Mechanistic Investigation of RhI-Catalyzed Cycloisomerization of Benzylallene-Internal Alkynes via C-H Activation

Treatment of the benzylallene-internal alkynes with [RhCl(CO)2]2 effected a cycloisomerization via a Csp2-H bond activation to produce the tricyclo[9.4.0.03,8]pentadecapentaene skeleton. The reaction mechanism via formation of the rhodabicyclo[4.3.0] intermediates and σ-bond metathesis between the Csp2-H bond on the benzene ring and the Csp2-RhIII bond was proposed. In addition, a plausible alternative mechanism for the previously reported cycloisomerization of the benzylallene-terminal alkynes could also be proposed. © 2017 American Chemical Society.Embargo Period 12 month

Sphingomyelinase and ceramide inhibit formation of F-actin ring in and bone resorption by rabbit mature osteoclasts

AbstractRecent studies have demonstrated that ceramide plays an important role as a second messenger in many kinds of cells. However, it is not known whether apoptosis of and bone resorption by mature osteoclasts are mediated via sphingomyelinase (SMase) and ceramide. Thus, we examined the possible involvement of SMase and ceramide in the induction of apoptosis in and bone resorption by rabbit mature osteoclasts. SMase and C2-ceramide inhibited strongly F-actin ring formation of and bone resorption by the osteoclasts. However, the osteoclast apoptosis was not induced by C2-ceramide. The ceramide inhibition of the bone resorption was suppressed by dl-threo-dihydrosphingosine, an inhibitor of sphingosine kinase. In addition, we observed that sphingosine-1-phosphate is able to inhibit bone resorption by the osteoclasts. These results suggest an important role of the sphingomyelin pathway in bone resorption by rabbit mature osteoclasts

Role of Inflammation in Coronary Epicardial and Microvascular Dysfunction

There is accumulating evidence highlighting a close relationship between inflammation and coronary microvascular dysfunction (CMD) in various experimental and clinical settings, with major clinical implications. Chronic low-grade vascular inflammation plays important roles in the underlying mechanisms behind CMD, especially in patients with coronary artery disease, obesity, heart failure with preserved ejection fraction and chronic inflammatory rheumatoid diseases. The central mechanisms of coronary vasomotion abnormalities comprise enhanced coronary vasoconstrictor reactivity, reduced endothelium-dependent and -independent coronary vasodilator capacity and increased coronary microvascular resistance, where inflammatory mediators and responses are substantially involved. How to modulate CMD to improve clinical outcomes of patients with the disorder and whether CMD management by targeting inflammatory responses can benefit patients remain challenging questions in need of further research. This review provides a concise overview of the current knowledge of the involvement of inflammation in the pathophysiology and molecular mechanisms of CMD from bench to bedside

Relation between Fractal Inhomogeneity and In/Nb-Arrangement in Pb(In1/2Nb1/2)O3

Relaxor ferroelectrics show substantial responses to electric fields. The key difference from normal ferroelectrics is a temperature-dependent inhomogeneous structure and its dynamics. The lead-based complex perovskite Pb(In1/2Nb1/2)O3 is an intriguing system in which the inhomogeneous structure can be controlled by thermal treatment. Herein, we report investigations of the phase transitions in single crystals of Pb(In1/2Nb1/2)O3 via changing the degree of randomness in which In and Nb occupy the B site of the ABO3 perovskite structure. We studied the dynamic properties of the structure using inelastic light scattering and the static properties using diffuse X-ray scattering. These properties depend on the degree of randomness with which the B site is occupied. When the distribution of occupied In/Nb sites is regular, the antiferroelectric phase is stabilised by a change in the collective transverse-acoustic wave, which suppresses long-range ferroelectric order and the growth of the inhomogeneous structure. However, when the B site is occupied randomly, a fractal structure grows as the temperature decreases below T*~475 K, and nanosized ferroelectric domains are produced by the percolation of self-similar and static polar nanoregions

Pathophysiology and Diagnosis of Coronary Functional Abnormalities

Approximately one-half of patients undergoing diagnostic coronary angiography for angina have no significant coronary atherosclerotic stenosis. This clinical condition has recently been described as ischaemia with non-obstructive coronary arteries (INOCA). Coronary functional abnormalities are central to the pathogenesis of INOCA, including epicardial coronary spasm and coronary microvascular dysfunction composed of a variable combination of increased vasoconstrictive reactivity and/or reduced vasodilator function. During the last decade – in INOCA patients in particular – evidence for the prognostic impact of coronary functional abnormalities has accumulated and various non-invasive and invasive diagnostic techniques have enabled the evaluation of coronary vasomotor function in a comprehensive manner. In this review, the authors briefly summarise the recent advances in the understanding of pathophysiology and diagnosis of epicardial coronary artery spasm and coronary microvascular dysfunction

Wie nicht-lineare Zeitrepräsentationen zukunftsbezogene Urteile und Entscheidungen beeinflussen können : ein entwicklungspsychologischer Ansatz

Die vorliegende Arbeit untersuchte in drei Experimenten den Einfluss der Zeit auf Bewertungen und Entscheidungen in unterschiedlichen Altersstufen. Experiment 1 beschäftigte sich mit dem Einfluss des Zeithorizontes auf die Beurteilung der Riskantheit einer Investition sowie auf das Investitionsverhalten bei 12-Jährigen. Im Gegensatz zu typischen Ergebnissen von Erwachsenen führte bei den Kindern eine lange Zeitspanne zwischen Investition und Erfolgsfeedback zur Annahme eines höheren Risikos und damit zu geringeren Investitionen. In Experiment 2 wurde die Bewertung materieller und nicht-materieller Werte, deren Erhalt verzögert war, bei 12-Jährigen und Erwachsenen untersucht. Dabei zeigte sich, dass Erwachsene Geld als materiellen Wert und Hilfe als nicht-materiellen Wert in ähnlicher Weise mit zunehmender Verzögerung abwerteten. Die Kinder hingegen werteten das verzögerte Geld deutlich stärker ab als Erwachsene, die Hilfe jedoch gar nicht. In Experiment 3 wurde die Entwicklung des Wissens über exponentielles Mengenwachstum in verschiedenen Altersgruppen untersucht. So schätzten 13-Jährige ein solches Wachstum normativ, doch bereits 9-Jährige unterschieden in ihren Schätzungen bedeutsam zwischen exponentiellem und linearem Wachstum, was für ein frühes intuitives Wissen in diesem Bereich spricht. Im Anschluss wurde ein Modell zur altersabhängigen Zeitrepräsentation entwickelt, das versucht, den Einfluss der Zeitrepräsentation in allen drei Experimenten zu erklären. Three experiments were conducted to examine the role of time on judgments and decisions in different age groups. Experiment 1 investigated the influence of the time horizon on 12-year-olds judgments of riskiness and amount of investment into an endeavour. In contrast to typical results of adults, a long time span between the investment and a feedback about its success yielded judgments of higher riskiness and, thus, lower investments in children. Experiment 2 assessed 12-year-olds and adults evaluation of material and immaterial values, whose receipt was either immediate or delayed. Results showed similar subjective discount rates for delayed money (i.e. material value) and delayed help (i.e. immaterial value) in adults. However, children discounted the delayed money more than adults, but they devaluated the delayed help not at all. Experiment 3 investigated the development of knowledge about exponential growth in children, aged 7 to 13 years, and adults. Only 13-year-olds showed a normative estimation of exponential growth. However, 9-year-olds already differentiated between exponential and linear growth in their estimations. This result points to an early intuitive knowledge in this domain. Finally, a model of age-related time representation was proposed to explain the role of time representation in the three experiments

A key to the species of Keetia (Rubiaceae: Vanguerieae) in West Africa, with three new, threatened species from Guinea and Ivory Coast

Keetia susu Cheek and K. futa Cheek from the Republic of Guinea, and K. abouabou Cheek from Ivory Coast are described here. Each species is assessed using the IUCN standard as, respectively, Vulnerable, Endangered and Critically Endangered. Each species is illustrated and mapped. A key to the 16 species of Keetia in West Africa (Senegal to Benin) is provided. The number of species of Keetia currently accepted is now known to total 35

Field experiments in labor economics

In this thesis I show with three studies how field experiments can enhance our understanding of labor markets. Economists traditionally assume that individuals exclusively respond to monetary incentives. As a consequence, if workers have no prospect of future employment at the firm and pay is not contingent on their performance, a wage change should not affect effort. Some economists, however, have recognized that this narrow view of human motivation may severely limit our progress in understanding incentives. In Chapters 2 and 3, I investigate the role of psychological motives like the desire to reciprocate in the context of a real‐life work environment. The first experiment explores the impact of a wage increase on work performance when there is no economic reason for workers to change their effort. I find that workers reciprocate a generous wage with higher performance, particularly those workers who care about fairness and felt underpaid prior to the wage increase. The second experiment investigates the effects of a wage cut on performance when either all workers in a team or only some of them suffer the cut. I show that a general pay cut reduces performance, while a wage cut for only some of the workers reduces their performance more than twice as much. This finding demonstrates the powerful force of social comparison and the need to build the social nature of humans into economic theory. In Chapter 4, I examine the joint effects of monetary incentives and social interaction on work performance. Many jobs offer wage schemes that create positive or negative externalities on coworkers. Whether or not workers have the possibility to interact socially at work may distort the intended incentives of these schemes. I find that under relative incentives, when own effort imposes a negative externality on the coworker’s income, social interaction works against monetary incentives and leads to low performance due to collusion. However, the more workers differ in skills the less able they are to sustain collusive agreements. In der vorliegenden Dissertation zeige ich anhand von drei Studien wie Feldexperimente unser Verständnis von Arbeitsmärkten verbessern können. Ökonomen gehen traditionell davon aus, dass Individuen ausschliesslich auf materielle Anreize reagieren. Wenn also Arbeitskräfte keine Aussicht auf eine langfristige Anstellung haben und deren Lohn nicht von der Leistung abhängt, dann sollte eine Lohnveränderung keinen Einfluss auf die Arbeitsleistung haben. Manche Ökonomen haben jedoch erkannt, dass diese Sichtweise des menschlichen Verhaltens beschränkt ist und unseren Fortschritt im Verständnis von Anreizen bremsen kann. In den Kapiteln 2 und 3 untersuche ich die Bedeutung von psychologischen Motiven wie Fairness oder Reziprozität in echten Arbeitsumgebungen. Das erste Experiment untersucht den Einfluss einer Lohnerhöhung auf die Arbeitsleistung, wenn Arbeitskräfte keinen ökonomischen Grund haben, ihren Arbeitseinsatz zu ändern. Diese Studie zeigt, dass Arbeitskräfte einen grosszügigen Lohn mit höherer Arbeitsleistung erwidern. Dies gilt besonders für diejenigen, die Fairness als wichtig empfinden und sich vor der Lohnerhöhung unterbezahlt fühlten. Das zweite Experiment untersucht die Wirkung einer Lohnkürzung auf die Arbeitsleistung, wenn entweder das ganze Team oder nur einen Teil davon betroffen ist. Diese Studie zeigt auf, dass eine generelle Lohnkürzung die Arbeitsleistung senkt, wohingegen eine Lohnkürzung nur für einzelne Arbeitskräfte deren Leistung um mehr als das Doppelte reduziert. Diese Erkenntnis unterstreicht die Bedeutung von sozialen Motiven und die Notwendigkeit einer Veränderung des Menschenbilds in der Ökonomie. In Kapitel 4 erforsche ich den gemeinsamen Einfluss von materiellen Anreizen und sozialer Interaktion auf die Arbeitsleistung. Viele Firmen bieten Lohnsysteme an, bei welchen die eigene Leistung vor‐ oder nachteilhafte Nebeneffekte auf das Einkommen der Arbeitskollegen hat. Soziale Interaktion am Arbeitsplatz kann dabei die Anreize dieser Lohnsysteme verzerren. Diese Studie findet heraus, dass bei Entlohnung der Arbeitskräfte durch Turnieranreize, d.h. wenn die eigene Leistung sich nachteilhaft auf das Einkommen der Arbeitskollegen auswirkt, soziale Interaktion die Anreize ausser Kraft setzt und zu geheimen Absprachen führt. Wenn hingegen Arbeitskräfte sehr unterschiedliche Fähigkeiten besitzen, dann sind geheime Absprachen schwieriger aufrecht zu halten

Immunohistochemical analysis of brain lesions using S100B and glial fibrillary acidic protein antibodies in arundic acid- (ONO-2506) treated stroke-prone spontaneously hypertensive rats

Stroke-prone spontaneously hypertensive rats (SHRSP) used as a model of essential hypertension cause a high incidence of brain stroke on the course of hypertension. Incidences and sizes of brain lesions are known to relate to the astrocyte activities. Therefore, relation between brain damage and the expression profile of the astrocytes was investigated with morphometric and immunohistochemical analyses using astrocyte marker antibodies of S100B and glial fibrillary acidic protein (GFAP) with or without arundic acid administration, a suppressor on the activation of astrocytes. Arundic acid extended the average life span of SHRSP. An increase in brain tissue weight was inhibited concomitant with a lower rate of gliosis/hemosiderin deposit/scarring in brain lesions. S100B- or GFAP-positive dot and filamentous structures were decreased in arundic acid-treated SHRSP, and this effect was most pronounced in the cerebral cortex, white matter, and pons, and less so in the hippocampus, diencephalon, midbrain, and cerebellum. Blood pressure decreased after administration of arundic acid in the high-dose group (100 mg/kg/day arundic acid), but not in the low-dose group (30 mg/kg/day). These data indicate that arundic acid can prevent hypertension-induced stroke, and may inhibit the enlargement of the stroke lesion by preventing the inflammatory changes caused by overproduction of the S100B protein in the astrocytes