Entwicklung von Bipolar-Grenzflächen Brennstoffzellen für den Einsatz von Fe-N/C basierten Kathoden Elektroden

In this work, the concept of a bipolar interface membrane electrode assembly (MEA) for the utilization of the platinum group metal (PGM) - free ORR catalyst Fe-N/C is investigated for the first time. More specifically, the bipolar MEA discussed in this work means the combination of an alkaline cathode electrode and an acidic anode electrode separated by a proton exchange membrane (PEM). This bipolar MEA architecture is mainly motivated by the attempt to minimize the amount of PGM material in fuel cell systems while simultaneously providing a less corrosive environment for the PGM-free material, which would compensate for the main challenges of monopolar PEMFC and anion exchange membrane fuel cell (AEMFC) technology. It is demonstrated that the bipolar MEA architecture could be a promising alternative to conventional, monopolar MEA concepts for the employment of Fe-N/C. Moreover, this work highlights and identifies the main challenges of bipolar interface fuel cells (BPIFC) with Fe-N/C-based CCLs, both experimentally and theoretically analyzed. The following results significantly contributed to the development of the BPIFCs with Fe-N/C based CCLs: • By directly depositing the PEM on the alkaline cathode electrode, the highest power density to date for a BPIFC with a PGM-free CCL could be achieved. A direct influence of the bipolar interface on the fuel cell performance was demonstrated. Electrochemical impedance spectroscopy for the first time experimentally proved the contribution of the water formation reaction at the bipolar junction to the measureable charge transfer resistance • Variations of the directly deposited AEM content on the CCL have shown that the AEM can be used to some extent to regulate water transport into the porous layers and that electrode flooding is one of the main reasons for performance losses • Theoretical considerations regarding the water management in BPIFCs with thick PGM-free electrodes suggest a dual function of the cathode electrode, in which the CCL, in contrast to conventional fuel cell systems, can adopt an additional role similar to that of gas diffusion substrates • The introduction of a two-layer CCL architectures, with varied ionomer content or with altered wettability properties, verified the altered requirements for the watermanagement within BPIFCs that Fe-N/C as cathode catalyst materialIn dieser Arbeit wird zum ersten Mal das Konzept eine Membran-Elektroden-Einheit (MEA) mit bipolarer Grenzfläche für die Nutzung des platingruppenmetall (PGM)-freien ORRKatalysators Fe-N/C untersucht. Genauer gesagt, bedeutet die in dieser Arbeit diskutierte bipolare MEA Architektur die Kombination einer alkalischen Kathodenelektrode und einer sauren Anodenelektrode, die durch eine Protonenaustauschmembran (PEM) getrennt sind. Diese bipolare Architektur ist hauptsächlich durch den Versuch motiviert, die Menge an PGMMaterial in Brennstoffzellensystemen zu minimieren und gleichzeitig eine weniger korrosive Umgebung für das PGM-freie Material zu schaffen, was die größten Herausforderungen der monopolaren PEMFC- und Anionenaustauschmembran-Brennstoffzellentechnologie (AEMFC) lösen würde. Es wird gezeigt, dass die bipolare MEA-Architektur eine vielversprechende Alternative zu herkömmlichen, monopolaren MEA-Konzepten für den Einsatz von Fe-N/C sein könnte. Darüber hinaus werden in dieser Arbeit die wichtigsten Herausforderungen von BPIFCs mit Fe-N/C-basierten CCLs hervorgehoben und identifiziert, die sowohl experimentell als auch theoretisch analysiert werden. Die folgenden Ergebnisse haben wesentlich zur Entwicklung der BPIFCs mit Fe-N/C-basierten CCLs beigetragen: • Durch die direkte Abscheidung der PEM auf der alkalischen Kathodenelektrode konnte die bisher höchste Leistungsdichte für eine BPIFC mit einer PGM-freien CCL erreicht werden. Es wurde ein direkter Einfluss der bipolaren Schnittstelle auf die Leistung der Brennstoffzelle nachgewiesen. Elektrochemische Impedanzspektroskopie-Daten konnten erstmals experimentell den Beitrag der Wasserbildungsreaktion an der bipolaren Grenzfläche zum messbaren Ladungstransferwiderstand nachweisen • Variationen des AEM-Gehalts haben gezeigt, dass dieser zum Teil zur Regulierung des Wassertransports in die porösen Schichten genutzt werden kann und dass die Überflutung der Elektroden einer der Hauptgründe für Leistungseinbußen ist • Theoretische Überlegungen zum Wassermanagement in BPIFCs mit dicken PGMfreien Elektroden legen eine Doppelfunktion der Kathodenelektrode nahe, bei der die CCL im Gegensatz zu konventionellen Brennstoffzellensystemen eine zusätzliche Rolle ähnlich der von Gasdiffusionssubstraten übernehmen kann. • Die Einführung einer zweischichtigen CCL-Architektur mit unterschiedlichem Ionomergehalt oder mit veränderten Benetzungseigenschaften hat die veränderten Anforderungen an das Wassermanagement in BPIFCs mit Fe-N/C als Kathodenkatalysatormaterial bestätigt

Is antibacterial treatment intensity lower in elderly patients? A retrospective cohort study in a German surgical intensive care unit

Background: Demographic change concurrent with medical progress leads to an increasing number of elderly patients in intensive care units (ICUs). Antibacterial treatment is an important, often life-saving, aspect of intensive care but burdened by the associated antimicrobial resistance risk. Elderly patients are simultaneously at greater risk of infections and may be more restrictively treated because, generally, treatment intensity declines with age. We therefore described utilization of antibacterials in ICU patients older and younger than 80 years and examined differences in the intensity of antibacterial therapy between both groups. Methods: We analysed 17,464 valid admissions from the electronic patient data management system of our surgical ICU from April 2006 – October 2013. Antibacterial treatment rates were defined as days of treatment (exposed patient days) relative to patient days of ICU stay and calculated for old and young patients. Rates were compared in zero-inflated Poisson regression models adjusted for patients’ sex, mean SAPS II- and TISS-scores, and calendar years yielding adjusted rate ratios (aRRs). Rate ratios exceeding 1 represent higher rates in old patients reflecting greater treatment intensity in old compared to younger patients. Results: Observed antibacterial treatment rates were lower in patients 80 years and older compared to younger patients (30.97 and 39.73 exposed patient days per 100 patient days in the ICU, respectively). No difference in treatment intensity, however, was found from zero-inflated Poisson regression models permitting more adequate consideration of patient days with low treatment probability: for all antibacterials the adjusted rate ratio (aRR) was 1.02 (95%CI: 0.98–1.07). Treatment intensities were higher in elderly patients for penicillins (aRR 1.37 (95%CI: 1.26–1.48)), cephalosporins (aRR 1.20 (95%CI: 1.09–1.31)), carbapenems (aRR 1.35 (95%CI: 1.20–1.50)), fluoroquinolones (aRR 1.17 (95%CI: 1.05–1.30), and imidazoles (aRR 1.34 (95%CI: 1.23–1.46)). Conclusions: Elderly patients were generally less likely to be treated with antibacterials. This observation, however, did not persist in patients with comparable treatment probability. In these, antibacterial treatment intensity did not differ between younger and older ICU patients, for some antibacterial classes treatment intensity was even higher in the latter. Patient-level covariates are instrumental for a nuanced evaluation of age-effects in antibacterial treatment in the ICU

CT fluoroscopy‐guided pancreas transplant biopsies: a retrospective evaluation of predictors of complications and success rates

To identify predictors of biopsy success and complications in CT-guided pancreas transplant (PTX) core biopsy. We retrospectively identified all CT fluoroscopy-guided PTX biopsies performed at our institution (2000-2017) and included 187 biopsies in 99 patients. Potential predictors related to patient characteristics (age, gender, body mass index (BMI), PTX age, PTX volume) and procedure characteristics (biopsy depth, needle size, access path, number of samples, interventionalist's experience) were correlated with biopsy success (sufficient tissue for histologic diagnosis) and the occurrence of complications. Biopsy success (72.2%) was more likely to be obtained in men [+25.3% (10.9, 39.7)] and when the intervention was performed by an experienced interventionalist [+27.2% (8.1, 46.2)]. Complications (5.9%) occurred more frequently in patients with higher PTX age [OR: 1.014 (1.002, 1.026)] and when many (3-4) tissue samples were obtained [+8.7% (-2.3, 19.7)]. Multivariable regression analysis confirmed male gender [OR: 3.741 (1.736, 8.059)] and high experience [OR: 2.923 (1.255, 6.808)] (biopsy success) as well as older PTX age [OR: 1.019 (1.002, 1.035)] and obtaining many samples [OR: 4.880 (1.240, 19.203)] (complications) as independent predictors. Our results suggest that CT-guided PTX biopsy should be performed by an experienced interventionalist to achieve higher success rates, and not more than two tissue samples should be obtained to reduce complications. Caution is in order in patients with older transplants because of higher complication rates

Green-up selection by red deer in heterogeneous, human-dominated landscapes of Central Europe

The forage maturation hypothesis (FMH) assumes that herbivores cope with the trade-off between digestibility and biomass in forage by selecting vegetation at intermediate growth. The green wave hypothesis (GWH) extends the FMH to suggest how spatiotemporal heterogeneity in plant quality shapes migratory movements of herbivores. Growing empirical support for these hypotheses mainly comes from studies in vast landscapes with large-scale habitat heterogeneity. It is unclear, however, to what extent ungulates surf green waves in human-altered landscapes with small-scale heterogeneity in terms of land use and topography. We used plant phenological proxies derived from Sentinel 2 satellite data to analyze the habitat selection of 93 collared red deer (Cervus elaphus) in montane and alpine habitats. Using a step selection analysis, we investigated how plant phenology, that is, the instantaneous rate of green-up (IRG) and normalized difference vegetation index (NDVI), and a set of variables describing topography and human presence influenced red deer resource selection in open habitats. We learned that red deer selected areas with high biomass at green-up and avoided habitats with possible exposure to human activity. Additionally, landscape structure and topography strongly influenced spatial behavior of red deer. We further compared cumulative access to high-quality forage across migrant strategies and found migrants gained better access than residents. Many migratory individuals surfed the green wave, and their surfing behavior, however, became less pronounced with decreasing distance to settlements. Within the constraints of topography and human land use, red deer track spring green-up on a fine spatiotemporal scale and follow the green wave across landscapes in migration movements. Thus, they benefit from high-quality forage even in human-dominated landscapes with small-scale heterogeneity and vegetation emerging in a heterogenic, dynamic mosaic

Neural processing of emotional facial stimuli in specific phobia: An fMRI study

Background Patients with specific phobia (SP) show altered brain activation when confronted with phobia-specific stimuli. It is unclear whether this pathogenic activation pattern generalizes to other emotional stimuli. This study addresses this question by employing a well-powered sample while implementing an established paradigm using nonspecific aversive facial stimuli. Methods N = 111 patients with SP, spider subtype, and N = 111 healthy controls (HCs) performed a supraliminal emotional face-matching paradigm contrasting aversive faces versus shapes in a 3-T magnetic resonance imaging scanner. We performed region of interest (ROI) analyses for the amygdala, the insula, and the anterior cingulate cortex using univariate as well as machine-learning-based multivariate statistics based on this data. Additionally, we investigated functional connectivity by means of psychophysiological interaction (PPI). Results Although the presentation of emotional faces showed significant activation in all three ROIs across both groups, no group differences emerged in all ROIs. Across both groups and in the HC > SP contrast, PPI analyses showed significant task-related connectivity of brain areas typically linked to higher-order emotion processing with the amygdala. The machine learning approach based on whole-brain activity patterns could significantly differentiate the groups with 73% balanced accuracy. Conclusions Patients suffering from SP are characterized by differences in the connectivity of the amygdala and areas typically linked to emotional processing in response to aversive facial stimuli (inferior parietal cortex, fusiform gyrus, middle cingulate, postcentral cortex, and insula). This might implicate a subtle difference in the processing of nonspecific emotional stimuli and warrants more research furthering our understanding of neurofunctional alteration in patients with SP.Deutsche Forschungsgemeinschaft http://dx.doi.org/10.13039/501100001659Peer Reviewe

Singlet Fission in Pyrene‐Fused Azaacene Dimers

Singlet fission has emerged as a promising strategy to avoid the loss of extra energy through thermalization in solar cells. A family of dimers consisting of nitrogen‐doped pyrene‐fused acenes that undergo singlet fission with triplet quantum yields as high as 125 % are presented. They provide new perspectives for nitrogenated polycyclic aromatic hydrocarbons and for the design of new materials for singlet fission

The neural signature of psychomotor disturbance in depression.

Up to 70% of patients with major depressive disorder present with psychomotor disturbance (PmD), but at the present time understanding of its pathophysiology is limited. In this study, we capitalized on a large sample of patients to examine the neural correlates of PmD in depression. This study included 820 healthy participants and 699 patients with remitted (n = 402) or current (n = 297) depression. Patients were further categorized as having psychomotor retardation, agitation, or no PmD. We compared resting-state functional connectivity (ROI-to-ROI) between nodes of the cerebral motor network between the groups, including primary motor cortex, supplementary motor area, sensory cortex, superior parietal lobe, caudate, putamen, pallidum, thalamus, and cerebellum. Additionally, we examined network topology of the motor network using graph theory. Among the currently depressed 55% had PmD (15% agitation, 29% retardation, and 11% concurrent agitation and retardation), while 16% of the remitted patients had PmD (8% retardation and 8% agitation). When compared with controls, currently depressed patients with PmD showed higher thalamo-cortical and pallido-cortical connectivity, but no network topology alterations. Currently depressed patients with retardation only had higher thalamo-cortical connectivity, while those with agitation had predominant higher pallido-cortical connectivity. Currently depressed patients without PmD showed higher thalamo-cortical, pallido-cortical, and cortico-cortical connectivity, as well as altered network topology compared to healthy controls. Remitted patients with PmD showed no differences in single connections but altered network topology, while remitted patients without PmD did not differ from healthy controls in any measure. We found evidence for compensatory increased cortico-cortical resting-state functional connectivity that may prevent psychomotor disturbance in current depression, but may perturb network topology. Agitation and retardation show specific connectivity signatures. Motor network topology is slightly altered in remitted patients arguing for persistent changes in depression. These alterations in functional connectivity may be addressed with non-invasive brain stimulation

Intramolecular Triplet Diffusion Facilitates Triplet Dissociation in a Pentacene Hexamer

Triplet dynamics in singlet fission depend strongly on the strength of the electronic coupling. Covalent systems in solution offer precise control over such couplings. Nonetheless, efficient free triplet generation remains elusive in most systems, as the intermediate triplet pair 1(T1T1) is prone to triplet‐triplet annihilation due to its spatial confinement. In the solid state, entropically driven triplet diffusion assists in the spatial separation of triplets, resulting in higher yields of free triplets. Control over electronic coupling in the solid state is, however, challenging given its sensitivity to molecular packing. We have thus developed a hexameric system (HexPnc) to enable solid‐state‐like triplet diffusion at the molecular scale. This system is realized by covalently tethering three pentacene dimers to a central subphthalocyanine scaffold. Transient absorption spectroscopy, complemented by theoretical structural optimizations and steady‐state spectroscopy, reveals that triplet diffusion is indeed facilitated due to intramolecular cluster formation. The yield of free triplets in HexPnc is increased by a factor of up to 14 compared to the corresponding dimeric reference (DiPnc). Thus, HexPnc establishes crucial design aspects for achieving efficient triplet dissociation in strongly coupled systems by providing avenues for diffusive separation of 1(T1T1), while, concomitantly, retaining strong interchromophore coupling which preserves rapid formation of 1(T1T1).Efficient free triplet generation via singlet fission remains elusive in covalent systems. We have developed a hexameric pentacene system, in which three pentacene dimers are covalently linked to a central subphthalocyanine scaffold. This allows for an entropically driven triplet diffusion, resulting in higher yields of free triplets, and establishes crucial design aspects for achieving efficient triplet dissociation in strongly coupled systems. image Deutsche Forschungsgemeinschaft http://dx.doi.org/10.13039/50110000165

Interaction of developmental factors and ordinary stressful life events on brain structure in adults

An interplay of early environmental and genetic risk factors with recent stressful life events (SLEs) in adulthood increases the risk for adverse mental health outcomes. The interaction of early risk and current SLEs on brain structure has hardly been investigated. Whole brain voxel-based morphometry analysis was performed in N = 786 (64.6% female, mean age = 33.39) healthy subjects to identify correlations of brain clusters with commonplace recent SLEs. Genetic and early environmental risk factors, operationalized as those for severe psychopathology (i.e., polygenic scores for neuroticism, childhood maltreatment, urban upbringing and paternal age) were assessed as modulators of the impact of SLEs on the brain. SLEs were negatively correlated with grey matter volume in the left medial orbitofrontal cortex (mOFC, FWE p = 0.003). This association was present for both, positive and negative, life events. Cognitive-emotional variables, i.e., neuroticism, perceived stress, trait anxiety, intelligence, and current depressive symptoms did not account for the SLE-mOFC association. Further, genetic and environmental risk factors were not correlated with grey matter volume in the left mOFC cluster and did not affect the association between SLEs and left mOFC grey matter volume. The orbitofrontal cortex has been implicated in stress-related psychopathology, particularly major depression in previous studies. We find that SLEs are associated with this area. Important early life risk factors do not interact with current SLEs on brain morphology in healthy subjects

Mega-analysis of association between obesity and cortical morphology in bipolar disorders:ENIGMA study in 2832 participants

Background: Obesity is highly prevalent and disabling, especially in individuals with severe mental illness including bipolar disorders (BD). The brain is a target organ for both obesity and BD. Yet, we do not understand how cortical brain alterations in BD and obesity interact. Methods: We obtained body mass index (BMI) and MRI-derived regional cortical thickness, surface area from 1231 BD and 1601 control individuals from 13 countries within the ENIGMA-BD Working Group. We jointly modeled the statistical effects of BD and BMI on brain structure using mixed effects and tested for interaction and mediation. We also investigated the impact of medications on the BMI-related associations. Results: BMI and BD additively impacted the structure of many of the same brain regions. Both BMI and BD were negatively associated with cortical thickness, but not surface area. In most regions the number of jointly used psychiatric medication classes remained associated with lower cortical thickness when controlling for BMI. In a single region, fusiform gyrus, about a third of the negative association between number of jointly used psychiatric medications and cortical thickness was mediated by association between the number of medications and higher BMI. Conclusions: We confirmed consistent associations between higher BMI and lower cortical thickness, but not surface area, across the cerebral mantle, in regions which were also associated with BD. Higher BMI in people with BD indicated more pronounced brain alterations. BMI is important for understanding the neuroanatomical changes in BD and the effects of psychiatric medications on the brain.</p