Social Justice in the EU and OECD. Bertelsmann Stiftung Index Report 2019

With the onset of the economic and financial crisis, social justice has deteriorated – on average – in the OECD and EU countries surveyed by the SJI.1 While the Social Justice Index shows a slight but ongoing upward trend since economic recovery began in 2014, the overall score remains below the pre-crisis level. In addition, there are still striking discrepancies with regard to available opportunities to participate in society in the 41 countries surveyed

Interaction Of Hydrogen With A Pd(210)- And A Ni(210) Surface

Titelseite und Inhaltsverzeichnis 0\. Einleitung 5 1\. Allgemeiner Teil 7 1.2. Die (210)-Oberfläche 7 1.2. Allgemeines zur H-Adsorption 10 1.3. Dissoziation von Wasserstoff auf Metalloberflächen 13 1.4. Zur Bindung von Wasserstoffmolekülen an Metalloberflächen 23 1.5. Beispiele für molekularen Wasserstoff auf Metalloberflächen 30 2\. Experimenteller Teil 35 2.1. Augerelektronenspektroskopie (AES) 35 2.3. Beugung langsamer Elektronen (LEED) 37 2.3. Thermodesorptionsspektroskopie (TDS) 40 2.4. Änderung der Austrittsarbeit 44 2.5. Photoemissionsspektroskopie (UPS) 47 2.6. Schwingungsspektroskopie (HREELS) 53 2.7. Apparativer Aufbau 60 2.8. Substrate 63 2.9. Probenpräparation 65 Motivation 67 3\. Untersuchungen der reinen Wasserstoffsysteme H2/Pd(210) und H2/Ni(210) 69 3.1. Wechselwirkung von Wasserstoff mit einer Pd(210)-Oberfläche 69 3.2. Wechselwirkung von Wasserstoff mit einer Ni(210)-Oberfläche 86 4\. Zur konkurrierenden Adsorption von atomaren und molekularen Wasserstoff 101 5\. Untersuchungen zum Subsurface-Zustand 118 6\. Das H2/CO/Pd(210)-Koadsorptionssystem 130 6.1. Das reine CO/Pd(210)-System 131 6.2. Die H/CO Koadsorption auf der Pd(210)-Oberfläche 138 6.3. Diskussion 144 7\. Diskussion 150 8.1. Zusammenfassung 167 8.2. Summary 169 9\. Literatur 1718 In der vorliegenden Arbeit wurde die Wechselwirkung von Wasserstoff mit einer Pd(210)- und Ni(210)-Oberfläche mit Hilfe von Thermodesorptionsspektren (TDS), Messungen der Austrittsarbeitsänderung (DF), Photoemissionsspektren (UPS), Elektronenenergieverlustspektren (HREELS) und H2/D2-Isotopenaustausch- Messungen untersucht. Das H2-Adsorptionsverhalten stimmt für beide Oberflächen stark überein: Bei Temperaturen größer als 100K adsorbiert Wasserstoff spontan dissoziativ und bildet unter Erhöhung der Austrittsarbeit drei atomare Bindungszustände. Wird die Adsorptionstemperatur auf 50K reduziert, adsorbiert der Wasserstoff zusätzlich molekular in zwei Chemisorptionszustände. Dabei wird die Austrittsarbeit vermindert. Die molekulare Natur dieser Zustände wurde mit Hilfe von H2/D2-Austauschexperimenten, durch die Beobachtung einer H-H-Schwingungsbande im HREELS und der Detektion von s-H2/Pd- bzw. s*-H2/Pd- Bindungszuständen im UPS belegt. Neben den relativ hohen Desorptionstemperaturen weist auch die energetische Lage der Signale in den HREEL- und UP-Spektren eine chemisorptive Wechselwirkung nach. Die in den UP- Spektren beobachtete H2-induzierte Änderung der d-Bandstruktur kann mit einem Bindungsmodell entsprechend dem s-Hin/p-Rückbindungs-Synergismus nach Dewar- Chatt-Duncanson bzw. Blyholder erklärt werden. Die Beobachtung von chemisorbierten H2-Molekülen auf einer Übergangsoberfläche ist ungewöhnlich. Nach dem Harris-Andersson-Modell sollte auf Übergangsmetallen die Dissoziation spontan erfolgen, auf Edelmetallen hingegen inhibiert sein. Hier können bei Temperaturen kleiner als 10K molekular physisorbierter Wasserstoff stabilisiert werden. Das heißt, es besteht nur eine schwache Van-der-Waals-Wechselwirkung zwischen Molekül und Oberfläche. Das einzige weitere Beispiel von molekular chemisorbiertem Wasserstoff auf einer Übergangsmetalloberfläche ist das von A.-S. Mårtensson untersuchte H2/Ni(510)-System. Ist diese gestuften Ni(110)-Oberfläche mit atomarem Wasserstoff gesättigt, adsorbiert weiterer Wasserstoff molekular an den Stufen. Aus HREELS-Daten ergibt sich eine on top Adsorption. Wir machen ähnliche Beobachtungen: Während die atomare Adsorption auf der Pd(210)- bzw. Ni(210)-Oberfläche in hochkoordinierte Plätze erfolgt, adsorbiert das Molekül on top auf Substratatomen der ersten Lage. DF\- und TD- Experimente deuten darauf hin, daß zur Stabilisierung der molekularen Zustände eine partielle atomare Vorbelegung der Oberfläche notwendig ist. Mit Hilfe des in einer Kooperation mit einer Theoretischen Gruppe (A. Groß an der TU München) entwickelten Adsorptionsmodells wird den verschiedenen molekularen Desorptionssignalen derselbe Adsorptionsplatz bei unterschiedlicher atomarer Vorbedeckung zugeordnet. Der molekulare Adsorptionsplatz on top an den gering koordinierten Substratatomen der ersten Lage ist gleichzeitig der Dissoziationsplatz. Ändert sich aufgrund der benachbarten atomaren Adsorption von Wasserstoff die d-Bandstruktur und damit die Reaktivität dieser ausgezeichneten Substratatome, wird der dort gebildete molekulare Vorläufer- Zustand stabilisiert. Die in dieser Arbeit vorgestellten Systeme unterscheiden sich im Hinblick auf die Besetzung des Subsurface-Zustandes. Für die Pd(210)-Oberfläche wird eine Absorption von Wasserstoff in oberflächennahe Zwischengitterplätze beobachtet, für die H2/Ni(210)-Oberfläche nicht. Dabei ist mit Besetzung des Subsurface- Zustandes keine Änderung der Austrittsarbeit oder die Detektion eines Schwingungsverlustes im HREELS verbunden. In den TD-Spektren wird der Absorption ein schmales Niedertemperatur-Signal zugeordnet. Diese Beobachtung wird mit Hilfe des von Okuyama entwickelten Stamping-Modells diskutiert. Eine H-Absorption wurde bereits für andere offene Pd-Oberflächen ( (110) und (310) ) beobachtet und gilt als besondere Elementeigenschaft von Palladium. Im Unterschied zu den Pd(110)- und Pd(310)-Oberflächen ist zur Absorption in den Pd(210)-Kristall keine Rekonstruktion nötig. Dies und die Beobachtung der Abhängigkeit der Absorptionsgeschwindigkeit von der Probenpräparation ist Anlaß dafür die Existenz eines zur Absorption notwendigen Strukturensembles auf der nicht-rekonstruierten Pd(210)-Oberfläche zu diskutieren. Als solches wird der vierfachkoordinierte Muldenplatz und sein benachbarter dreifachkoordinierter (111)-Mikrofacettenplatz identifiziert. Daneben wurde auch die H/CO-Koadsorption auf der Pd(210)-Oberfläche untersucht. Wenn Wasserstoff präadsorbiert und anschließend CO dosiert wird, beobachten wir eine H/CO-Komplexbildung. Dies wird durch die Detektion eines sogenannten S-Signals im H2-TD-Spektrum und eines nH-O-Schwingungsverlustes im HREELS belegt. Im Gegensatz zu anderen Koadsorptionssystemen desorbiert der S-Wasserstoff nicht bei den niedrigeren Temperaturen des Desorptionsbereiches, sondern simultan mit dem Stabilsten der CO-Zustände. Dies deutet auf eine ungewöhnlich stabile Komplex-Bildung hin.8 This work presents investigations of the interaction of hydrogen with a Pd(210) and Ni(210) surface using LEED (low energy electron diffraction), thermal desorption spectroscopy (TDS), work-function measurements (DF),vibrational loss measurements (HREELS), and isotope exchange experiments. The interaction of hydrogen with both surfaces is very similar. For temperatures above 100K, hydrogen chemisorbs spontaneously forming atoms in three binding states (b1, b2, b3). The atomic adsorption leads to a work function increase. If the temperature is reduced to 50K, hydrogen additionally chemisorbs into two molecular states (g1, g2). In contrast to the b-adsorption, the population of g-states induces a work-function decrease. The molecular nature of the g-states was confirmed by observation of the H-H vibration mode in HREELS, by the detection of the s-H2/Pd- and s*-H2/Pd- bonding in UPS, and by H2/D2-exchange experiments. The energy range of the HREELS- and UPS-signals and the relatively high desorption temperature in TD-spectra verify a real chemisorptive interaction between molecule and surface. We consider a side-on complex configuration which allows a s/s*-synergism equivalent to the Blyholder backbonding mechanism for CO chemisorption or the classical Dewar-Chatt-Duncanson model for the bonding situation in olefine or other organometallic complexes. A molecular chemisorption of H2 on a transition metal surface is unusual. In general, hydrogen adsorbs dissociatively. While on noble metals the dissociation is hindered by a sizable energy barrier, it occurs spontaneously on transition metal surfaces. If molecular adsorption states exist, they are usually very weakly bound in shallow physisorption wells; beyond, it requires surface temperatures below 20K to stabilize those states. At Ni(510), molecular chemisorption has been observed at surface temperatures up to 125K, presumably at the steps, but only after the surface was passivated with a dense atomic layer. We made similar observations, namely the coexistence of chemisorbed molecular and atomic hydrogen on the relatively open Pd(210) and Ni(210) surfaces although the surfaces were not fully passivated. While the atomic adsorption takes place in high coordinated sites, the molecule adsorbs on top. It is very difficult to identify experimentally the exact location and nature of the hydrogen adsorption states. In order to obtain this microscopic information, A. Groß et al. performed DFT calculations. The results suggest that the hydrogen molecule is first attracted to the top Pd atoms. At the clean Pd(210) surface, no stable molecular adsorption state should exist and the hydrogen molecule dissociates into the higher coordinated sites. Due to the presence of atomic hydrogen on the surface however, this behavior changed considerably. The presence of hydrogen atoms leads to a molecular adsorption state at the top site. That the top site`s reactivity is hardly influenced by the pre-adsorbed hydrogen atoms can be traced back to the induced change in the local density of states. In the case of Pd, we observed the absorption of hydrogen atoms which reside ?close to the surface?. Evidence for such a ?subsurface state? is a low- temperature thermal desorption feature which cannot be saturated, combined with a vanishing work function change and negligible vibrational loss contributions of the respective H state. We discuss our observations using the stamping model developed by Okuyama. The hydrogen absorption has already been observed on other open palladium surfaces and is considered as a specific feature of the element palladium. But in contrast to other open Pd surfaces, the Pd(210) surface need not to reconstruct for absorption. Futhermore, the absorption velocity depends on the preparation of the sample. Both observations give rise to the assumption that a certain ensemble of substrate atoms necessary for chemisorption exists on the non-reconstructed Pd(210) surface. We can identify this ensemble as the four-fold coordinated hollow site and the neighbouring three-fold coordinated site. In addition, we examined the H/CO-coadsorption on the Pd(210) surface. If the Pd crystal was first exposed to hydrogen and then to carbon monoxid, we observed the formation of H/CO-complexes. This observation was verified by the detection of a so-called S desorption signal in TDS and by a O-H vibrational loss in HREELS. In contrast to other coadsorption systems the S-hydrogen does not desorb in the low temperature area. Rather, hydrogen desorbs simultaneously with the strongly bound carbon monoxid, indicating an unusually stable complex

Neural basis of somatosensory target detection independent of uncertainty, relevance, and reports

Research on somatosensory awareness has yielded highly diverse findings with putative neural correlates ranging from activity within somatosensory cortex to activation of widely distributed frontoparietal networks. Divergent results from previous studies may reside in cognitive processes that often coincide with stimulus awareness in experimental settings. To scrutinise the specific relevance of regions implied in the target detection network, we used functional magnetic resonance imaging (n = 27) on a novel somatosensory detection task that explicitly controls for stimulus uncertainty, behavioural relevance, overt reports, and motor responses. Using Bayesian Model Selection, we show that responses reflecting target detection are restricted to secondary somatosensory cortex, whereas activity in insular, cingulate, and motor regions is best explained in terms of stimulus uncertainty and overt reports. Our results emphasise the role of sensory-specific cortex for the emergence of perceptual awareness and dissect the contribution of the frontoparietal network to classical detection tasks

Characterization of Epidermal Wound Healing in a Human Skin Organ Culture Model: Acceleration by Transplanted Keratinocytes1

Few data are available on early regeneration of human epidermis in vivo. We have established a supravital skin organ culture model for epidermal wound healing by setting a central defect (3 mm diameter) in freshly excised skin specimens and culturing under air exposure. Re-epithelialization was followed for up to 7 d by histology and immunohistologic analysis of various markers for differentiation and proliferation. In 12 of 19 cases (63%; 5% fetal calf serum) or six of 21 cases (29%; 2% fetal calf serum), the wounds were re-epithelialized spontaneously after 7 d. After transplantation to the wounds of 1–2 × 106 dissociated allogenic cultured epidermal or about 1 × 106 autologous outer root sheath keratinocytes, 18 of 21 cases (86%; 5% fetal calf serum) or 17 of 21 cases (81%; 2% fetal calf serum) were healed within the same period. Histologically, early neoepithelium (3 d) was disordered after keratinocyte transplantation, whereas later (7 d) it had gained a more ordered stratification, exhibiting a thin discontinuous granular and a compact horny layer. At this stage, not only hyperproliferative (CK 6) but also, abundantly, maturation-associated cytokeratins (CK 1, CK 10) were detected immunohistochemically. Analyses of regenerated epidermis after transplantation of (i) keratinocytes labeled in vitro with BrdU and (ii) heterosexual keratinocytes by immunohistochemistry and fluorescence in situ hybridization for the Y chromosome, respectively, clearly showed that external keratinocytes are physically integrated into the regenerated epidermis and extendedly contribute to its formation. The data presented here demonstrate improvement and acceleration of epidermal re-epithelialization by transplantation of keratinocytes

Deciduous enamel 3D microwear texture analysis as an indicator of childhood diet in medieval Canterbury, England

This study conducted the first three dimensional microwear texture analysis of human deciduous teeth to reconstruct the physical properties of medieval childhood diet (age 1-8yrs) at St Gregory's Priory and Cemetery (11th to 16th century AD) in Canterbury, England. Occlusal texture complexity surfaces of maxillary molars from juvenile skeletons (n=44) were examined to assess dietary hardness. Anisotropy values were calculated to reconstruct dietary toughness, as well as jaw movements during chewing. Evidence of weaning was sought, and variation in the physical properties of food was assessed against age and socio-economic status. Results indicate that weaning had already commenced in the youngest children. Diet became tougher from four years of age, and harder from age six. Variation in microwear texture surfaces was related to historical textual evidence that refers to lifestyle developments for these age groups. Diet did not vary with socio-economic status, which differs to previously reported patterns for adults. We conclude, microwear texture analyses can provide a non-destructive tool for revealing subtle aspects of childhood diet in the past

Bayesian Sensitivity Analysis of Flight Parameters in a Hard-Landing Analysis Process

A flight parameter sensor simulation model was developed to assess the conservatism of the landing gear component loads calculated using a typical hard-landing analysis process. Conservatism exists due to factors of safety that are incorporated into any hard-landing analysis process to account for uncertainty in the measurement of certain flight parameters. The flight parameter sensor simulation model consists of 1) an aircraft and landing gear dynamic model to determine the “actual” landing gear loads during a hard landing; 2) an aircraft sensor and data acquisition model to represent the aircraft sensors and flight data recorder systems to investigate the effect of signal processing on the flight parameters; and 3) an automated hard-landing analysis process, representative of that used by airframe and equipment manufacturers, to determine the “simulated” landing gear loads. Using a technique of Bayesian sensitivity analysis, a number of flight parameters are varied in the flight parameter sensor simulation model to gain an understanding of the sensitivity of the difference between actual and simulated loads to the individual flight parameters in symmetric and asymmetric two-point landings. This study shows that the error can be reduced by learning the true value of the following flight parameters: longitudinal tire–runway friction coefficient, aircraft vertical acceleration (related to vertical descent velocity), lateral acceleration (related to lateral velocity), Euler roll angle, mass, center of gravity position, and main landing gear tire type. It was also shown that, due to the modeling techniques used, shock absorber servicing state and tire pressure do not contribute significantly to the error

Lower Respiratory Tract Infections in Pediatric Patients with Severe Neurological Impairments: Clinical Observations and Perspectives in a Palliative Care Unit

Pediatric palliative care (PPC) patients with a severe neurologic impairment (SNI) suffer considerable morbidity and increased mortality from lower respiratory tract infections (LRTIs). The indication and choice of antibiotic therapy for bacterial LRTIs are often challenging given the lack of evidence-based treatment recommendations for this vulnerable patient population. We conducted an observational study before the SARS-CoV-2 pandemic in an eight-bed pediatric palliative care inpatient unit. During two years of surveillance, we diagnosed and treated 33 cases of a bacterial LRTI in patients with an SNI; 5 patients were hospitalized with an LRTI more than once. Two patients died from complications due to LRTIs during hospitalization. Three patients (15%) were colonized with multidrug-resistant organisms. An initial antibiotic treatment failed in one-third of the cases; a successful therapy of the LRTI was achieved with broad-spectrum and extended-spectrum penicillins (n = 13; in combination with β-lactamase inhibitors for n = 5 cases), cephalosporins (n = 13: n = 4 second-generation and n = 9 third-generation cephalosporins; in combination with other substances for n = 5 cases), ciprofloxacin (n = 3), and meropenem plus vancomycin (n = 2) or meropenem (n = 1). A respiratory specimen was obtained in 66.7% of cases with P. aeruginosa, E. coli, and K. pneumoniae accounting for the majority of the detected species. In most cases, there was no definite confirmation that the LRTI was caused by the species detected. The diagnostics and treatment of bacterial LRTIs in PPC patients with an SNI are challenging. The lack of controlled studies and the heterogeneity of this population often necessitate an individual approach. This lack of controlled studies may partly be compensated by a set of diagnostic and antibiotic stewardship criteria