The influence of the electrolyte on the electrochemical behavior of PTMA as cathodic electrode material

The TEMPO-based polymer PTMA is a standard material for the research of organic radical batteries and displays a high capacity and a high rate stability at elevated currents when used with lithium-ion battery electrolytes. However, these electrolytes are the source of safety concerns and cause the dissolution of the organic electrode active material in the electrolyte, which limits the cycle life and leads to increased self-discharge. The aim of this thesis is to investigate the complex interactions and the resulting electrochemical behavior of PTMA-based electrodes in combination with different alternative electrolytes. The integrated publications establish the important role of the electrolyte for organic active materials and the lack of studies on this topic. Subsequently, the great influence of the electrolyte composition and concentration on the performance of PTMA-based electrodes is highlighted. In particular, a positive effect of highly concentrated electrolytes on the stability and self-discharge of PTMA-based electrodes is revealed. Based on this, the use of aprotic and protic ionic liquids as electrolytes for PTMA is investigated. There, a superior performance for PTMA in FSI--based aprotic ionic liquids is obtained. Lastly, the important aspect of self-discharge of PTMA with respect to current, rest time and electrolyte is studied. It is shown that the self-discharge mechanism strongly depends on the applied charging current, which is affected by the transport properties of the used electrolyte. The results of this dissertation show that the electrochemical behavior of PTMA is significantly affected by the alternative electrolytes. It is evident that with the use of different electrolyte concepts, the performance of PTMA can be optimized in a task-specific manner. In addition, the studies show that the electrolyte of an electrochemical investigation setup can be understood as a tool that can influence and elucidate the processes within the cells

Depth-Resolved Phase Analysis of Expanded Austenite Formed in Austenitic Stainless Steel

Expanded austenite γN formed after nitrogen insertion into austenitic stainless steel and CoCr alloys is known as a hard and very wear resistant phase. Nevertheless, no single composition and lattice expansion can describe this phase with nitrogen in solid solution. Using in situ X-ray diffraction (XRD) during ion beam sputtering of expanded austenite allows a detailed depth-dependent phase analysis, correlated with the nitrogen depth profiles obtained by time-of-flight secondary ion mass spectrometry (ToF-SIMS) or glow discharge optical emission spectroscopy (GDOES). Additionally, in-plane XRD measurements at selected depths were performed for strain analysis. Surprisingly, an anomalous peak splitting for the (200) expanded peak was observed for some samples during nitriding and sputter etching, indicating a layered structure only for {200} oriented grains. The strain analysis as a function of depth and orientation of scattering vector (parallel/perpendicular to the surface) is inconclusive. © 2020 by the authors. Licensee MDPI, Basel, Switzerland

Application of next-generation sequencing to Enterobacter hormaechei subspecies analysis during a neonatal intensive care unit outbreak

Introduction: The Enterobacter cloacae complex (ECC) species are potential neonatal pathogens, and ECC strains are among the most commonly encountered Enterobacter spp. associated with nosocomial bloodstream infections. Outbreaks caused by ECC can lead to significant morbidity and mortality in susceptible neonates. At the molecular level, ECC exhibits genomic heterogeneity, with six closely related species and subspecies. Genetic variability poses a challenge in accurately identifying outbreaks by determining the clonality of ECC isolates. This difficulty is further compounded by the limitations of the commonly used molecular typing methods, such as pulsed field gel electrophoresis, which do not provide reliable accuracy in distinguishing between ECC strains and can lead to incorrect conclusions. Next-generation sequencing (NGS) offers superior resolution in determining strain relatedness. Therefore, we investigated the clinical pertinence of incorporating NGS into existing bundle measures to enhance patient management during an outbreak of ECC in a level-3 neonatal intensive care unit (NICU) in Germany. Methods: As the standard of care, all neonates on the NICU received weekly microbiological swabs (nasopharyngeal and rectal) and analysis of endotracheal secretion, where feasible. During the 2.5-month outbreak, colonisation with ECC was detected in n = 10 neonates. The phylogenetic relationship and potential antimicrobial resistance genes as well as mobile genetic elements were identified via bacterial whole-genome sequencing (WGS) using Illumina MiSeq followed by in silico data analysis. Results: Although all ECC isolates exhibited almost identical antimicrobial susceptibility patterns, the WGS data revealed the involvement of four different ECC clones. The isolates could be characterised as Enterobacter hormaechei subspecies steigerwaltii (n = 6, clonal), subsp. hoffmannii (n = 3, two clones) and subsp. oharae (n = 1). Despite the collection of environmental samples, no source of this diffuse outbreak could be identified. A new standardised operating procedure was implemented to enhance the management of neonates colonised with MRGN. This collaborative approach involved both parents and medical professionals and successfully prevented further transmission of ECC. Conclusions: Initially, it was believed that the NICU outbreak was caused by a single ECC clone due to the similarity in antibiotic resistance. However, our findings show that antibiotic susceptibility patterns can be misleading in investigating outbreaks of multi-drug-resistant ECC. In contrast, bacterial WGS accurately identified ECC at the clonal level, which significantly helped to delineate the nature of the observed outbreak

Emulsion polymerizations for a sustainable preparation of efficient TEMPO‐based electrodes

Organic polymer‐based batteries represent a promising alternative to present‐day metal‐based systems and a valuable step toward printable and customizable energy storage devices. However, most scientific work is focussed on the development of new redox‐active organic materials, while straightforward manufacturing and sustainable materials and production will be a necessary key for the transformation to mass market applications. Here, a new synthetic approach for 2,2,6,6‐tetramethyl‐4‐piperinidyl‐ N ‐oxyl (TEMPO)‐based polymer particles by emulsion polymerization and their electrochemical investigation are reported. The developed emulsion polymerization protocol based on an aqueous reaction medium allowed the sustainable synthesis of a redox‐active electrode material, combined with simple variation of the polymer particle size, which enabled the preparation of nanoparticles from 35 to 138 nm. Their application in cell experiments revealed a significant effect of the size of the active‐polymer particles on the performance of poly(2,2,6,6‐tetramethyl‐4‐piperinidyl‐ N ‐oxyl methacrylate) (PTMA)‐based electrodes. In particular rate capabilities were found to be reduced with larger diameters. Nevertheless, all cells based on the different particles revealed the ability to recover from temporary capacity loss due to application of very high charge/discharge rates.Sustainable and efficient organic electrode : A new synthetic approach for polymers for organic batteries includes an emulsion polymerization with adjustable particle sizes in aqueous dispersions and allows the sustainable manufacturing of active materials and composite electrodes. The electrochemical investigation shows that the influence of particle sizes and the resulting morphologies of composite films on the cell performance is as important as the active material itself

An online international comparison of palliative care identification in primary care using the Surprise Question.

BACKGROUND The Surprise Question ('Would I be surprised if this patient died within 12 months?') identifies patients in the last year of life. It is unclear if 'surprised' means the same for each clinician, and whether their responses are internally consistent. AIM To determine the consistency with which the Surprise Question is used. DESIGN A cross-sectional online study of participants located in Belgium, Germany, Italy, The Netherlands, Switzerland and UK. Participants completed 20 hypothetical patient summaries ('vignettes'). Primary outcome measure: continuous estimate of probability of death within 12 months (0% [certain survival]-100% [certain death]). A threshold (probability estimate above which Surprise Question responses were consistently 'no') and an inconsistency range (range of probability estimates where respondents vacillated between responses) were calculated. Univariable and multivariable linear regression explored differences in consistency. Trial registration: NCT03697213. SETTING/PARTICIPANTS Registered General Practitioners (GPs). Of the 307 GPs who started the study, 250 completed 15 or more vignettes. RESULTS Participants had a consistency threshold of 49.8% (SD 22.7) and inconsistency range of 17% (SD 22.4). Italy had a significantly higher threshold than other countries (p = 0.002). There was also a difference in threshold levels depending on age of clinician, for every yearly increase, participants had a higher threshold. There was no difference in inconsistency between countries (p = 0.53). CONCLUSIONS There is variation between clinicians regarding the use of the Surprise Question. Over half of GPs were not internally consistent in their responses to the Surprise Question. Future research with standardised terms and real patients is warranted

Closely related Campylobacter jejuni strains from different sources reveal a generalist rather than a specialist lifestyle

Background: Campylobacter jejuni and Campylobacter coli are human intestinal pathogens of global importance. Zoonotic transmission from livestock animals or animal-derived food is the likely cause for most of these infections. However, little is known about their general and host-specific mechanisms of colonization, or virulence and pathogenicity factors. In certain hosts, Campylobacter species colonize persistently and do not cause disease, while they cause acute intestinal disease in humans. Results: Here, we investigate putative host-specificity using phenotypic characterization and genome-wide analysis of genetically closely related C. jejuni strains from different sources. A collection of 473 fresh Campylobacter isolates from Germany was assembled between 2006 and 2010 and characterized using MLST. A subset of closely related C. jejuni strains of the highly prevalent sequence type ST-21 was selected from different hosts and isolation sources. PCR typing of strain-variable genes provided evidence that some genes differed between these strains. Furthermore, phenotypic variation of these strains was tested using the following criteria: metabolic variation, protein expression patterns, and eukaryotic cell interaction. The results demonstrated remarkable phenotypic diversity within the ST-21 group, which however did not correlate with isolation source. Whole genome sequencing was performed for five ST-21 strains from chicken, human, bovine, and food sources, in order to gain insight into ST-21 genome diversity. The comparisons showed extensive genomic diversity, primarily due to recombination and gain of phage-related genes. By contrast, no genomic features associated with isolation source or host were identified. Conclusions: The genome information and phenotypic data obtained in vitro and in a chicken infection model provided little evidence of fixed adaptation to a specific host. Instead, the dominant C. jejuni ST-21 appeared to be characterized by phenotypic flexibility and high genetic microdiversity, revealing properties of a generalist. High genetic flexibility might allow generalist variants of C. jejuni to reversibly express diverse fitness factors in changing environments

Photoelectron spectroscopy and dissociative photoionization of fulminic acid, HCNO

We report a joint experimental and computational study of the photoelectron spectroscopy and the dissociative photoionization of fulminic acid, HCNO. The molecule is of interest to astrochemistry and astrobiology as a potential precursor of prebiotic molecules. Synchrotron radiation was used as the photon source. Dispersive photoelectron spectra were recorded from 10~eV to 22~eV, covering four band systems in the HCNO cation and an ionization energy of 10.83~eV was determined. Transitions into the Renner-Teller distorted $X^+{}^2\Pi$ state of the cation were simulated using wavepacket dynamics based on a vibronic coupling Hamiltonian. Very good agreement between experiment and theory is obtained. While the first excited state of the cation shows only a broad and unstructured spectrum, the next two higher states exhibit a well-resolved vibrational progression. Transitions into the excited electronic states of \cation{HCNO}{+} were not simulated, due to the large number of electronic states that contribute to these transitions. Nevertheless, a qualitative assignment is given, based on the character of the orbitals involved in the transitions. The dissociative photoionization was investigated by photoelectron-photoion coincidence spectroscopy. The breakdown diagram shows evidence for isomerization from \cation{HCNO}{+} to \cation{HNCO}{+} on the cationic potential energy surface. Zero Kelvin appearance energies for the daughter ions \cation{HCO}{+} and \cation{NCO}{+} have been derived

The question of access to the Japanese market

This survey focuses on the question of how market structure and different corporate organisational forms might affect access to the Japanese market for industrial goods. The question is how and whether keiretsu corporate structures in Japan constitute an important unofficial barrier in access to the Japanese market for manufactured goods

Structural basis for type VI secreted peptidoglycan DL-endopeptidase function, specificity and neutralization in <em>Serratia marcescens</em>

Some Gram-negative bacteria target their competitors by exploiting the type VI secretion system to extrude toxic effector proteins. To prevent self-harm, these bacteria also produce highly specific immunity proteins that neutralize these antagonistic effectors. Here, the peptidoglycan endopeptidase specificity of two type VI secretion-system-associated effectors from Serratia marcescens is characterized. These small secreted proteins, Ssp1 and Ssp2, cleave between γ-d-glutamic acid and l-meso-diaminopimelic acid with different specificities. Ssp2 degrades the acceptor part of cross-linked tetratetrapeptides. Ssp1 displays greater promiscuity and cleaves monomeric tripeptides, tetrapeptides and pentapeptides and dimeric tetratetra and tetrapenta muropeptides on both the acceptor and donor strands. Functional assays confirm the identity of a catalytic cysteine in these endopeptidases and crystal structures provide information on the structure–activity relationships of Ssp1 and, by comparison, of related effectors. Functional assays also reveal that neutralization of these effectors by their cognate immunity proteins, which are called resistance-associated proteins (Raps), contributes an essential role to cell fitness. The structures of two immunity proteins, Rap1a and Rap2a, responsible for the neutralization of Ssp1 and Ssp2-like endopeptidases, respectively, revealed two distinct folds, with that of Rap1a not having previously been observed. The structure of the Ssp1–Rap1a complex revealed a tightly bound heteromeric assembly with two effector molecules flanking a Rap1a dimer. A highly effective steric block of the Ssp1 active site forms the basis of effector neutralization. Comparisons with Ssp2–Rap2a orthologues suggest that the specificity of these immunity proteins for neutralizing effectors is fold-dependent and that in cases where the fold is conserved sequence differences contribute to the specificity of effector–immunity protein interactions

Correlations between SO2 flux, seismicity, and outgassing activity at the open vent of Villarrica volcano, Chile

The characteristics of the open vent activity of Villarrica volcano, Chile, were studied in detail by integrating visual observations of the lava lake, analysis of the seismic tremor, and measurements of SO2 flux. The outgassing activity comprises a persistent gas plume emission from the bottom of the crater as well as frequent explosive events. Three main styles of bubble bursting were identified at the surface of the active lava lake: seething magma, small short-lived lava fountains, and Strombolian explosions. Seething magma consists of continual burst of relatively small bubbles (a few meters in diameter) with varying strength over the entire surface of the lava lake. Small lava fountains, seen as a vigorous extension of seething magma, commonly have durations of 20–120 s and reach 10–40 m high above the lava lake. Correlations between seismicity and visual observations indicate that the seismic tremor is mostly caused by the explosive outgassing activity. Furthermore, for different periods between 2000 and 2006, during which the activity remained comparable, the real-time seismic amplitude measurement system (RSAM) and SO2 emission rates show a very good correlation. Higher SO2 emissions appeared to be related to higher levels of the lava lake, stronger bubble bursting activity, and changes in the morphology and texture of the crater floor. Background (low) levels of activity correspond to a lava lake located >80 m below the crater rim, small and/or blocky morphology of the roof, seismic amplitude (RSAM) lower than 25 units, few volcano-tectonic earthquakes, and daily averages of SO2 emissions lower than 600 Mg/d