact on farmers' choices of extension methods. Based on these findings, the government and the concerned stakeholders should take farmers' socio-economic and institutional traits into account when selecting and commissioning agricultural extension methods. This could help to develop contextually relevant extension strategies that are more likely to be chosen and appreciated by farmers. Furthermore, such strategies can aid policymakers in designing extension programs that cater to farmers' needs and concerns. In conclusion, farmers' socio-economic and institutional affiliation should be taken into consideration when selecting agricultural extension methods.