100 research outputs found

    Platinum recycling going green via induced surface potential alteration enabling fast and efficient dissolution

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    The recycling of precious metals, for example, platinum, is an essential aspect of sustainability for the modern industry and energy sectors. However, due to its resistance to corrosion, platinum-leaching techniques rely on high reagent consumption and hazardous processes, for example, boiling aqua regia; a mixture of concentrated nitric and hydrochloric acid. Here we demonstrate that complete dissolution of metallic platinum can be achieved by induced surface potential alteration, an 'electrode-less' process utilizing alternatively oxidative and reductive gases. This concept for platinum recycling exploits the so-called transient dissolution mechanism, triggered by a repetitive change in platinum surface oxidation state, without using any external electric current or electrodes. The effective performance in non-toxic low-concentrated acid and at room temperature is a strong benefit of this approach, potentially rendering recycling of industrial catalysts, including but not limited to platinum-based systems, more sustainable

    Molecular basis for functional diversity among microbial Nep1-like proteins

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    Necrosis and ethylene-inducing peptide 1 (Nep1)-like proteins (NLPs) are secreted by several phytopathogenic microorganisms. They trigger necrosis in various eudicot plants upon binding to plant sphingolipid glycosylinositol phosphorylceramides (GIPC). Interestingly, HaNLP3 from the obligate biotroph oomycete Hyaloperonospora arabidopsidis does not induce necrosis. We determined the crystal structure of HaNLP3 and showed that it adopts the NLP fold. However, the conformations of the loops surrounding the GIPC headgroup-binding cavity differ from those of cytotoxic Pythium aphanidermatum NLPPya. Essential dynamics extracted from \u3bcs-long molecular dynamics (MD) simulations reveals a limited conformational plasticity of the GIPC-binding cavity in HaNLP3 relative to toxic NLPs. This likely precludes HaNLP3 binding to GIPCs, which is the underlying reason for the lack of toxicity. This study reveals that mutations at key protein regions cause a switch between nontoxic and toxic phenotypes within the same protein scaffold. Altogether, these data provide evidence that protein flexibility is a distinguishing trait of toxic NLPs and highlight structural determinants for a potential functional diversification of non-toxic NLPs utilized by biotrophic plant pathogens

    Archaeal aminoacyl-tRNA synthetases interact with the ribosome to recycle tRNAs

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    Aminoacyl-tRNA synthetases (aaRS) are essential enzymes catalyzing the formation of aminoacyl-tRNAs, the immediate precursors for encoded peptides in ribosomal protein synthesis. Previous studies have suggested a link between tRNA aminoacylation and high-molecular-weight cellular complexes such as the cytoskeleton or ribosomes. However, the structural basis of these interactions and potential mechanistic implications are not well understood. To biochemically characterize these interactions we have used a system of two interacting archaeal aaRSs: an atypical methanogenic-type seryl-tRNA synthetase and an archaeal ArgRS. More specifically, we have shown by thermophoresis and surface plasmon resonance that these two aaRSs bind to the large ribosomal subunit with micromolar affinities. We have identified the L7/L12 stalk and the proteins located near the stalk base as the main sites for aaRS binding. Finally, we have performed a bioinformatics analysis of synonymous codons in the Methanothermobacter thermautotrophicus genome that supports a mechanism in which the deacylated tRNAs may be recharged by aaRSs bound to the ribosome and reused at the next occurrence of a codon encoding the same amino acid. These results suggest a mechanism of tRNA recycling in which aaRSs associate with the L7/L12 stalk region to recapture the tRNAs released from the preceding ribosome in polysome

    The Painters

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    ConspectusThe foreseeable worldwide energy and environmental challenges demand renewable alternative sources, energy conversion, and storage technologies. Therefore, electrochemical energy conversion devices like fuel cells, electrolyzes, and supercapacitors along with photoelectrochemical devices and batteries have high potential to become increasingly important in the near future. Catalytic performance in electrochemical energy conversion results from the tailored properties of complex nanometer-sized metal and metal oxide particles, as well as support nanostructures. Exposed facets, surface defects, and other structural and compositional features of the catalyst nanoparticles affect the electrocatalytic performance to varying degrees. The characterization of the nanometer-size and atomic regime of electrocatalysts and its evolution over time are therefore paramount for an improved understanding and significant optimization of such important technologies like electrolyzers or fuel cells. Transmission electron microscopy (TEM) and scanning transmission electron microscope (STEM) are to a great extent nondestructive characterization tools that provide structural, morphological, and compositional information with nanoscale or even atomic resolution. Due to recent marked advancement in electron microscopy equipment such as aberration corrections and monochromators, such insightful information is now accessible in many institutions around the world and provides huge benefit to everyone using electron microscopy characterization in general.Classical <i>ex situ</i> TEM characterization of random catalyst locations however suffers from two limitations regarding catalysis. First, the necessary low operation pressures in the range of 10<sup>–6</sup> to 10<sup>–9</sup> mbar for TEM are not in line with typical reaction conditions, especially considering electrocatalytic solid–liquid interfaces, so that the active state cannot be assessed. Second, and somewhat related, is the lack of time resolution for the evaluation of alterations of the usually highly heterogeneous nanomaterials. Two methods offer a solution to these shortcomings, namely, identical location TEM (IL-TEM) and electrochemical in situ liquid TEM. The former is already well established and has delivered novel insights particularly into degradation processes; however, characterization is still performed in vacuum. The latter circumvents this issue by using dedicated <i>in situ</i> TEM holders but introduces extremely demanding technical challenges. Although the introduction of revolutionizing thin SiN window cells, which elegantly confine the specimen from vacuum, has allowed demonstration of the potential of the <i>in situ</i> approach, the reproducibility and data interpretation is still limited predominately due to the strong interaction of the electron beam with the supporting electrolyte and electrode material. Because of the importance of understanding the nanoelectrochemical structure–function relationship, this Account aims to convey a timely perspective on the opportunities and particularly the challenges in electrochemical identical location TEM and <i>in situ</i> liquid cell TEM with a focus on electrochemical energy conversion

    Nanotubular TiOxNy-Supported Ir Single Atoms and Clusters as Thin-Film Electrocatalysts for Oxygen Evolution in Acid Media

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    A versatile approach to the production of cluster- and single atom-based thin-film electrode composites is presented. The developed TiOxNy–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 TiO2–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/TiOxNy–Ir interface as a result of the anodic oxidation mechanism. The developed TiOxNy–Ir catalyst exhibits very high oxygen evolution reaction activity in 0.1 M HClO4, reaching 1460 A g–1Ir 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

    Enhancing oxygen evolution functionality through anodization and nitridation of compositionally complex alloy

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    Compositionally complex materials (CCMs) have recently attracted great interest in electrocatalytic applications. To date, very few materials were systematically developed and tested due to the highly difficult preparation of high-surface-area CCMs. In this work, a surface of a compositionally complex FeCoNiCuZn alloy (CCA) was nitridated with subsequent anodization leading to morphological and compositional modifications. Notably, the electrochemical surface area and surface roughness as well as the electrocatalytic activity of the anodized material exhibit significant enhancement. Oxygen evolution reaction (OER) activity by the anodized CCN (CCN–AO) proceeds with remarkably small overpotential (233 mV) at 10 mA cm−2 in 1 M KOH. Experimental characterization indicates that the oxidation state of Co plays a critical role in the Fe–Co–Ni electrocatalyst. The developed approach and design strategy open up immense prospects in the preparation of a new, affordable, scalable and effective type of complex and high-performance electrocatalytic electrodes with tunable properties

    Interconversion between bound and free conformations of LexA orchestrates the bacterial SOS response

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    The bacterial SOS response is essential for the maintenance of genomes, and also modulates antibiotic resistance and controls multidrug tolerance in subpopulations of cells known as persisters. In Escherichia coli, the SOS system is controlled by the interplay of the dimeric LexA transcriptional repressor with an inducer, the active RecA filament, which forms at sites of DNA damage and activates LexA for self-cleavage. Our aim was to understand how RecA filament formation at any chromosomal location can induce the SOS system, which could explain the mechanism for precise timing of induction of SOS genes. Here, we show that stimulated self-cleavage of the LexA repressor is prevented by binding to specific DNA operator targets. Distance measurements using pulse electron paramagnetic resonance spectroscopy reveal that in unbound LexA, the DNA-binding domains sample different conformations. One of these conformations is captured when LexA is bound to operator targets and this precludes interaction by RecA. Hence, the conformational flexibility of unbound LexA is the key element in establishing a co-ordinated SOS response. We show that, while LexA exhibits diverse dissociation rates from operators, it interacts extremely rapidly with DNA target sites. Modulation of LexA activity changes the occurrence of persister cells in bacterial populations

    Overview of cattle diseases listed under category C, D or E in the animal health law for wich control programmes are in place within Europe

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    13 páginas, 5 figuras, 3 tablas.The COST action “Standardising output-based surveillance to control non-regulated diseases of cattle in the European Union (SOUND control),” aims to harmonise the results of surveillance and control programmes (CPs) for non-EU regulated cattle diseases to facilitate safe trade and improve overall control of cattle infectious diseases. In this paper we aimed to provide an overview on the diversity of control for these diseases in Europe. A non-EU regulated cattle disease was defined as an infectious disease of cattle with no or limited control at EU level, which is not included in the European Union Animal health law Categories A or B under Commission Implementing Regulation (EU) 2020/2002. A CP was defined as surveillance and/or intervention strategies designed to lower the incidence, prevalence, mortality or prove freedom from a specific disease in a region or country. Passive surveillance, and active surveillance of breeding bulls under Council Directive 88/407/EEC were not considered as CPs. A questionnaire was designed to obtain country-specific information about CPs for each disease. Animal health experts from 33 European countries completed the questionnaire. Overall, there are 23 diseases for which a CP exists in one or more of the countries studied. The diseases for which CPs exist in the highest number of countries are enzootic bovine leukosis, bluetongue, infectious bovine rhinotracheitis, bovine viral diarrhoea and anthrax (CPs reported by between 16 and 31 countries). Every participating country has on average, 6 CPs (min–max: 1–13) in place. Most programmes are implemented at a national level (86%) and are applied to both dairy and non-dairy cattle (75%). Approximately one-third of the CPs are voluntary, and the funding structure is divided between government and private resources. Countries that have eradicated diseases like enzootic bovine leukosis, bluetongue, infectious bovine rhinotracheitis and bovine viral diarrhoea have implemented CPs for other diseases to further improve the health status of cattle in their country. The control of non-EU regulated cattle diseases is very heterogenous in Europe. Therefore, the standardising of the outputs of these programmes to enable comparison represents a challenge.Peer reviewe

    Infectious bovine rhinotracheitis control program in Slovakia

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    As for other European countries, IBR is a significant cause of financial losses in cattle in Slovakia. The State Veterinary and Food Administration of the Slovak Republic prepared a voluntary IBR control program for cattle farms in 1995, which was implemented in 1996. In subsequent years, 48-119 farms/year enrolled in the voluntary IBR control program. Since the end of 2006, the IBR control program became compulsory by law for all cattle farms in Slovakia. Serology was used to identify infected animals using a conventional ELISA amongst non-vaccinated cattle and a gE specific ELISA in cattle vaccinated with marker vaccine. Eradication is based on culling when the serological prevalence of IBR in a herd is below 15%. When the prevalence is higher than 15%, the culling is combined with the application of a marker vaccine. A radical method where all animals are slaughtered is used with the agreement of the farmer when appropriate, especially for very small herds. Depending upon the selected eradication method, the antibody positive cattle can be gradually replaced in the herds to eliminate financial losses due to the disease. The movement of cattle is under strict control requiring a health certificate issued by the state veterinary authority and the movement must be recorded in the central livestock registry. The next step for herds is monitoring to achieve official IBR-free status. Based on the official figures from The State Veterinary and Food Administration, 60.2% herds were free of IBR in Slovakia in 2020

    Evaluation of solid carvedilol-loaded SMEDDS produced by the spray drying method and a study of related substances

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    In this study, various formulations of solidified carvedilol-loaded SMEDDS with high SMEDDS loading (up to 67% w/w) were produced with the spray drying process using various porous silica-based carriers. The process yield was improved with higher atomization gas flow rate during the spray drying process and with prolonged mixing time of dispersion of liquid SMEDDS and solid porous carriers prior to the spray drying process. Depending on the choice of the carrier and the SMEDDS:carrier ratio in solid SMEDDS, different drug loading, self-microemulsifying properties, drug release rates, and released drug fractions were obtained. The products exhibited fast drug release due to preserved self-microemulsifying properties and the absence of crystalline carvedilol, which was confirmed with XRD and Raman mapping. A decrease in drug content during the stability study was observed and investigated. This was at least partially attributed to the chemical degradation of the drug. Key degradation products determined by the LC-MS method were amides formed by in situ reaction of carvedilol with fatty acids present in the oily phase of SMEDDS
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