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[Display omitted] • ZnO was prepared directly on cotton fabric using a completely green synthesis method. • Plant waste from food processing or invasive alien species was used for the preparation of reducing agents. • Different properties of cotton can be designed according to the reducing agent used. • Sustainable hydrophilic or hydrophobic cotton with excellent UV-protection was produced. An extensive study on using plant waste aqueous extracts as natural chemicals for in-situ synthesis of zinc oxide (ZnO) on cotton is presented. Reducing agents were prepared from green tea leaves (GT), pomegranate peels (PG), and staghorn sumac leaves (SsL) and drupes (SsD), and the alkaline medium from discarded wood ash. Zinc acetate was found to be more appropriate precursor than zinc nitrate. Formation of ZnO on cotton was confirmed by energy dispersive spectroscopy, X-ray photoelectron spectroscopy and X-ray diffraction analysis (XRD). The inductively coupled plasma mass spectrometry and X-ray fluorescence results showed the highest amount of ZnO on cotton was formed using PG and SsL extracts, which was also confirmed with scanning electron microscopy and UV/visible spectroscopy. The ZnO-functionalised samples exhibited excellent UV-blocking ability and different wetting properties (hydrophilic or hydrophobic) depending on the reducing agent used due to their different total phenolic content. This study shows that by choosing the plant waste source as a reducing agent for ZnO formation directly on cotton, the properties of cotton can be designed to be hydrophilic or hydrophobic with excellent UV-blocking properties. The XRD results of ex-situ synthesis prove that the short reaction time enables the formation of ZnO. [ABSTRACT FROM AUTHOR]

• Electrochemical stability of Rh/C was studied by accelerated degradation protocols. • IL-SEM and ex-situ TEM were used to study local nanoscale degradation mechanisms. • EFC-ICP-MS was used to track Rh dissolution during degradation tests. • Severe degradation of Rh/C occurs during cycling between 0.05 V RHE and 1.4 V RHE. • Degradation of Rh/C occurs via dissolution followed by re-deposition. Electrochemical stability of a commercial Rh/C catalyst has been studied in an acidic electrolyte by accelerated degradation protocols (ADP) which involved 5000 rapid voltammetric scans (1 V/s) in two potential regions: ADP1 was performed between 0.4 V RHE and 1.4 V RHE , while ADP2 was performed between 0.05 V RHE and 1.4 V RHE. Degradation of Rh/C was monitored by the changes in Rh electrochemical surface area (ECSA) and electrocatalytic activity for hydrogen evolution (HER) and oxygen reduction (ORR). Rh/C catalyst was particularly stable during ADP1 showing only a minor loss of ECSA, while its electrocatalytic activity for HER and ORR was practically unaffected, which was further corroborated with identical location SEM (IL-SEM) imaging. In the case of ADP2, severe degradation of Rh/C occurred followed by substantial decay in its electrocatalytic activity. Coupling of the electrochemical flow cell (EFC) with ICP-MS revealed much higher Rh dissolution in ADP2 than in ADP1. IL-SEM in combination with ex-situ TEM imaging showed that degradation of the Rh/C sample is not homogeneous during ADP2, as dissolution prevails on certain locations, while dissolution followed by re-deposition occurs on others. According to the results obtained in this work, Rh/C catalysts are exceptionally sensitive to the sudden potential jumps between particularly low and high values. [Display omitted] [ABSTRACT FROM AUTHOR]

Upon exposure to an electrochemical environment, structural properties of nanoparticulate electrocatalysts at the atomic scale are not stagnant but rather dynamic. These have a direct effect on catalysts' performance via structure-property relationships. The active surface structure is constantly changing via complex phenomena dependant on their nature and reaction conditions. State-of-the-art transmission electron microscopy (TEM) can already provide us with atomically precise structures of individual nanoparticles, which are a key to exploring structure-property relations. However, with the analysis of random nanoparticles with unknown structural history, it is impossible to realise the exact structural alternation mechanisms. In order to study these phenomena operando, in-situ or quasi-in-situ methods need to be developed and used. In the present study, we highlight a recently introduced methodological approach named modified floating electrode (MFE), which enables the assessment of (i) proton exchange membrane fuel cell (PEMFC) cathode oxygen reduction reaction (ORR) at the industry-relevant current densities and (ii) atomic-level structural changes of the same nanoparticle, via identical location scanning electron microscopy (SEM) and TEM approach (IL-SEM and IL-TEM), in one measurement. Careful analysis and comparison of atomically resolved high-resolution scanning TEM (HR-STEM) images of the same nanoparticle before and after MFE measurements were conducted via homemade microscopy image analysis algorithms. We reveal structural changes on the atomic-scale of the industrial benchmark Pt-Co nanoalloy ORR electrocatalyst upon exposure to electrochemical activation and high ORR current densities. Observing and comparing the detailed structure and morphology of the same nanoparticle reveals atomic-scale processes such as particle anisotropic etching and redeposition, besides other processes such as particle necking, anti-necking, pore formation, particle movement, coalescence, etc. The understanding of the dynamics behind these changes is crucial for the interpretation of ORR electrocatalyst's activity and stability. Our bottom-up approach enables direct investigation of nanoparticles' structure-stability relationships. [ABSTRACT FROM AUTHOR]

Hyperaccumulating plants are able to (hyper)accumulate high concentrations of metal(loid)s in their above-ground tissues without any signs of toxicity. Studies on the root-associated microbiome have been previously conducted in relation to hyperaccumulators, yet much remains unknown about the interactions between hyperaccumulating hosts and their microbiomes, as well as the dynamics within these microbial communities. Here, we assess the impact of the plant host on shaping microbial communities of three naturally occurring populations of Noccaea species in Slovenia: Noccaea praecox and co-occurring N. caerulescens from the non-metalliferous site and N. praecox from the metalliferous site. We investigated the effect of metal enrichment on microbial communities and explored the interactions within microbial groups and their environment. The abundance of bacterial phyla was more homogeneous than fungal classes across all three Noccaea populations and across the three root-associated compartments (roots, rhizosphere, and bulk soil). While most fungal and bacterial Operational Taxonomic Units (OTUs) were found at both sites, the metalliferous site comprised more unique OTUs in the root and rhizosphere compartments than the non-metalliferous site. In contrast to fungi, bacteria exhibited differentially significant abundance between the metalliferous and non-metalliferous sites as well as statistically significant correlations with most of the soil parameters. Results revealed N. caerulescens had the highest number of negative correlations between the bacterial phyla, whereas the population from the metalliferous site had the fewest. This decrease was accompanied by a big perturbation in the bacterial community at the metalliferous site, indicating increased selection between the bacterial taxa and the formation of potentially less stable rhizobiomes. These findings provide fundamentals for future research on the dynamics between hyperaccumulators and their associated microbiome., (© 2024. The Author(s).)

Most biosynthetic gene clusters (BGC) encoding the synthesis of important microbial secondary metabolites, such as antibiotics, are either silent or poorly expressed; therefore, to ensure a strong pipeline of novel antibiotics, there is a need to develop rapid and efficient strain development approaches. This study uses comparative genome analysis to instruct rational strain improvement, using Streptomyces rimosus , the producer of the important antibiotic oxytetracycline (OTC) as a model system. Sequencing of the genomes of two industrial strains M4018 and R6-500, developed independently from a common ancestor, identified large DNA rearrangements located at the chromosome end. We evaluated the effect of these genome deletions on the parental S. rimosus Type Strain (ATCC 10970) genome where introduction of a 145 kb deletion close to the OTC BGC in the Type Strain resulted in massive OTC overproduction, achieving titers that were equivalent to M4018 and R6-500. Transcriptome data supported the hypothesis that the reason for such an increase in OTC biosynthesis was due to enhanced transcription of the OTC BGC and not due to enhanced substrate supply. We also observed changes in the expression of other cryptic BGCs; some metabolites, undetectable in ATCC 10970, were now produced at high titers. This study demonstrated for the first time that the main force behind BGC overexpression is genome rearrangement. This new approach demonstrates great potential to activate cryptic gene clusters of yet unexplored natural products of medical and industrial value.IMPORTANCEThere is a critical need to develop novel antibiotics to combat antimicrobial resistance. Streptomyces species are very rich source of antibiotics, typically encoding 20-60 biosynthetic gene clusters (BGCs). However, under laboratory conditions, most are either silent or poorly expressed so that their products are only detectable at nanogram quantities, which hampers drug development efforts. To address this subject, we used comparative genome analysis of industrial Streptomyces rimosus strains producing high titers of a broad spectrum antibiotic oxytetracycline (OTC), developed during decades of industrial strain improvement. Interestingly, large-scale chromosomal deletions were observed. Based on this information, we carried out targeted genome deletions in the native strain S. rimosus ATCC 10970, and we show that a targeted deletion in the vicinity of the OTC BGC significantly induced expression of the OTC BGC, as well as some other silent BGCs, thus suggesting that this approach may be a useful way to identify new natural products., Competing Interests: University of Ljubljana Biotechnical faculty filed a patent application relating to the findings of this work (inventors: Hrvoje Petković, Alen Pšeničnik, and Lucija Slemc).

Lithium lanthanum titanate (LLTO) perovskite is one of the most promising electrolytes for all-solid-state batteries, but its performance is limited by the presence of grain boundaries (GBs). The fraction of GBs can be significantly reduced by the preparation of coarse-grained LLTO ceramics. In this work, we describe an alternative approach to the fabrication of ceramics with large LLTO grains based on self-seeded grain growth. In compositions with the starting stoichiometry for the Li 0.20 La 0.60 TiO 3 phase and with a high excess addition of Li (Li:La:Ti = 11:15:25), microstructure development starts with the formation of the layered RP-type Li 2 La 2 Ti 3 O 10 phase. Grains with many RP-type defects initially develop into large platelets with thicknesses of up to 10 μm and lengths over 100 μm. Microstructure development continues with the crystallization of LLTO perovskite, epitaxially on the platelets and as smaller grains with thinner in-grain RP-lamellae. Theoretical calculations confirmed that the formation of RP-type sequences is energetically favored and precedes the formation of the LLTO perovskite phase. At around 1250 °C, the RP-type sequences become thermally unstable and gradually recrystallize to LLTO via the ionic exchange between the Li-rich RP-layers and the neighboring Ti and La layers as shown by quantitative HAADF-STEM. At higher sintering temperatures, LLTO grains become free of RP-type defects and the small grains recrystallize onto the large platelike seed grains via Ostwald ripening. The final microstructure is coarse-grained LLTO with total ionic conductivity in the range of 1 × 10 -4 S/cm.

A current trend in the investigation of state-of-the-art Pt-alloys as proton exchange membrane fuel cell (PEMFC) electrocatalysts is to study their long-term stability as a bottleneck for their full commercialization. Although many parameters have been appropriately addressed, there are still certain issues that must be considered. Here, the stability of an experimental Pt-Co/C electrocatalyst is investigated by high-temperature accelerated degradation tests (HT-ADTs) in a high-temperature disk electrode (HT-DE) setup, allowing the imitation of close-to-real operational conditions in terms of temperature (60 °C). Although the US Department of Energy (DoE) protocol has been chosen as the basis of the study (30,000 trapezoidal wave cycling steps between 0.6 and 0.95 V RHE with a 3 s hold time at both the lower potential limit (LPL) and the upper potential limit (UPL)), this works demonstrates that limiting both the LPL and UPL (from 0.6-0.95 to 0.7-0.85 V RHE ) can dramatically reduce the degradation rate of state-of-the-art Pt-alloy electrocatalysts. This has been additionally confirmed with the use of an electrochemical flow cell coupled to inductively coupled plasma mass spectrometry (EFC-ICP-MS), which enables real-time monitoring of the dissolution mechanisms of Pt and Co. In line with the HT-DE methodology observations, a dramatic decrease in the total dissolution of Pt and Co has once again been observed upon narrowing the potential window to 0.7-0.85 V RHE rather than 0.6-0.95 V RHE . Additionally, the effect of the potential hold time at both LPL and UPL on metal dissolution has also been investigated. The findings demonstrate that the dissolution rate of both metals is proportional to the hold time at UPL regardless of the applied potential window, whereas the hold time at the LPL does not appear to be as detrimental to the stability of metals., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Phenols, and especially their nitrated analogues, are ubiquitous pollutants and known carcinogens which have already been linked to forest decline. Although nitrophenols have been widely recognized as harmful to different aquatic and terrestrial organisms, we could not find any literature assessing their toxicity to terrestrial plants. Maize (monocot) and sunflower (dicot) were exposed to phenolic pollutants, guaiacol (GUA) and 4-nitroguaiacol (4NG), through a hydroponics system under controlled conditions in a growth chamber. Their acute physiological response was studied during a two-week root exposure to different concentrations of xenobiotics (0.1, 1.0, and 10 mM). The exposure visibly affected plant growth and the effect increased with increasing xenobiotic concentration. In general, 4NG affected plants more than GUA. Moreover, sunflower exhibited an adaptive response, especially to low and moderate GUA concentrations. The integrity of both plant species deteriorated during the exposure: biomass and photochemical pigment content were significantly reduced, which reflected in the poorer photochemical efficiency of photosystem II. Our results imply that 4NG is taken up by sunflower plants, where it could enter a lignin biosynthesis pathway., (© 2024. The Author(s).)

Nitroguaiacols are typical constituents of biomass-burning emissions, including absorbing aerosols which contribute to climate change. Although they are also harmful to humans and plants, their atmospheric fate and lifetimes are still very speculative. Therefore, in this work, the photolysis kinetics of aqueous-phase 4-nitroguaiacol (4NG) and 5-nitroguaiacol (5NG), and the resulting photo-formed products were investigated under artificial sunlight, observing also the effect of sunlight on the absorption properties of the solutions. We found the photolysis of 5NG slower than that of 4NG, whereas the absorbance in the visible range prevailed in the 5NG solutions at the end of experiments. Although we identified dinitroguaiacol as one of the 4NG photolysis products, which increased light absorption of 4NG-containing solutions, considerably more chromophores formed in the 5NG photolyzed solutions, implying its stronger potential for secondary BrC formation in the atmosphere. In general, denitration, carbon loss, hydroxylation, nitration, and carbon gain were characteristic of 4NG phototransformation, while carbon loss, hydroxylation, and carbon gain were observed in the case of 5NG. The photolysis kinetics was found of the first order at low precursor concentrations (<0.45 mM), resulting in their lifetimes in the order of days (125 and 167 h illumination for 4NG and 5NG, respectively), which suggests long-range transport of the investigated compounds in the atmosphere and proposes their use as biomass-burning aerosol tracer compounds., 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., (Copyright © 2023 Delić, Skube, Šala and Kroflič.)

This study aims to investigate the potential benefits of adapting the ablating grid in two-dimensional (2D) and three-dimensional (3D) laser ablation inductively coupled plasma mass spectrometry in a single pulse mapping mode. The goals include enhancing the accuracy of surface sampling of element distributions, improving the control of depth-related sampling, smoothing the post-ablation surface for layer-by-layer sampling, and increasing the image quality. To emulate the capabilities of currently unavailable laser ablation stages, a computational approach using geometrical modeling was employed to compound square or round experimentally obtained 3D crater profiles on variable orthogonal or hexagonal ablation grids. These grids were optimized by minimizing surface roughness as a function of average ablation depth, followed by simulating the post-ablation surface and related image quality. An online application (https://laicpms-apps.ki.si/webapps/home/) is available for users to virtually experiment with contracting/expanding orthogonal and hexagonal ablation grids for generic 3D super-Gaussian laser crater profiles, allowing for exploration of the resulting post-ablation surface layer roughness and depth.

Laser ablation (LA) in combination with inductively coupled plasma time-of-flight mass spectrometry (ICP-TOFMS) enables monitoring of elements from the entire mass range for every pixel, regardless of the isotopes of interest for a certain application. This provides nontargeted multi-element (bio-)imaging capabilities and the unique possibility to screen for elements that were initially not expected in the sample. Quantification of a large range of elements is limited as the preparation of highly multiplexed calibration standards for bioimaging applications by LA-ICP-(TOF)MS is challenging. In this study, we have developed a workflow for semiquantitative analysis by LA-ICP-TOFMS based on multi-element gelatin micro-droplet standards. The presented approach is intended for the mapping of biological samples due to the requirement of matrix-matched standards for accurate quantification in LA-ICPMS, a prerequisite that is given by the use of gelatin-based standards. A library of response factors was constructed based on 72 elements for the semiquantitative calculations. The presented method was evaluated in two stages: (i) on gelatin samples with known elemental concentrations and (ii) on real-world samples that included prime examples of bioimaging (mouse spleen and tumor tissue). The developed semiquantification approach was based on 10 elements as calibration standards and provided the determination of 136 nuclides of 63 elements, with errors below 25%, and for half of the nuclides, below 10%. A web application for quantification and semiquantification of LA-ICP(-TOF)MS data was developed, and a detailed description is presented to easily allow others to use the presented method.

A versatile approach to the production of cluster- and single atom-based thin-film electrode composites is presented. The developed TiO x N y -Ir catalyst was prepared from sputtered Ti-Ir alloy constituted of 0.8 ± 0.2 at % Ir in α-Ti solid solution. The Ti-Ir solid solution on the Ti metal foil substrate was anodically oxidized to form amorphous TiO 2 -Ir and later subjected to heat treatment in air and in ammonia to prepare the final catalyst. Detailed morphological, structural, compositional, and electrochemical characterization revealed a nanoporous film with Ir single atoms and clusters that are present throughout the entire film thickness and concentrated at the Ti/TiO x N y -Ir interface as a result of the anodic oxidation mechanism. The developed TiO x N y -Ir catalyst exhibits very high oxygen evolution reaction activity in 0.1 M HClO 4 , reaching 1460 A g -1 Ir at 1.6 V vs reference hydrogen electrode. The new preparation concept of single atom- and cluster-based thin-film catalysts has wide potential applications in electrocatalysis and beyond. In the present paper, a detailed description of the new and unique method and a high-performance thin film catalyst are provided along with directions for the future development of high-performance cluster and single-atom catalysts prepared from solid solutions., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

The design of catalysts with stable and finely dispersed platinum or platinum alloy nanoparticles on the carbon support is key in controlling the performance of proton exchange membrane (PEM) fuel cells. In the present work, an intermetallic PtCo/C catalyst is synthesized via double-passivation galvanic displacement. TEM and XRD confirm a significantly narrowed particle size distribution for the catalyst particles compared to commercial benchmark catalysts (Umicore PtCo/C). Only about 10% of the mass fraction of PtCo particles show a diameter larger than 8 nm, whereas this is up to or even more than 35% for the reference systems. This directly results in a considerable increase in electrochemically active surface area (96 m 2 g -1 vs. >70 m 2 g -1 ), which confirms the more efficient usage of precious catalyst metal in the novel catalyst. Single-cell tests validate this finding by improved PEM fuel cell performance. Reducing the cathode catalyst loading from 0.4 mg cm -2 to 0.25 mg cm -2 resulted in a power density drop at an application-relevant 0.7 V of only 4% for the novel catalyst, compared to the 10% and 20% for the commercial benchmarks reference catalysts., Competing Interests: The authors declare no competing financial interest., (This journal is © The Royal Society of Chemistry.)

In this work, we developed and optimized a method for the analysis of PAHs and nitro-PAHs in atmospheric particulate matter (PM) samples by using thermal desorption gas chromatography coupled with electron ionization single quadrupole mass spectrometry (TD-GC-(EI)-MS). The method uses thermal desorption from a PM on a filter sample as means of sample introduction to a column and obviates the need for complex extraction procedures, which are time-consuming and require environmentally unfriendly solvents. Moreover, the possibility of systematic errors is minimized and a significantly smaller amount of sample is required compared to traditional techniques requiring a pre-extraction step (approx. 10-times). Thirteen PAHs and three nitro-PAHs were used during method development. Although Tenax cartridges are typically used to capture volatile pollutants from the air, we found that glass-wool liner is the most suitable trap for the examined analytes after desorption from a quartz filter. Among the various instrument parameters which were tested and optimized, TD desorption flow and hold time, and temperature of the cooled injection system (CIS) proved to be most critical. We also found out that the matrix effect is especially pronounced in the case of high PM loadings, which should be kept in mind when planning the analysis. After the optimization, standard reference materials (ERM-CZ100 and NIST 1648a) were used for partial method validation and finally, real PM 10 and PM 2.5 samples from two Slovenian cities were successfully analyzed., 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 © 2022 Elsevier B.V. All rights reserved.)

Synthesis of zinc oxide (ZnO) nanoparticles (NPs) was mediated by plant extracts to assist in the reduction of zinc atoms during the synthesis and act as a capping agent during annealing. The preparation used ethanolic extracts from the roots of Japanese knotweed ( Fallopia japonica ). Two major outcomes could be made. (i) A synergistic effect of multiple polyphenolic components in the extract is needed to achieve the capping effect of crystallite growth during thermal annealing at 450 °C characterized by an exponential growth factor ( n ) of 4.4 compared to n = 3 for bare ZnO. (ii) Synergism between the ZnO NPs and plant extracts resulted in superior antimicrobial activity against both Gram-positive bacteria, e.g. , Staphylococcus aureus , and Gram-negative bacteria, e.g. , Escherichia coli and Campylobacter jejuni . The materials were also tested for their antimicrobial activity against S. aureus under ultraviolet (UV) illumination. Also here, the photocatalyst prepared with plant extracts was found to be superior. The residues of the plant extract molecules on the surface of the catalyst were identified as the main cause of the observed differences, as proved by thermal gravimetry. Such a preparation using ethanolic extract of Fallopia japonica could serve as a more controlled synthesis of ZnO and potentially other metal oxides, with low environmental impact and high abundance in nature., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

The lack of efficient and durable proton exchange membrane fuel cell electrocatalysts for the oxygen reduction reaction is still restraining the present hydrogen technology. Graphene-based carbon materials have emerged as a potential solution to replace the existing carbon black (CB) supports; however, their potential was never fully exploited as a commercial solution because of their more demanding properties. Here, a unique and industrially scalable synthesis of platinum-based electrocatalysts on graphene derivative (GD) supports is presented. With an innovative approach, highly homogeneous as well as high metal loaded platinum-alloy (up to 60 wt %) intermetallic catalysts on GDs are achieved. Accelerated degradation tests show enhanced durability when compared to the CB-supported analogues including the commercial benchmark. Additionally, in combination with X-ray photoelectron spectroscopy Auger characterization and Raman spectroscopy, a clear connection between the sp 2 content and structural defects in carbon materials with the catalyst durability is observed. Advanced gas diffusion electrode results show that the GD-supported catalysts exhibit excellent mass activities and possess the properties necessary to reach high currents if utilized correctly. We show record-high peak power densities in comparison to the prior best literature on platinum-based GD-supported materials which is promising information for future application., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

Pt-alloy (Pt-M) nanoparticles (NPs) with less-expensive 3d transition metals (M = Ni, Cu, Co) supported on high-surface-area carbon supports are currently the state-of-the-art (SoA) solution to reach the production phase in proton exchange membrane fuel cells (PEMFCs). However, while Pt-M electrocatalysts show promise in terms of increased activity for oxygen reduction reaction (ORR) and, thus, cost reductions from the significantly lower use of expensive and rare Pt, key challenges in terms of synthesis, activation, and stability remain to unlock their true potential. This work systematically tackles them with a combination of electrocatalyst synthesis and characterization methodologies including thin-film rotating disc electrodes (TF-RDEs), an electrochemical flow cell linked to an inductively coupled plasma mass spectrometer (EFC-ICP-MS), and testing in 50 cm 2 membrane electrode assemblies (MEAs). In the first part of the present work, we highlight the crucial importance of the chemical activation (dealloying) step on the performance of Pt-M electrocatalysts in the MEA at high current densities (HCDs). In addition, we provide the scientific community with a preliminary and facile method of distinguishing between a "poorly" and "adequately" dealloyed (activated) Pt-alloy electrocatalyst using a much simpler and affordable TF-RDE methodology using the well-known CO-stripping process. Since the transition-metal cations can also be introduced in a PEMFC due to the degradation of the Pt-M NPs, the second part of the work focuses on presenting clear evidence on the direct impact of the lower voltage limit (LVL) on the stability of Pt-M electrocatalysts. The data suggests that in addition to intrinsic improvements in stability, significant improvements in the PEMFC lifetime can also be obtained via the correct MEA design and applied limits of operation, namely, restricting not just the upper but equally important also the lower operation voltage., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

Nitroaromatic compounds (NACs) as important constituents of atmospheric humic-like substances (HULIS) and brown carbon (BrC) affect the Earth's climate and pose a serious environmental hazard. We investigated seasonal size-segregated NACs in aerosol samples from the urban background environment in Ljubljana, Slovenia. Total concentrations of twenty NACs in PM 15.6 were on average from 0.51 ng m -3 (summer) to 109 ng m -3 (winter), and contributed the most to submicron aerosols (more than 74%). Besides 4-nitrocatechol (4NC) as the prevailing species, methylnitrocatechols (MNCs) and nitrophenols (NPs), we reported on some very rarely mentioned, but also on five novel NACs (i.e., 3H4NBA: 3-hydroxy-4-nitrobenzoic acid, 3MeO4NP: 3-methoxy-4-nitrophenol, 4Et5NC: 4-ethyl-5-nitrocatechol, 3Et5NC: 3-ethyl-5-nitrocatechol and 3MeO5NC: 3-methoxy-5-nitrocatechol). Concentrations of 3MeO5NC, 4Et5NC and 3Et5NC were enhanced during cold seasons, contributing up to 11% to total NAC in winter. In cold season, NAC size distributions were characterized with the peaks in the broader size range of 0.305-1.01 μm (accumulation mode), with 4NC and alkyl-nitrocatechols (∑(M/Et)NC) as the most abundant, followed by 4-nitrosyringol, nitrophenols and nitroguaiacols. In spring, a pronounced peak of ∑(M/Et)NC was observed in the accumulation mode (0.305-0.56 μm) as well as in the coarse one. A strong correlation of all NACs with ∑(M/Et)NC and levoglucosan indicates that primary emissions of wood burning were the most important source of NACs, but their secondary formation (e.g., aqueous-phase at higher ambient RH) in cold season could also be a significant one. In warmer season, NACs may be mostly derived from traffic-related aromatic VOCs. The contribution of NACs to the light absorption of the aqueous extracts was up to 10-times higher (contribution to Abs 365 up to 31%) than their mass contributions to WSOC (up to 3%) of corresponding size-segregated aerosols, confirming that most of the identified NACs are strong BrC chromophores., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

Streptomyces rimosus ATCC 10970 is the parental strain of industrial strains used for the commercial production of the important antibiotic oxytetracycline. As an actinobacterium with a large linear chromosome containing numerous long repeat regions, high GC content, and a single giant linear plasmid (GLP), these genomes are challenging to assemble. Here, we apply a hybrid sequencing approach relying on the combination of short- and long-read next-generation sequencing platforms and whole-genome restriction analysis by using pulsed-field gel electrophoresis (PFGE) to produce a high-quality reference genome for this biotechnologically important bacterium. By using PFGE to separate and isolate plasmid DNA from chromosomal DNA, we successfully sequenced the GLP using Nanopore data alone. Using this approach, we compared the sequence of GLP in the parent strain ATCC 10970 with those found in two semi-industrial progenitor strains, R6-500 and M4018. Sequencing of the GLP of these three S. rimosus strains shed light on several rearrangements accompanied by transposase genes, suggesting that transposases play an important role in plasmid and genome plasticity in S. rimosus . The polished annotation of secondary metabolite biosynthetic pathways compared to metabolite analysis in the ATCC 10970 strain also refined our knowledge of the secondary metabolite arsenal of these strains. The proposed methodology is highly applicable to a variety of sequencing projects, as evidenced by the reliable assemblies obtained. IMPORTANCE The genomes of Streptomyces species are difficult to assemble due to long repeats, extrachromosomal elements (giant linear plasmids [GLPs]), rearrangements, and high GC content. To improve the quality of the S. rimosus ATCC 10970 genome, producer of oxytetracycline, we validated the assembly of GLPs by applying a new approach to combine pulsed-field gel electrophoresis separation and GLP isolation and sequenced the isolated GLP with Oxford Nanopore technology. By examining the sequenced plasmids of ATCC 10970 and two industrial progenitor strains, R6-500 and M4018, we identified large GLP rearrangements. Analysis of the assembled plasmid sequences shed light on the role of transposases in genome plasticity of this species. The new methodological approach developed for Nanopore sequencing is highly applicable to a variety of sequencing projects. In addition, we present the annotated reference genome sequence of ATCC 10970 with a detailed analysis of the biosynthetic gene clusters.

Two different morphologies of ferroelectric bismuth titanate (Bi 4 Ti 3 O 12 ) nanoparticles, i.e. , nanoplatelets and nanowires, were synthesized by changing the concentration of NaOH during a hydrothermal treatment of precipitated Ti 4+ and Bi 3+ ions. The nanoparticles' crystal structures were characterized using atomic-resolution imaging with a C S -probe-corrected scanning-transmission electron microscope in combination with X-ray diffractometry and Raman spectroscopy. The nanoplatelets (10 nm thick and from 50 nm to 200 nm wide) exhibit the Aurivillius-type layered-perovskite crystal structure that is characteristic of Bi 4 Ti 3 O 12 , whereas the nanowires (from 15 nm to 35 nm wide and from several hundreds of nm to several μm long) exhibit an entirely new structure with an orthorhombic unit cell ( a = 3.804(1) Å, b = 11.816(3) Å, and c = 9.704(1) Å). The nanowire structure is composed of two structural layers alternating along the orthorhombic c -direction: a structural layer composed of two parallel layers of Bi atoms that resembles the (Bi 2 O 2 ) 2+ layer of the Aurivillius structure, and a structural layer composed of two parallel layers of Ti atoms, where every sixth Ti is replaced with Bi. Observations of the ferroelectric domains with transmission electron and piezo-response force microscopy indicated the ferroelectric nature of both nanostructures. The nanowire structure is a metastable polymorph of the bismuth titanate stabilized at the nanoscale. With annealing at temperatures above 500 °C the nanowire structure topotactically transforms into the Aurivillius structure.

Salinity is a growing global concern that affects the yield of crop species, including tomato ( Solanum lycopersicum ). Its wild relative Solanum chilense was reported to have halophyte properties. We compared salt resistance of both species during the reproductive phase, with a special focus on sodium localization in the flowers. Plants were exposed to NaCl from the seedling stage. Salinity decreased the number of inflorescences in both species but the number of flowers per inflorescence and sepal length only in S. lycopersicum . External salt supply decreased the stamen length in S. chilense , and it was associated with a decrease in pollen production and an increase in pollen viability. Although the fruit set was not affected by salinity, fruit weight and size decreased in S. lycopersicum . Concentrations and localization of Na, K, Mg, and Ca differed in reproductive structures of both species. Inflorescences and fruits of S. chilense accumulated more Na than S. lycopersicum . Sodium was mainly located in male floral organs of S. chilense but in non-reproductive floral organs in S. lycopersicum . The expression of Na transporter genes differed in flowers of both species. Overall, our results indicated that S. chilense was more salt-resistant than S. lycopersicum during the reproductive phase and that differences could be partly related to dissimilarities in element distribution and transport in flowers.

Degradation of carbon-supported Pt nanocatalysts in fuel cells and electrolyzers hinders widespread commercialization of these green technologies. Transition between oxidized and reduced states of Pt during fast potential spikes triggers significant Pt dissolution. Therefore, designing Pt-based catalysts able to withstand such conditions is of critical importance. We report here on a strategy to suppress Pt dissolution by using an organic matrix tris(aza)pentacene (TAP) as an alternative support material for Pt. The major benefit of TAP is its potential-dependent conductivity in aqueous media, which was directly evidenced by electrochemical impedance spectroscopy. At potentials below ∼0.45 V RHE , TAP is protonated and its conductivity is improved, which enables supported Pt to run hydrogen reactions. At potentials corresponding to Pt oxidation/reduction (>∼0.45 V RHE ), TAP is deprotonated and its conductivity is restricted. Tunable conductivity of TAP enhanced the durability of the Pt/TAP with respect to Pt/C when these two materials were subjected to the same degradation protocol (0.1 M HClO 4 electrolyte, 3000 voltammetric scans, 1 V/s, 0.05-1.4 V RHE ). The exceptional stability of Pt/TAP composite on a nanoscale level was confirmed by identical location TEM imaging before and after the used degradation protocol. Suppression of transient Pt dissolution from Pt/TAP with respect to the Pt/C benchmark was directly measured in a setup consisting of an electrochemical flow cell connected to inductively coupled plasma-mass spectrometry., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

Elemental LA-ICPMS mapping in continuous scanning mode gathers the counts generated upon laser ablation in line scanning mode. Acquisition of counts can be performed for each single laser pulse separately or by summing the counts of multiple laser pulses. Conventionally, pixels in an LA-ICPMS map are associated with spot-resolved single laser pulses (zero-dimensional, 0D), but also sub-pixel convolution strategies are in use, associated with one-dimensional (1D) or two-dimensional (2D) overlapping laser shots, and where possible followed by deblurring. The imaging quality of several 0D, 1D, and 2D LA-ICPMS strategies were compared for mapping of (ultra)low-concentration samples, both via computational and experimental approaches. The data presented will be helpful to make the right decision about the best possible LA-ICPMS mapping strategy for the highest image quality., (Copyright © 2021 Elsevier B.V. All rights reserved.)

First data on polycyclic aromatic hydrocarbons (PAHs) and nitro-aromatic compounds (NACs) in aerosols as well as of PAHs, polychlorinated biphenyls (PCBs) and NACs in bulk and wet atmospheric deposition samples were simultaneously obtained during 6-month-long field campaign at the costal central Adriatic area. Special attention was given to open-fire biomass burning episodes as extreme events common for the overall Mediterranean coastal area in order to gain a better understanding of the atmospheric variabilities and potential sources of trace organic pollutants in coastal environments. Diesel and gasoline combustion related to land and maritime traffic as well as occasional open-fire episodes (forest fires) were found to be the dominant pollution sources of PAHs in PM 10 particles. NACs were determined almost exclusively in samples affected by biomass burning episodes. Open-fire episodes had a strong contribution to the overall NACs atmospheric deposition fluxes. Several chlorinated congeners of PCBs were predominantly contributed in deposition samples., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Achieving highly active and stable oxygen reduction reaction performance at low platinum-group-metal loadings remains one of the grand challenges in the proton-exchange membrane fuel cells community. Currently, state-of-the-art electrocatalysts are high-surface-area-carbon-supported nanoalloys of platinum with different transition metals (Cu, Ni, Fe, and Co). Despite years of focused research, the established structure-property relationships are not able to explain and predict the electrochemical performance and behavior of the real nanoparticulate systems. In the first part of this work, we reveal the complexity of commercially available platinum-based electrocatalysts and their electrochemical behavior. In the second part, we introduce a bottom-up approach where atomically resolved properties, structural changes, and strain analysis are recorded as well as analyzed on an individual nanoparticle before and after electrochemical conditions (e.g. high current density). Our methodology offers a new level of understanding of structure-stability relationships of practically viable nanoparticulate systems., Competing Interests: The authors declare no competing interests., (© 2021 The Author(s).)

In the past decade, the development of single particle-inductively coupled plasma mass spectrometry (SP-ICPMS) has revolutionized the field of nanometallomics. Besides differentiation between dissolved and particulate metal signals, SP-ICPMS can quantify the nanoparticle (NP) number concentration and size. Because SP-ICPMS is limited to characterization of NPs in solution, we show how solid sampling by laser ablation (LA) adds spatial-resolution characteristics for localized NP analysis in biomaterials. Using custom-made gelatin standards doped with dissolved gold and commercial or synthesized gold nanoparticles, LA-SP-ICPMS conditions such as laser fluence, beam size, and dwell time were optimized for NP analysis to minimize NP degradation, peak overlap, and interferences from dissolved gold. A data-processing algorithm to retrieve the NP number concentration and size was developed for this purpose. As a proof-of-concept, a sunflower-root-sample cross-section, originating from a sunflower plant exposed to gold NPs, was successfully imaged using the optimized LA-SP-ICPMS conditions for localized NP characterization.