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Bottom Ashes from Municipal Solid Waste Incinerators and Waste to Energy plants represent an interesting source of secondary raw materials for many applications, like urban mining and inclusion in concrete, and road pavement. However, Bottom Ashes may contain potentially toxic elements, whose actual toxicity depends essentially on their oxidation state and mineralogical environment. For this reason, a representative sample of bottom ashes from Parma Waste to Energy plant has been selected to investigate the chemical speciation of Cr, Ni, Pb, Co, Zn and Cu by means of complementary techniques: Scanning Electron Microscopy with Energy Dispersive X-Ray Spectroscopy (SEM-EDS), micro X-Ray Fluorescence (µ-XRF) mapping and X-Ray Absorption Near Edge Structure (XANES) measurements by synchrotron radiation. This multi-technique approach allowed to obtain a general image of the mineralogical and chemical environment in which these elements are found. SEM-EDS analyses show the presence of Zn and Pb both in minerals and in glass matrix. Cr has been detected in the form of oxide and in spinel structure (chromite) whereas Co and Cu are found as alloy or metal inclusions. µ-XRF mapping reveals that Cu, Ni and Cr are generally associated to Na, K and Si suggesting their presence in glass matrix. XANES investigations exhibit that Cu has a variable oxidation state that suggesting its presence in the form of oxide, hydroxide, acetate and metal. Zn is mainly found as +II and in a number of different phases (including Zn-carbonates, in agreement with SEM-EDS data). Cr has been found only as +III, with XANES features resembling those of chromite, whereas as +VI was never identified. Ni and Co were found either as metal form and oxides. Pb spectra show a good match with oxides.

Abstract Coccolithophores, marine calcifying phytoplankton, are important primary producers impacting the global carbon cycle at different timescales. Their biomineral structures, the calcite containing coccoliths, are among the most elaborate hard parts of any organism. Understanding the morphogenesis of coccoliths is not only relevant in the context of coccolithophore eco-physiology but will also inform biomineralization and crystal design research more generally. The recent discovery of a silicon (Si) requirement for crystal shaping in some coccolithophores has opened up a new avenue of biomineralization research. In order to develop a mechanistic understanding of the role of Si, the presence and localization of this chemical element in coccoliths needs to be known. Here, we document for the first time the uneven Si distribution in Helicosphaera carteri coccoliths through three synchrotron-based techniques employing X-ray Fluorescence and Infrared Spectromicroscopy. The enrichment of Si in specific areas of the coccoliths point to a targeted role of this element in the coccolith formation. Our findings mark a key step in biomineralization research because it opens the door for a detailed mechanistic understanding of the role Si plays in shaping coccolith crystals.

Abstract Aggregation of volcanic ash is known to significantly impact sedimentation from volcanic plumes. The study of particle aggregates during tephra fallout is crucial to increase our understanding of both ash aggregation and sedimentation. In this work, we describe key features of ash aggregates and ash sedimentation associated with eleven Vulcanian explosions at Sakurajima Volcano (Japan) based on state-of-the-art sampling techniques. We identified five types of aggregates of both Particle Cluster (PC) and Accretionary Pellet (AP) categories. In particular, we found that PCs and the first and third type of APs can coexist within the same eruption in rainy conditions. We also found that the aerodynamic properties of aggregates (e.g., terminal velocity and density) depend on their type. In addition, grainsize analysis revealed that characteristics of the grainsize distributions (GSDs) of tephra samples correlate with the typology of the aggregates identified. In fact, bimodal GSDs correlate with the presence of cored clusters (PC3) and liquid pellets (AP3), while unimodal GSDs correlate either with the occurrence of ash clusters (PC1) or with the large particles (coarse ash) coated by fine ash (PC2).

DC-SIGN (CD209) and L-SIGN (CD209L) are two C-type lectin receptors (CLRs) that facilitate SARS-CoV-2 infections as viral co-receptors. SARS-CoV-2 manipulates both DC-SIGN and L-SIGN for enhanced infection, leading to interest in developing receptor antagonists. Despite their structural similarity (82% sequence identity), they function differently. DC-SIGN, found in dendritic cells, shapes the immune response by recognizing pathogen-associated carbohydrate patterns. In contrast, L-SIGN, expressed in airway epithelial endothelial cells, is not directly involved in immunity. COVID-19's primary threat is the hyperactivation of the immune system, potentially reinforced if DC-SIGN engages with exogenous ligands. Therefore, L-SIGN, co-localized with ACE2-expressing cells in the respiratory tract, is a more suitable target for anti-adhesion therapy. However, designing a selective ligand for L-SIGN is challenging due to the high sequence identity of the Carbohydrate Recognition Domains (CRDs) of the two lectins. We here present Man84, a mannose ring modified with a methylene guanidine triazole at position 2. It binds L-SIGN with a K of 12.7μM ± 1 μM (ITC) and is the first known L-SIGN selective ligand, showing 50-fold selectivity over DC-SIGN (SPR). The X-ray structure of the L-SIGN CRD/Man84 complex reveals the guanidinium group's role in achieving steric and electrostatic complementarity with L-SIGN. This allows us to trace the source of selectivity to a single amino acid difference between the two CRDs. NMR analysis confirms the binding mode in solution, highlighting Man84's conformational selection upon complex formation. Dimeric versions of Man84 achieve additional selectivity and avidity in the low nanomolar range. These compounds selectively inhibit L-SIGN dependent trans-infection by SARS-CoV-2 and Ebola virus. Man84 and its dimeric constructs display the best affinity and avidity reported to date for low-valency glycomimetics targeting CLRs. They are promising tools for competing with SARS-CoV-2 anchoring in the respiratory tract and have potential for other medical applications.D of 12.7μM ± 1 μM (ITC) and is the first known L-SIGN selective ligand, showing 50-fold selectivity over DC-SIGN (SPR). The X-ray structure of the L-SIGN CRD/Man84 complex reveals the guanidinium group's role in achieving steric and electrostatic complementarity with L-SIGN. This allows us to trace the source of selectivity to a single amino acid difference between the two CRDs. NMR analysis confirms the binding mode in solution, highlighting Man84's conformational selection upon complex formation. Dimeric versions of Man84 achieve additional selectivity and avidity in the low nanomolar range. These compounds selectively inhibit L-SIGN dependent trans-infection by SARS-CoV-2 and Ebola virus. Man84 and its dimeric constructs display the best affinity and avidity reported to date for low-valency glycomimetics targeting CLRs. They are promising tools for competing with SARS-CoV-2 anchoring in the respiratory tract and have potential for other medical applications., Competing Interests: The authors declare the following competing financial interest(s): S. P., C. D., M. T., F. F., and A. B. declare the filing of a patent covering the use of glycomimetic L-SIGN ligands as antagonist, anti-viral adhesion, and for targeting human L-SIGN-expressing cells., (This journal is © The Royal Society of Chemistry.)

Multivalent lectin-glycan interactions (MLGIs) are widespread and vital for biology, making them attractive therapeutic targets. Unfortunately, the structural and biophysical mechanisms of several key MLGIs remain poorly understood, limiting our ability to design spatially matched glycoconjugates as potential therapeutics against specific MLGIs. We have recently demonstrated that natural oligomannose-coated nanoparticles are powerful probes for MLGIs. They can provide not only quantitative affinity and binding thermodynamic data but also key structural information ( e.g , binding site orientation and mode) useful for designing glycoconjugate therapeutics against specific MLGIs. Despite success, how designing parameters ( e.g ., glycan type, density, and scaffold size) control their MLGI biophysical and antiviral properties remains to be elucidated. A synthetic pseudodimannose (psDiMan) ligand has been shown to selectively bind to a dendritic cell surface tetrameric lectin, DC-SIGN, over some other multimeric lectins sharing monovalent mannose specificity but having distinct cellular functions. Herein, we display psDiMan polyvalently onto gold nanoparticles (GNPs) of varying sizes ( e.g ., ∼5 and ∼13 nm, denoted as G5- and G13 psDiMan hereafter) to probe how the scaffold size and glycan display control their MLGI properties with DC-SIGN and the closely related lectin DC-SIGNR. We show that G5/13 psDiMan binds strongly to DC-SIGN, with sub-nM K s, with affinity being enhanced with increasing scaffold size, whereas they show apparently no or only weak binding to DC-SIGNR. Interestingly, there is a minimal, GNP-size-dependent, glycan density threshold for forming strong binding with DC-SIGN. By combining temperature-dependent affinity and Van't Hoff analyses, we have developed a new GNP fluorescence quenching assay for MLGI thermodynamics, revealing that DC-SIGN-G d s, with affinity being enhanced with increasing scaffold size, whereas they show apparently no or only weak binding to DC-SIGNR. Interestingly, there is a minimal, GNP-size-dependent, glycan density threshold for forming strong binding with DC-SIGN. By combining temperature-dependent affinity and Van't Hoff analyses, we have developed a new GNP fluorescence quenching assay for MLGI thermodynamics, revealing that DC-SIGN-G x -psDiMan binding is enthalpy-driven, with a standard binding Δ H 0 of ∼ -95 kJ mol -1 , which is ∼4-fold that of the monovalent binding and is comparable to that measured by isothermal titration calorimetry. We further reveal that the enhanced DC-SIGN affinity with G x -psDiMan with increasing GNP scaffold size is due to reduced binding entropy penalty and not due to enhanced favorable binding enthalpy. We further show that DC-SIGN binds tetravalently to a single G x -psDiMan, irrespective of the GNP size, whereas DC-SIGNR binding is dependent on GNP size, with no apparent binding with G5, and weak cross-linking with G13. Finally, we show that G x -psDiMans potently inhibit DC-SIGN-dependent augmentation of cellular entry of Ebola pseudoviruses with sub-nM EC 50 values, whereas they exhibit no significant (for G5) or weak (for G13) inhibition against DC-SIGNR-augmented viral entry, consistent to their MLGI properties with DC-SIGNR in solution. These results have established G x -psDiMan as a versatile new tool for probing MLGI affinity, selectivity, and thermodynamics, as well as GNP-glycan antiviral properties., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Bryophytes desiccate rapidly when relative humidity decreases. The capacity to withstand dehydration depends on several ecological and physiological factors. Volatile organic compounds (VOCs) may have a role in enhancing tolerance to desiccating bryophytes. However, the functions of VOCs in bryophytes have received little attention so far. We aimed to investigate the impact of a dehydration-rehydration treatment on primary carbon metabolism and volatile terpenes (VTs) in three bryophytes with contrasting ecological traits: Vessicularia dubyana, Porella platyphylla and Pleurochaete squarrosa. First, we confirmed the desiccation sensitivity gradient of the species. Under fully hydrated conditions, the photosynthetic rate (A) was inversely associated with stress tolerance, with a lower rate in more tolerant species. The partial recovery of A in P. platyphylla and P. squarrosa after rehydration confirmed the desiccation tolerance of these two species. On the other hand, A did not recover after rehydration in V. dubyana. Regarding VT, each species exhibited a distinct VT profile under optimum hydration, with the highest VT pool found in the more desiccation-sensitive species (V. dubyana). However, the observed species-specific VT pattern could be associated with the ecological habitat of each species. P. squarrosa, a moss of dry habitats, may synthesize mainly non-volatile secondary metabolites as stress-defensive compounds. On the other hand, V. dubyana, commonly found submerged, may need to invest photosynthetically assimilated carbon to synthesize a higher amount of VTs to cope with transient water stress occurrence. Further research on the functions of VTs in bryophytes is needed to deepen our understanding of their ecological significance., (© 2024 The Author(s). Physiologia Plantarum published by John Wiley & Sons Ltd on behalf of Scandinavian Plant Physiology Society.)

In this manuscript, a comprehensive study is presented on Fe-based electrocatalysts with mono, bi, and tri-metallic compositions, emphasizing the influence of processing-structure correlations on the electrocatalytic activity for the oxygen reduction reaction (ORR) in the alkaline medium. These electrocatalysts were synthesized through the mixing of transition metal phthalocyanines (TM-Pc) with conductive carbon support, followed by controlled thermal treatment at specific temperatures (600 °C and 900 °C). An extensive analysis was conducted, employing various techniques, including X-ray Absorption Spectroscopy (XAS), Transmission Electron Microscopy (TEM), and X-ray Diffraction (XRD), providing valuable insights into the structural characteristics of the synthesized nanoparticles. Importantly, an increase in the Fe-Pc weight percentage from 10% to 30% enhanced the ORR activity, although not proportionally. Furthermore, a comparative analysis between mono, bi, and tri-metallic samples subjected to different functionalization temperatures highlighted the superior electrocatalytic activity of electrocatalysts functionalized at 600 °C, particularly Fe 600 and Fe-Ni-Cu 600. These electrocatalysts featured E on values of 0.96 V vs. RHE and E 1/2 values of 0.9 V vs. RHE, with the added benefit of reduced anionic peroxide production. The potential of these Fe-based electrocatalysts to enhance ORR efficiency is underscored by this research, contributing to the development of more effective and sustainable electrocatalysts for energy conversion technologies.

In this contribution, a comprehensive study of nanostructured Bi 2 Te 3 (BT) thermoelectric material was performed using a combination of synchrotron radiation-based techniques such as XAFS, and XRF, along with some other laboratory techniques such as XRD, XPS, FESEM, and HRTEM. This study aims to track the change in morphological, compositional, average and local/electronic structures of Bi 2 Te 3 of two different phases; nanostructure (thin film) and nanopowders (NPs). Bi 2 Te 3 nanomaterial was fabricated as pellets using zone melting process in a one step process, while Bi 2 Te 3 thin film was deposited on sodalime glass substrate using a vacuum thermal evaporation technique. Synchrotron radiation-based Bi L III -edge fluorescence-mode X-ray absorption fine structure (XAFS) technique was performed to probe locally the electronic and fine structures of BT thin film around the Bi atom, while transmission-mode XAFS was used for BT NPs distributed in the PVP matrix. The structural features of the collected Bi L III XANES spectra of thin film and powder samples of BT are compared with the simulated XANES spectrum of BT calculated using FDMNES code at 5 Å cluster size. Combining different off-line structural characterization techniques (XRD, FESEM, XPS, and HRTEM), along with those of synchrotron radiation-based techniques (XAFS and XRF) is necessary for complementary and supported average crystal, chemical, morphological and local electronic structural analyses for unveiling the variation between Bi 2 Te 3 in the nanostructure/thin film and nanopowder morphology, and then connecting between the structural features and functions of BT in two different morphologies. After that, we measured the Seebeck coefficient and the power factor values for both the BT nanopowder and thin film., Competing Interests: The authors declare no competing interests or non-financial interests., (This journal is © The Royal Society of Chemistry.)

Plants are central to complex networks of multitrophic interactions. Increasing evidence suggests that beneficial microorganisms (BMs) may be used as plant biostimulants and pest biocontrol agents. We investigated whether tomato ( Solanum lycopersicum ) plants are thoroughly colonized by the endophytic and entomopathogenic fungus Beauveria bassiana , and how such colonization affects physiological parameters and the phenotype of plants grown under unstressed conditions or exposed to the pathogenic fungus Botrytis cinerea . As a positive control, a strain of the well-known biocontrol agent and growth inducer Trichoderma afroharzianum was used. As multitrophic interactions are often driven by (or have consequences on) volatile organic compounds (VOCs) released by plants constitutively or after induction by abiotic or biotic stresses, VOC emissions were also studied. Both B. bassiana and T. afroharzianum induced a significant but transient (one to two-day-long) reduction of stomatal conductance, which may indicate rapid activation of defensive (rejection) responses, but also limited photosynthesis. At later stages, our results demonstrated a successful and complete plant colonization by B. bassiana , which induced higher photosynthesis and lower respiration rates, improved growth of roots, stems, leaves, earlier flowering, higher number of fruits and yield in tomato plants. Beauveria bassiana also helped tomato plants fight B. cinerea , whose symptoms in leaves were almost entirely relieved with respect to control plants. Less VOCs were emitted when plants were colonized by B. bassiana or infected by B. cinerea , alone or in combination, suggesting no activation of VOC-dependent defensive mechanisms in response to both fungi., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest. The author(s) declared that they were an editorial board member of Frontiers, at the time of submission. This had no impact on the peer review process and the final decision., (Copyright © 2023 Russo, Winkler, Ghirardo, Monti, Pollastri, Ruocco, Schnitzler and Loreto.)

Although the characterization of the sticking and aggregation probability is essential to the description of volcanic ash dispersal and sedimentation, there is still no general model describing the sticking probability of volcanic ash. Experiments of dry particle-plate collisions in an enclosed box were carried out to characterize quantitatively the sticking efficiency of volcanic particles and silica beads in a limit case scenario where the mass of one of the particles is much greater than the others. Silica beads and volcanic particles from a Sakurajima Vulcanian eruption were filmed impacting a glass plate with a High-Speed Camera. The sticking probability is calculated from an equation depending on the particle diameter, impact velocity, and two experimental parameters (a, q). Particle size was found to dominantly control the sticking probability, with small particles more likely sticking on the glass plate than large particles. These experiments represent a significant step forward in the quantification of the sticking efficiency of fine volcanic ash (< 63 μm)., (© 2023. The Author(s).)

This research investigates the high-pressure behavior of the Ca(Ti 0.95 Ge 0.05 )O 3 perovskite, a candidate of the locked-tilt perovskite family (orthorhombic compounds characterized by the absence of changes in the octahedral tilt and volume reduction under pressure controlled solely by isotropic compression). The study combines experimental high-pressure synchrotron diffraction data with density functional theory (DFT) calculations, complemented by the X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS), to understand the structural evolution of the perovskite under pressure. The results show that CTG undergoes nearly isotropic compression with the same compressibility along all three unit-cell axes (i.e., K a 0 = K b 0 = K c 0 , giving a normalized cell distortion factor with pressure d norm ( P ) = 1). However, a modest increase in octahedral tilting with pressure is revealed by DFT calculations, qualifying CTG as a new type of GdFeO 3 -type perovskite that exhibits both isotropic compression and nonlocked tilting. This finding complements two existing types: perovskites with anisotropic compression and tilting changes and those with isotropic compression and locked tilting. The multimethod approach provides valuable insights into the structural evolution of locked-tilt perovskites under high pressure and establishes a protocol for the efficient study of complex high-pressure systems. The results have implications for the design of new functional materials with desirable properties.

Pyrolysis in an inert atmosphere is a widely applied route to convert tannery wastes into reusable materials. In the present study, the Cr(III) conversion into the toxic hexavalent form in the pyrolyzed tannery waste referred to as KEU was investigated. Ageing experiments and leaching tests demonstrated that the Cr(III)-Cr(VI) inter-conversion occurs in the presence of air at ambient temperature, enhanced by wet environmental conditions. Microstructural analysis revealed that the Cr-primary mineral assemblage formed during pyrolysis (Cr-bearing srebrodolskite and Cr-magnetite spinel) destabilized upon spray water cooling in the last stage of the process. In the evolution from the higher to the lower temperature mineralogy, Cr is incorporated into newly formed CrOOH flakes which likely react in air forming extractable Cr(VI) species. This property transforms KEU from an inert waste to a hazardous material when exposed to ordinary ambient conditions., (© 2023. Springer Nature Limited.)

Layered double hydroxides (LDHs), whose formation is strongly related to OH - concentration, have attracted significant interest in various fields. However, the effect of the real-time change of OH - concentration on LDHs' formation has not been fully explored due to the unsuitability of the existing synthesis methods for in situ characterization. Here, the deliberately designed combination of NH 3 gas diffusion and in situ pH measurement provides a solution to the above problem. The obtained results revealed the formation mechanism and also guided us to synthesize a library of LDHs with the desired attributes in water at room temperature without using any additives. After evaluating their oxygen evolution reaction performance, we found that FeNi-LDH with a Fe/Ni ratio of 25/75 exhibits one of the best performances so far reported., (© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

The local structure of the active sites is one of the key aspects of establishing the nature of the catalytic activity of the systems. In this work, a detailed structural investigation of the Rh-CeO 2 catalysts prepared by the co-precipitation method was carried out. The application of a variety of physicochemical methods such as XRD, Raman spectroscopy, XPS, TEM, TPR-H 2 , and XAS revealed the presence of highly dispersed Rh 3+ species in the catalysts: Rh 3+ single ions and RhO x clusters. The substitution of Ce 4+ ions by Rh 3+ species, which provided a strong distortion of the CeO 2 lattice, is shown. XAS data ensured the refinement of the Rh local structure. It was shown that single Rh 3+ sites located next to each other can merge the formation of RhO x clusters with Rh local environment close to the one in Rh 2 O 3 and CeRh 2 O 5 oxides. The distortion of the CeO 2 lattice around single and cluster rhodium species had a beneficial effect on the catalytic activity of the samples in low-temperature CO oxidation (LTO-CO). TEM, XAS, and in situ XRD data allowed establishing the structural transformations of the catalysts under Red-Ox treatments. The reduction treatment led to Rhn metallic cluster formation localized on defects of the reduced CeO 2- δ . The reduced sample demonstrated efficient CO conversion at 0 °C. However, this system was not stable: its contact with air led to ceria reoxidation and partial reoxidation of Rh to highly dispersed Rh 3+ species at room temperature, while heating in an oxidizing atmosphere resulted in the complete reoxidation of metallic rhodium species. The results of the work shed light on the structural aspects of the reversibility of the Rh-CeO 2 catalysts based on the highly dispersed Rh 3+ species under treatment in the reaction conditions.

Isoprene-emitting plants are better protected against thermal and oxidative stresses, which is a desirable trait in a climate-changing (drier and warmer) world. Here we compared the ecophysiological performances of transgenic isoprene-emitting and wild-type non-emitting tobacco plants during water stress and after re-watering in actual environmental conditions (400 ppm of CO 2 and 28 °C of average daily temperature) and in a future climate scenario (600 ppm of CO 2 and 32 °C of average daily temperature). Furthermore, we intended to complement the present knowledge on the mechanisms involved in isoprene-induced resistance to water deficit stress by examining the proteome of transgenic isoprene-emitting and wild-type non-emitting tobacco plants during water stress and after re-watering in actual climate. Isoprene emitters maintained higher photosynthesis and electron transport rates under moderate stress in future climate conditions. However, physiological resistance to water stress in the isoprene-emitting plants was not as marked as expected in actual climate conditions, perhaps because the stress developed rapidly. In actual climate, isoprene emission capacity affected the tobacco proteomic profile, in particular by upregulating proteins associated with stress protection. Our results strengthen the hypothesis that isoprene biosynthesis is related to metabolic changes at the gene and protein levels involved in the activation of general stress defensive mechanisms of plants.

The description of the formation of ash aggregates is crucial to our understanding of tephra dispersal and, therefore, to the forecasting of volcanic ash concentration in the atmosphere. Regardless of the importance of electrostatic processes, particle and aggregate charge is of complex determination both in the field and in the laboratory. We have measured the bulk charge carried by single aggregates at Sakurajima volcano (Japan) by inverting the sedimentation trajectory across two high-voltage copper plates filmed using a high-speed camera. Some aggregates were filmed during their breakage caused by the external electric field, which revealed the presence of inner highly charged multipoles with bulk charge up to one order of magnitude larger than the bulk aggregate. This electrical multipolar nature reveals the key role played by multipoles in aggregate formation and the shielding effect of aggregation on particle charge.

Background: DNA ligases are crucial for DNA repair and cell replication since they catalyze the final steps in which DNA breaks are joined. DNA Ligase III (LIG3) exerts a pivotal role in Alternative-Non-Homologous End Joining Repair (Alt-NHEJ), an error-prone DNA repair pathway often up-regulated in genomically unstable cancer, such as Multiple Myeloma (MM). Based on the three-dimensional (3D) LIG3 structure, we performed a computational screening to identify LIG3-targeting natural compounds as potential candidates to counteract Alt-NHEJ activity in MM., Methods: Virtual screening was conducted by interrogating the Phenol Explorer database. Validation of binding to LIG3 recombinant protein was performed by Saturation Transfer Difference (STD)-nuclear magnetic resonance (NMR) experiments. Cell viability was analyzed by Cell Titer-Glo assay; apoptosis was evaluated by flow cytometric analysis following Annexin V-7AAD staining. Alt-NHEJ repair modulation was evaluated using plasmid re-joining assay and Cytoscan HD. DNA Damage Response protein levels were analyzed by Western blot of whole and fractionated protein extracts and immunofluorescence analysis. The mitochondrial DNA (mtDNA) copy number was determined by qPCR. In vivo activity was evaluated in NOD-SCID mice subcutaneously engrafted with MM cells., Results: Here, we provide evidence that a natural flavonoid Rhamnetin (RHM), selected by a computational approach, counteracts LIG3 activity and killed Alt-NHEJ-dependent MM cells. Indeed, Nuclear Magnetic Resonance (NMR) showed binding of RHM to LIG3 protein and functional experiments revealed that RHM interferes with LIG3-driven nuclear and mitochondrial DNA repair, leading to significant anti-MM activity in vitro and in vivo., Conclusion: Taken together, our findings provide proof of concept that RHM targets LIG3 addiction in MM and may represent therefore a novel promising anti-tumor natural agent to be investigated in an early clinical setting., (© 2022. The Author(s).)

Laser cladding with H13 steel powders was performed and the related material transformations were studied for the particles emitted during this process. Fractions of various sizes of the aerosol particles formed during the laser cladding were collected on a cascade impactor, while the electromobility and the aerodynamic size of the particles were measured using a scanning mobility particle spectrometer and an aerodynamic particle sizer, respectively. The aerosol particles deposited onto the impactor plates were analyzed using scanning electron microscopy−energy-dispersive X-ray spectroscopy, as well as total-reflection X-ray fluorescence and X-ray absorption near-edge structure spectroscopy. Both the concentration and mean oxidation state of the major components were correlated with the aerosol particle size. The ultrafine aerosol particles (with a diameter less than about 100 nm) were predominantly oxidized and formed as the result of an evaporation−oxidation−condensation process sequence. The larger particles (>200 nm in geometric diameter) were primarily the residues of the original metal powder and exhibited a composition change as compared to the as-received metal powder. Correlations between the changes in the concentration ratio of the components were detected and explained., Competing Interests: The authors declare no conflict of interest. The funders had no role in the design of the study; in the collection, analyses, or interpretation of data; in the writing of the manuscript; or in the decision to publish the results.

X-ray absorption spectroscopy (XAS) has been employed to carry out structural characterization of the local environment around mercury after the dissolution of the HgCl 2 molecule. A combined EXAFS (extended X-ray absorption fine structure) and XANES (X-ray absorption near edge structure) data analysis has been performed on the Hg L 3 -edge absorption spectra recorded on 0.1 M HgCl 2 solutions in water, methanol (MeOH), acetone and acetonitrile. The Hg-Cl distance determined by EXAFS (2.29(2)-2.31(2) Å) is always comparable to that found in the HgCl 2 crystal (2.31(2) Å), demonstrating that the HgCl 2 molecule dissolves in these solvents without dissociating. A small sensitivity of EXAFS to the solvent molecules interacting with HgCl 2 has been detected and indicates a high degree of configurational disorder associated with this contribution. XANES data analysis, which is less affected by the disorder, was therefore carried out for the first time on these systems to shed light into the still elusive structural arrangement of the solvent molecules around HgCl 2 . The obtained results show that, in aqueous and MeOH solutions, the XANES data are compatible with three solvent molecules arranged around the HgCl 2 unit to form a trigonal bipyramidal structure. The determination of the three-body Cl-Hg-Cl distribution shows a certain degree of uncertainty around the average 180° bond angle value, suggesting that the HgCl 2 molecule probably vibrates in the solution around a linear configuration.

Isoprene, a major biogenic volatile hydrocarbon of climate-relevance, indisputably mitigates abiotic stresses in emitting plants. However functional relevance of constitutive isoprene emission in unstressed plants remains contested. Isoprene and cytokinins (CKs) are synthesized from a common substrate and pathway in chloroplasts. It was postulated that isoprene emission may affect CK-metabolism. Using transgenic isoprene-emitting (IE) Arabidopsis and isoprene nonemitting (NE) RNA-interference grey poplars (paired with respective NE and IE genotypes), the life of individual IE and NE leaves from emergence to abscission was followed under stress-free conditions. We monitored plant growth rate, aboveground developmental phenotype, modelled leaf photosynthetic energy status, quantified the abundance of leaf CKs, analysed Arabidopsis and poplar leaf transcriptomes by RNA-sequencing in presence and absence of isoprene during leaf senescence. Isoprene emission by unstressed leaves enhanced the abundance of CKs (isopentenyl adenine and its precursor) by > 200%, significantly upregulated genes coding for CK-synthesis, CK-signalling and CK-degradation, hastened plant development, increased chloroplast metabolic rate, altered photosynthetic energy status, induced early leaf senescence in both Arabidopsis and poplar. IE leaves senesced sooner even in decapitated poplars where source-sink relationships and hormone homeostasis were perturbed. Constitutive isoprene emission significantly accelerates CK-led leaf and organismal development and induces early senescence independent of growth constraints. Isoprene emission provides an early-riser evolutionary advantage and shortens lifecycle duration to assist rapid diversification in unstressed emitters., (© 2021 The Authors. New Phytologist © 2021 New Phytologist Foundation.)

Synchrotron radiation-based techniques [X-ray absorption near-edge structure (XANES) and X-ray fluorescence (XRF)] combined with inductively coupled plasma-mass spectrometry (ICP-MS) were used for the assessment of heavy metals concentrations as well as lead (Pb) and nickel (Ni) speciation in airborne particulate matter (PM 10 ) over two residential sites in Greater Cairo. Nineteen 24 h high-volume samples collected at Giza (G) Square and Helwan (H) University (Egypt) were selected for this study. Mean concentrations of heavy metals in PM 10 at both sites were found to have the same descending order of Pb > Cu > Ni > Cd > Co > As, of which concentrations of Pb, Cu, Ni and Cd in H samples were higher than those in G samples. For Pb, synchrotron-based XRF results were in good agreement with concentrations obtained by ICP-MS. The XANES spectra of PM 10 at the Pb L 2 -edge and Ni K-edge were compared with those of Pb and Ni in model standard compounds to provide information on the potential oxidation states as well as the chemical forms of those elements. The data show that Pb has similar chemical environments in both series G and H with the predominance of Pb 2+ oxidation state. Nickel was found as Ni(OH) 2 , NiO and Ni metal in the analyzed samples. However, the content of Ni in the background filter shows a very strong interference with that of the collected PM 10 . Carcinogenic and non-carcinogenic risks resulting from the inhalation of the studied heavy metals were assessed for children and adult residents and were found below the safe limits, at both sites., (open access.)

Catalyst design is crucial for improving catalytic activity and product selectivity. In a bifunctional Ni/ZSM-5 zeolite type catalyst, catalytic properties are usually tuned via varying Al and Ni contents. While changes in acid properties associated with Al sites are usually closely investigated, Ni phases, however, receive inadequate attention. Herein, we present a systematic structural study of Ni in the Ni/ZSM-5 materials by using Ni K-edge XANES and EXAFS analyses, complemented by XRD and TEM, to resolve the changes in the local environment of Ni species induced by the different Al contents of the parent ZSM-5 prepared by a "green", template free technique. Ni species in Ni/ZSM-5 exist as NiO crystals (3-50 nm) and as charge compensating Ni 2+ cations. The Ni K-edge XANES and EXAFS results enabled the quantification of Ni-containing species. At a low Al to Si ratio ( n Al / n Si ≤ 0.04), the NiO nanoparticles predominate in the samples and account for over 65% of Ni phases. However, NiO is outnumbered by Ni 2+ cations attached to the zeolite framework in ZSM-5 with a high Al to Si ratio ( n Al / n Si = 0.05) due to a higher number of framework negative charges imparted by Al. The obtained results show that the number of highly reducible and active NiO crystals is strongly correlated with the framework Al sites present in ZSM-5 zeolites, which depend greatly on the synthesis conditions. Therefore, this kind of study is beneficial for any further investigation of the catalytic activities of Ni/ZSM-5 and other metal-modified bifunctional catalysts., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Synthesized small molecules are useful as tools to investigate hormonal signaling involved in plant growth and development. They are also important as agrochemicals to promote beneficial properties of crops in the field. We describe here the synthesis and mode of action of a novel growth-promoting chemical, A1. A1 stimulates enhanced growth in both shoot and root tissues of plants, acting by increasing both dry and fresh weight. This suggests that A1 not only promotes uptake of water but also increases production of cellular material. A1 treatment of Arabidopsis leads to the degradation of DELLA growth-inhibitory proteins suggesting that A1-mediated growth promotion is dependent upon this mechanism. We performed genetic analysis to confirm this and further dissect the mechanism of A1 action upon growth in Arabidopsis . A quintuple della mutant was insensitive to A1, confirming that the mode of action was indeed via a DELLA-dependent mechanism. The ga1-5 gibberellin synthesis mutant was similarly insensitive, suggesting that to promote growth in Arabidopsis A1 requires the presence of endogenous gibberellins. This was further suggested by the observation that double mutants of GID1 gibberellin receptor genes were insensitive to A1. Taken together, our data suggest that A1 acts to enhance sensitivity to endogenous gibberellins thus leading to observed enhanced growth via DELLA degradation. A1 and related compounds will be useful to identify novel signaling components involved in plant growth and development, and as agrochemicals suitable for a wide range of crop species., Competing Interests: The authors declare no competing interests., (© 2022 The Authors. Plant Direct published by American Society of Plant Biologists and the Society for Experimental Biology and John Wiley & Sons Ltd.)

The C-type lectin receptors DC-SIGN and L-SIGN bind to glycans on the SARS-CoV-2 spike glycoprotein and promote trans-infection of ACE2-expressing cells. We tested C2 triazole-modified mono- and pseudo-di-mannosides as inhibitors of DC/L-SIGN binding to a model mannosylated protein (Man-BSA) and to SARS-CoV2 spike, finding that they inhibit the interaction of both lectins with the spike glycoprotein in a Surface Plasmon Resonance (SPR) assay and are more potent than mannose by up to 36-fold (DC-SIGN) and 10-fold (L-SIGN). The molecules described here are the first known glycomimetic ligands of L-SIGN.

Arundo donax has been recognized as a promising crop for biomass production on marginal lands due to its superior productivity and stress tolerance. However, salt stress negatively impacts A. donax growth and photosynthesis. In this study, we tested whether the tolerance of A. donax to salinity stress can be enhanced by the addition of 5-aminolevulinic acid (ALA), a known promoter of plant growth and abiotic stress tolerance. Our results indicated that root exposure to ALA increased the ALA levels in leaves along the A. donax plant profile. ALA enhanced Na + accumulation in the roots of salt-stressed plants and, at the same time, lowered Na + concentration in leaves, while a reduced callose amount was found in the root tissue. ALA also improved the photosynthetic performance of salt-stressed apical leaves by stimulating stomatal opening and preventing an increase in the ratio between abscisic acid (ABA) and indol-3-acetic acid (IAA), without affecting leaf methanol emission and plant growth. Supply of ALA to the roots reduced isoprene fluxes from leaves of non-stressed plants, while it sustained isoprene fluxes along the profile of salt-stressed A. donax . Thus, ALA likely interacted with the methylerythritol 4-phosphate (MEP) pathway and modulate the synthesis of either ABA or isoprene under stressful conditions. Overall, our study highlights the effectiveness of ALA supply through soil fertirrigation in preserving the young apical developing leaves from the detrimental effects of salt stress, thus helping of A. donax to cope with salinity and favoring the recovery of the whole plant once the stress is removed.

Isoprene is a small lipophilic molecule synthesized in plastids and abundantly released into the atmosphere. Isoprene-emitting plants are better protected against abiotic stresses, but the mechanism of action of isoprene is still under debate. In this study, we compared the physiological responses and proteomic profiles of Arabidopsis which express the isoprene synthase (ISPS) gene and emit isoprene with those of non-emitting plants under both drought-stress (DS) and well-watered (WW) conditions. We aimed to investigate whether isoprene-emitting plants displayed a different proteomic profile that is consistent with the metabolic changes already reported. Only ISPS DS plants were able to maintain the same photosynthesis and fresh weight of WW plants. LC-MS/MS-based proteomic analysis revealed changes in protein abundance that were dependent on the capacity for emitting isoprene in addition to those caused by the DS. The majority of the proteins changed in response to the interaction between DS and isoprene emission. These include proteins that are associated with the activation of secondary metabolisms leading to ABA, trehalose, and proline accumulations. Overall, our proteomic data suggest that isoprene exerts its protective mechanism at different levels: under drought stress, isoprene affects the abundance of chloroplast proteins, confirming a strong direct or indirect antioxidant action and also modulates signaling and hormone pathways, especially those controlling ABA synthesis. Unexpectedly, isoprene also alters membrane trafficking.

Wild roses store and emit a large array of fragrant monoterpenes from their petals. Maximisation of fragrance coincides with floral maturation in many angiosperms, which enhances pollination efficiency, reduces floral predation, and improves plant fitness. We hypothesized that petal monoterpenes serve additional lifelong functions such as limiting metabolic damage from reactive oxygen species (ROS), and altering isoprenoid hormonal abundance to increase floral lifespan. Petal monoterpenes were quantified at three floral life-stages (unopened bud, open mature, and senescent) in 57 rose species and 16 subspecies originating from Asia, America, and Europe, and relationships among monoterpene richness, petal colour, ROS, hormones, and floral lifespan were analysed within a phylogenetic context. Three distinct types of petal monoterpene profiles, revealing significant developmental and functional differences, were identified: Type A, species where monoterpene abundance peaked in open mature flowers depleting thereafter; Type B, where monoterpenes peaked in senescing flowers increasing from bud stage, and a rare Type C (8 species) where monoterpenes depleted from bud stage to senescence. Cyclic monoterpenes peaked during early floral development, whereas acyclic monoterpenes (dominated by geraniol and its derivatives, often 100-fold more abundant than other monoterpenes) peaked during floral maturation in Type A and B roses. Early-diverging roses were geraniol-poor (often Type C) and white-petalled. Lifetime changes in hydrogen peroxide (H 2 O 2 ) revealed a significant negative regression with the levels of petal geraniol at all floral life-stages. Geraniol-poor Type C roses also showed higher cytokinins (in buds) and abscisic acid (in mature petals), and significantly shorter floral lifespan compared with geraniol-rich Type A and B roses. We conclude that geraniol enrichment, intensification of petal colour, and lower potential for H 2 O 2 -related oxidative damage characterise and likely contribute to longer floral lifespan in monoterpene-rich wild roses., (© 2020. The Author(s).)

The most common MXene composition Ti 3 C 2 T x (T = F, O) shows outstanding stability as anode for sodium ion batteries (100% of capacity retention after 530 cycles with charge efficiency >99.7%). However, the reversibility of the intercalation/deintercalation process is strongly affected by the synthesis parameters determining, in turn, significant differences in the material structure. This study proposes a new approach to identify the crystal features influencing the performances, using a structural model built with a multitechnique approach that allows exploring the short-range order of the lamella. The model is then used to determine the long-range order by inserting defective elements into the structure. With this strategy it is possible to fit the MXene diffraction patterns, obtain the structural parameters including the stoichiometric composition of the terminations (neutron data), and quantify the structural disorder which can be used to discriminate the phases with the best electrochemical properties.

After an episode of heat stress plants retain a cellular "memory" of this event, a phenomenon known as thermomemory. This mechanism allows plants to better cope against a subsequent heat event. Thermomemory occurs through the persistence of heat shock proteins (HSPs) synthesized after the first "priming" event. Maintenance of this thermomemory comes at the cost to growth though, therefore it is vital that the memory is reset when no longer required. Recently, it has been reported that autophagy is important for resetting the thermomemory. It has also been shown recently that in response to heat, Arabidopsis displays an increase in chloroplast free calcium concentration which is partially dependent on calcium sensing receptor (CAS) protein. It is not known what the purpose of this heat-activated calcium signal is. Therefore, we compared downstream responses to heat in wild type (WT) and cas mutants, as the latter produce a reduced chloroplast calcium signal to heat. We found that after thermopriming the cas mutants displayed a greater biomass and a reduced level of the small heat shock protein HSP 17.6 degradation compared to WT. cas mutants did not show an increase in free amino acid levels after thermopriming, suggesting reduced autophagy. These results suggest that heat-induced chloroplast calcium elevation is a positive signal for resetting of the thermomemory., (Crown Copyright © 2021. Published by Elsevier GmbH. All rights reserved.)

A thorough understanding of the implications of chronic low-dose exposure to engineered nanomaterials through the food chain is lacking. The present study aimed to characterize such a response in Cucurbita pepo L. (zucchini) upon exposure to a potential nanoscale fertilizer: copper oxide (CuO) nanoparticles. Zucchini was grown in soil amended with nano-CuO, bulk CuO (100 mg Kg -1 ), and CuSO 4 (320 mg Kg -1 ) from germination to flowering (60 days). Nano-CuO treatment had no impact on plant morphology or growth nor pollen formation and viability. The uptake of Cu was comparable in the plant tissues under all treatments. RNA-seq analyses on vegetative and reproductive tissues highlighted common and nanoscale-specific components of the response. Mitochondrial and chloroplast functions were uniquely modulated in response to nanomaterial exposure as compared with conventional bulk and salt forms. X-ray absorption spectroscopy showed that the Cu local structure changed upon nano-CuO internalization, suggesting potential nanoparticle biotransformation within the plant tissues. These findings demonstrate the potential positive physiological, cellular, and molecular response related to nano-CuO application as a plant fertilizer, highlighting the differential mechanisms involved in the exposure to Cu in nanoscale, bulk, or salt forms. Nano-CuO uniquely stimulates plant response in a way that can minimize agrochemical inputs to the environment and therefore could be an important strategy in nanoenabled agriculture.

Isoprene (C 5 H 8 ) is a small lipophilic, volatile organic compound (VOC), synthesized in chloroplasts of plants through the photosynthesis-dependent 2-C-methyl-D-erythritol 4-phosphate (MEP) pathway. Isoprene-emitting plants are better protected against thermal and oxidative stresses but only about 20% of the terrestrial plants are able to synthesize isoprene. Many studies have been performed to understand the still elusive isoprene protective mechanism. Isoprene reacts with, and quenches, many harmful reactive oxygen species (ROS) like singlet oxygen ( 1 O 2 ). A role for isoprene as antioxidant, made possible by its reduced state and conjugated double bonds, has been often suggested, and sometimes demonstrated. However, as isoprene is present at very low concentrations compared to other molecules, its antioxidant role is still controversial. Here we review updated evidences on the function(s) of isoprene, and outline contrasting indications on whether isoprene is an antioxidant directly scavenging ROS, or a membrane strengthener, or a modulator of genomic, proteomic and metabolomic profiles (perhaps as a secondary effect of ROS removal) eventually leading to priming of antioxidant plant defenses, or a signal of stress for neighbor plants alike other VOCs, or a hormone-like molecule, controlling the metabolic flux of other hormones made by the MEP pathway, or acting itself as a growth and development hormone.

Among the various methods employed in the synthesis of nanostructures, those involving high operating temperature and sharp thermal gradients often lead to the establishment of new exotic properties. Herein, we report on the formation of Cu-Ni metallic alloy nanoparticles with greatly enhanced stiffness achieved through direct-current transferred arc-thermal plasma assisted vapour-phase condensation. High pressure synchrotron X-ray powder diffraction (XRPD) at ambient temperature as well as XRPD in the temperature range 180 to 920 K, show that the thermal arc-plasma route resulted in alloy nanoparticles with much enhanced bulk modulus compared to their bulk counterparts. Such a behaviour may find an explanation in the sudden quenching assisted by the retention of a large amount of local strain due to alloying, combined with the perfect miscibility of the elemental components during the thermal plasma synthesis process.

A multi-instrumental approach combining highly sensitive Synchrotron Radiation-based techniques was used to provide information on the real composition of a dry black ink powder found in a bronze inkwell of the first century AD. The presence of Pb, Cu and Fe in the powder, revealed by XRF and ICP-OES data, leads to raise several hypotheses on their origin. The inkpot and its lid were also investigated by Hand-Held XRF, revealing a bronze alloy (Cu-Sn) with a certain amount of Fe and Pb. The lid was found to be particularly enriched in lead. XRPD, XAS and FTIR measurements showed a substantial presence of silicates and common clay minerals in the ink along with cerussite and malachite, Pb and Cu bearing-carbonates, respectively. These evidences support the hypothesis of an important contamination of the ink sample by the burial environment (soil) and the presence of degradation products of the bronze inkpot. The combined use of IR, Raman, and GC-MS evidenced that the black ink is mainly composed of amorphous carbon deriving from the combustion of organic material mixed with a natural binding agent, Arabic gum.

Cement-based stabilization is a widespread technique used for the treatment of contaminated soils. Despite its established application, the mechanisms involved in the stabilization of contaminants are not fully understood yet. This work aims to elucidate the fate of a real Pb contaminated soil amended with different binders, by studying Pb local environment prior and after the stabilization process. The study of a complex historically contaminated soil was coupled with the investigation of simplified artificial systems, developed to model Pb local structure in the unknown newly formed hybrid systems of soil and binders. The use of synchrotron-based element-specific X-ray absorption spectroscopy (XAS) permitted to probe the actual transformation of Pb environment in the real contaminated soil after the stabilization process. With the support of the model systems, we can propose as the main mechanism involved in Pb retention in sulfated soil treated with cement, the incorporation and/or adsorption of Pb on calcium silicate hydrates and ettringite., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Ru/Al 2 O 3 is a highly stable, but less active catalyst for methanation reactions. Herein we report an effective approach to significantly improve its performance in the methanation of CO 2 /H 2 mixtures. Highly active and stable Ru/γ-Al 2 O 3 catalysts were prepared by high-temperature treatment in the reductive reaction gas. Operando/in situ spectroscopy and STEM imaging reveals that the strongly improved activity, by factors of 5 and 14 for CO and CO 2 methanation, is accompanied by a flattening of the Ru nanoparticles and the formation of highly basic hydroxylated alumina sites. We propose a modification of the metal-support interactions (MSIs) as the origin of the increased activity, caused by modification of the Al 2 O 3 surface in the reductive atmosphere and an increased thermal mobility of the Ru nanoparticles, allowing their transfer to modified surface sites., (© 2020 The Authors. Published by Wiley-VCH GmbH.)

High temperature sintering (1200-1400 °C) has been performed on ZnO ceramics. An X-ray Absorption Fine Structure (XAFS) study shows that high sintering temperature introduces a constant amount of V O and V Zn defects without any significant effect on the crystal or electronic structure of Wurtzite ZnO. The combined effects of grain boundaries and voids are considered responsible for the apparent colossal dielectric constant ( ε ') > 10 4 at low frequency (∼10 2 Hz) for all the sintered ZnO ceramics. The superior contact among grains of the ZnO-1200 sample enhances both the interfacial and orientational polarization of the Zn 2+ -V O dipoles, which results in the increase of low and high frequency dielectric constants ( ε ') and the corresponding dielectric loss (tan  δ ) also increases. On the other hand, high temperature sintering of ZnO at 1300 °C and 1400 °C introduces voids at the expense of reduced grain and grain boundary contact areas, thus affecting both the interfacial and orientational polarization with corresponding reduction of dielectric constant ( ε ') and dielectric loss. Orientational polarizations due to Zn 2+ -V O dipoles are suggested to remain fixed and it is the microstructure which controls the dielectric properties of high temperature sintered ZnO ceramics., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Arundo donax L. is an invasive grass species with high tolerance to a wide range of environmental stresses. The response of potted A. donax plants to soil stress characterized by prolonged exposure (43 days) to salinity (+Na), to high concentration of phosphorus (+P), and to the combination of high Na and P (+NaP) followed by 14 days of recovery under optimal nutrient solution, was investigated along the entire time-course of the experiment. After an exposure of 43 days, salinity induced a progressive decline in stomatal conductance that hampered A. donax growth through diffusional limitations to photosynthesis and, when combined with high P, reduced the electron transport rate. Isoprene emission from A. donax leaves was stimulated as Na + concentration raised in leaves. Prolonged growth in P-enriched substrate did not significantly affect A. donax performance, but decreased isoprene emission from leaves. Prolonged exposure of A. donax to + NaP increased the leaf level of H 2 O 2 , stimulated the production of carbohydrates, phenylpropanoids, zeaxanthin and increased the de-epoxidation state of the xanthophylls. This might have resulted in a higher stress tolerance that allowed a fast and full recovery following stress relief. Moreover, the high amount of ABA-glucose ester accumulated in leaves of A. donax exposed to + NaP might have favored stomata re-opening further sustaining the observed prompt recovery of photosynthesis. Therefore, prolonged exposure to high P exacerbated the negative effects of salt stress in A. donax plants photosynthetic performances, but enhanced activation of physiological mechanisms that allowed a prompt and full recovery after stress., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Masson SAS. All rights reserved.)

Enormous efforts have been initiated in the production of biobased fuels and value-added chemicals via biorefinery owing to the scarcity of fossil resources and huge environmental synchronization. Herein, non-noble metal-based metal/mixed metal oxide supported on carbon employing a metal-organic framework as a sacrificial template is demonstrated for the first time in the selective hydrodeoxygenation (HDO) of biomass-derived furfural (FFR) to 2-methyl furan (MF). The aforementioned catalyst (referred to as Cu/CuFe 2 O 4 @C- A ) exhibited extraordinary catalytic proficiency (100% selectivity toward MF) compared with the conventional Cu/CuFe 2 O 4 @C- B catalyst which was prepared by the wet impregnation method. High-resolution transmission electron microscopy and synchrotron X-ray diffraction studies evidenced the existence of both metal (Cu) and mixed metal oxide (CuFe 2 O 4 ) phases, in which the metal could help in hydrogenation to alcohol and metal oxide could assist in the hydroxyl group removal step during HDO reaction. The stabilization of encapsulated metal/metal oxide nanoparticles in the carbon matrix, modulation of the electronic structure, and regulation of geometric effects in the Cu/CuFe 2 O 4 @C- A are thought to play an important role in its excellent catalytic performance, confirmed by X-ray photoelectron spectroscopy and X-ray absorption spectroscopy investigations. Furthermore, the structure and activity interconnection was confirmed by in situ attenuated total reflection-IR studies, which manifested the strong interfacial interaction between FFR and the Cu/CuFe 2 O 4 @C- A catalyst. This finding was further supported by NH 3 temperature-programmed desorption analysis, which suggested that the presence of more Lewis/weak acidic sites in this catalyst was beneficial for the hydrogenolysis step in HDO reaction. Additionally, H 2 temperature-programmed reduction studies revealed that the adsorption of H 2 was stronger on the Cu/CuFe 2 O 4 @C- A than that over the conventional Cu/CuFe 2 O 4 @C- B catalyst; thus, the former catalyst promoted activation of H 2 . A detailed kinetic analysis which demonstrated the lower activation energy barrier along with dual active sites attributed for the activation of the two separate reactions in the HDO process on the Cu/CuFe 2 O 4 @C- A catalyst. This work has great implication in developing a highly stable catalyst for the selective upgradation of biomass without deactivation of metal sites in extended catalytic cycles and opens the door of opportunity for developing a sustainably viable catalyst in biomass refinery industries.

The potential of Arundo donax to grow in degraded soils, characterized by excess of salinity (Na+), and phosphorus deficiency (-P) or excess (+P) also coupled with salinity (+NaP), was investigated by combining in vivo plant phenotyping, quantification of metabolites and ultrastructural imaging of leaves with a transcriptome-wide screening. Photosynthesis and growth were impaired by + Na, -P and + NaP. While + Na caused stomatal closure, enhanced biosynthesis of carotenoids, sucrose and isoprene and impaired anatomy of cell walls, +P negatively affected starch production and isoprene emission, and damaged chloroplasts. Finally, +NaP largely inhibited photosynthesis due to stomatal limitations, increased sugar content, induced/repressed a number of genes 10 time higher with respect to + P and + Na, and caused appearance of numerous and large plastoglobules and starch granules in chloroplasts. Our results show that A. donax is sensitive to unbalances of soil ion content, despite activation of defensive mechanisms that enhance plant resilience, growth and biomass production of A. donax under these conditions., (Copyright © 2019. Published by Elsevier B.V.)

Background: Consumer preference today is for the consumption of functional food and the reduction of chemical preservatives. Moreover, the antimicrobial properties and health-promoting qualities of plant secondary metabolites are well known. Due to forecasted climate changes and increasing human population, agricultural practices for saving water have become a concern. In the present study, the physiological responses of curly kale Brassica oleracea L. convar. Acephala (DC) var. sabellica to drought stress and the impact of water limitation on the concentration of selected secondary metabolites were investigated under laboratory-controlled conditions., Results: Results indicated that drought stress increased the content of trans-2-hexenal, phytol and δ-tocopherol, and decreased chlorophyll content. Moreover, drought stress increased antioxidant capacity and the expression of AOP2, a gene associated with the biosynthesis of aliphatic alkenyl glucosinolates, and of three genes - TGG1, TGGE and PEN2 - encoding for myrosinases, the enzymes involved in glucosinolate breakdown., Conclusion: The present study shows that water limitation during the growing phase might be exploited as a sustainable practice for producing curly kale with a high concentration of nutritionally important health-promoting bioactive metabolites. © 2019 Society of Chemical Industry., (© 2019 Society of Chemical Industry.)

At high temperatures, isoprene-emitting plants display a higher photosynthetic rate and a lower nonphotochemical quenching (NPQ) compared with nonemitting plants. The mechanism of this phenomenon, which may be very important under current climate warming, is still elusive. NPQ was dissected into its components, and chlorophyll fluorescence lifetime imaging microscopy (FLIM) was used to analyse the dynamics of excited chlorophyll relaxation in isoprene-emitting and nonemitting plants. Thylakoid membrane stiffness was also measured using atomic force microscope (AFM) to identify a possible mode of action of isoprene in improving photochemical efficiency and photosynthetic stability. We show that, when compared with nonemitters, isoprene-emitting tobacco plants exposed at high temperatures display a reduced increase of the NPQ energy-dependent component (qE) and stable (1) chlorophyll fluorescence lifetime; (2) amplitude of the fluorescence decay components; and (3) thylakoid membrane stiffness. Our study shows for the first time that isoprene maintains PSII stability at high temperatures by preventing the modifications of the surrounding environment, namely providing a more steady and homogeneous distribution of the light-absorbing centres and a stable thylakoid membrane stiffness. Isoprene photoprotects leaves with a mechanism alternative to NPQ, enabling plants to maintain a high photosynthetic rate at rising temperatures., (© 2019 The Authors. New Phytologist © 2019 New Phytologist Trust.)

The role of jasmonates in defense priming has been widely recognized. Priming is a physiological process by which a plant exposed to low doses of biotic or abiotic elicitors activates faster and/or stronger defense responses when subsequently challenged by a stress. In this work, we investigated the impact of MeJA-induced defense responses to mechanical wounding in rice ( Oryza sativa ). The proteome reprogramming of plants treated with MeJA, wounding or MeJA+wounding has been in-depth analyzed by using a combination of high throughput profiling techniques and bioinformatics tools. Gene Ontology analysis identified protein classes as defense/immunity proteins, hydrolases and oxidoreductases differentially enriched by the three treatments, although with different amplitude. Remarkably, proteins involved in photosynthesis or oxidative stress were significantly affected upon wounding in MeJA-primed plants. Although these identified proteins had been previously shown to play a role in defense responses, our study revealed that they are specifically associated with MeJA-priming. Additionally, we also showed that at the phenotypic level MeJA protects plants from oxidative stress and photosynthetic damage induced by wounding. Taken together, our results add novel insight into the molecular actors and physiological mechanisms orchestrated by MeJA in enhancing rice plants defenses after wounding., Competing Interests: The authors declare no conflict of interest

Previous research demonstrated that Pseudomonas chlororaphis subsp. aureofaciens strain M71, a plant growth promoting bacterium (PGPB), exerts beneficial effects on plant metabolism and primes tolerance mechanisms against biotic stresses in tomatoes. We designed an experiment to assess whether root colonization with P. chlororaphis is also able to improve tolerance to water stress in tomatoes. Our results show that inoculation with P. chlororaphis stimulates the antioxidant activity of well-watered tomatoes while maintaining a steady-state level of reactive oxygen species (ROS), increases the expression of genes encoding for the biosynthesis of leaf terpenes, stimulates the production of both the phytohormones ABA and IAA, in turn affecting plant shape (number of leaves) and height (length of internodes), without altering photosynthesis. Upon exposure to mild water stress conditions, an improved antioxidant activity in tomatoes 'primed' by P. chlororaphis inoculation limited the accumulation of reactive oxygen species (ROS) in leaves and thus enhanced tolerance, also through increase of the (osmolyte) proline content. Moreover, P. chlororaphis inoculation further enhanced the ABA level in leaves of water-stressed tomatoes allowing a more efficient modulation of stomatal closure that resulted in an improved water use efficiency (WUE) and biomass accumulation., (Copyright © 2018 Elsevier GmbH. All rights reserved.)

Vibrational spectroscopies (Fourier Transform Infra Red, FTIR, and Raman) are exceptionally valuable tools for the identification and crystal-chemical study of fibrous minerals, and asbestos amphiboles in particular. Raman spectroscopy has been widely applied in toxicological studies and thus a large corpus of reference data on regulated species is found in the literature. However, FTIR spectroscopy has been mostly used in crystal-chemical studies and very few data are found on asbestos amphiboles. This paper is intended to fill this gap. We report new FTIR data collected on a suite of well-characterized samples of the five regulated amphibole species: anthophyllite, amosite, and crocidolite, provided by the Union for International Cancer Control (UICC) Organization, and tremolite and actinolite, from two well-known occurrences. The data from these reference samples have been augmented by results from additional specimens to clarify some aspects of their spectroscopic features. We show that the FTIR spectra in both the OH-stretching region and in the lattice modes region can be effective for rapid identification of the asbestos type., Competing Interests: Conflicts of Interest: The authors declare no conflict of interest.

This work describes the nature of the potentially hazardous fibrous amphibole found in the Orani's feldspar mine (Sardinia, Italy). To identify its nature, a protocol of analysis including morphometric, chemical and crystallographic characterizations was applied. Thanks to this approach, it was possible to classify the observed fibres as tremolite after comparing chemical data, SEM/TEM observations, FTIR/ Raman spectra and X-ray diffraction data with those reported for a standard sample. The unit cell parameters of the investigated tremolite phase are a = 9.82(1) Å, b = 18.08(3) Å, c = 5.27(1) Å, and the angle β corresponds to 104.4(1)°. The mean concentration of asbestos tremolite in the Orani's feldspar is 0.28 wt%. Most of the fibres (0.26 wt%) are respirable 'regulated' fibres, representing a potential hazard. Because the total amount of tremolite in the sample is 0.6 wt%, a large fraction of it has a crystal habit other than fibrous-asbestiform or acicular. The obtained results allowed us to suggest possible solutions for a safe exploitation and mineral processing of the Orani's mine. The procedure proposed herein may be a general tool suitable to identify the mineralogical nature of fibrous minerals in raw materials and assess if they may represent a potential health/environmental hazard., (Copyright © 2018 Elsevier B.V. All rights reserved.)

The study of the mechanisms by which mineral fibres promote adverse effects in both animals and humans is a hot topic of multidisciplinary research with many aspects that still need to be elucidated. Besides length and diameter, a key parameter that determines the toxicity/pathogenicity of a fibre is biopersistence, one component of which is biodurability. In this paper, biodurability of mineral fibres of social and economic importance (chrysotile, amphibole asbestos and fibrous erionite) has been determined for the first time in a systematic comparative way from in vitro acellular dissolution experiments. Dissolution was possible using the Gamble solution as simulated lung fluid (pH = 4 and at body temperature) so to reproduce the macrophage phagolysosome environment. The investigated mineral fibres display very different dissolution rates. For a 0.25 μm thick fibre, the calculated dissolution time of chrysotile is in the range 94-177 days, very short if compared to that of amphibole fibres (49-245 years), and fibrous erionite (181 years). Diffraction and SEM data on the dissolution products evidence that chrysotile rapidly undergoes amorphization with the formation of a nanophasic silica-rich fibrous metastable pseudomorph as first dissolution step whereas amphibole asbestos and fibrous erionite show minor signs of dissolution even after 9-12 months.

Main Conclusion: AM symbiosis did not strongly affect Arundo donax performances under salt stress, although differences in the plants inoculated with two different fungi were recorded. The mechanisms at the basis of the improved tolerance to abiotic stresses by arbuscular mycorrhizal (AM) fungi have been investigated mainly focusing on food crops. In this work, the potential impact of AM symbiosis on the performance of a bioenergy crop, Arundo donax, under saline conditions was considered. Specifically, we tried to understand whether AM symbiosis helps this fast-growing plant, often widespread in marginal soils, withstand salt. A combined approach, involving eco-physiological, morphometric and biochemical measurements, was used and the effects of two different AM fungal species (Funneliformis mosseae and Rhizophagus irregularis) were compared. Results indicate that potted A. donax plants do not suffer permanent damage induced by salt stress, but photosynthesis and growth are considerably reduced. Since A. donax is a high-yield biomass crop, reduction of biomass might be a serious agronomical problem in saline conditions. At least under the presently experienced growth conditions, and plant-AM combinations, the negative effect of salt on plant performance was not rescued by AM fungal colonization. However, some changes in plant metabolisms were observed following AM-inoculation, including a significant increase in proline accumulation and a trend toward higher isoprene emission and higher H 2 O 2 , especially in plants colonized by R. irregularis. This suggests that AM fungal symbiosis influences plant metabolism, and plant-AM fungus combination is an important factor for improving plant performance and productivity, in presence or absence of stress conditions.

This data article presents the UK City LIFE 1 data set for the city of Birmingham, UK. UK City LIFE 1 is a new, comprehensive and holistic method for measuring the livable sustainability performance of UK cities. The Birmingham data set comprises 346 indicators structured simultaneously (1) within a four-tier, outcome-based framework in order to aid in their interpretation (e.g., promote healthy living and healthy long lives, minimize energy use, uncouple economic vitality from CO2 emissions) and (2) thematically in order to complement government and disciplinary siloes (e.g., health, energy, economy, climate change). Birmingham data for the indicators are presented within an Excel spreadsheet with their type, units, geographic area, year, source, link to secondary data files, data collection method, data availability and any relevant calculations and notes. This paper provides a detailed description of UK city LIFE 1 in order to enable comparable data sets to be produced for other UK cities. The Birmingham data set is made publically available at http://epapers.bham.ac.uk/3040/ to facilitate this and to enable further analyses. The UK City LIFE 1 Birmingham data set has been used to understand what is known and what is not known about the livable sustainability performance of the city and to inform how Birmingham City Council can take action now to improve its understanding and its performance into the future (see "Improving city-scale measures of livable sustainability: A study of urban measurement and assessment through application to the city of Birmingham, UK" Leach et al. [2]).