Modellkomplexe oligonuklearer Metalloproteine auf Basis von Salen-Liganden und Spin-Crossover-Verbindungen als Chemosensoren

Der erste Teil der hier vorgestellten Arbeit verfolgt die Synthese potentieller Modellverbindungen oligonuklearer Metalloproteine auf Basis von Salen-Liganden. Dazu wurden zwei Ligandensysteme mit unterschiedlich raumerfüllenden Alkyl-Substituenten modifiziert und auf ihre koordinativen Eigenschaften hin untersucht. Für das Ligandensystem auf Basis des Bis-(salicylidenamino)-propan-2-ols konnten fünf Derivate (H3L1, H3L2A,H3L2B, H3L3, H3L4), für das zweite verwendete Ligandensystem auf Basis des 1H-3,5-Bis-(salicylidenaminomethyl)-pyrazols konnten zwei weitere Derivate (H3L5A, H3L5B) dargestellt und zu Koordinationsverbindungen umgesetzt werden.rnFür den hier verwendeten Bis-(salicylidenamino)-propan-2-ol Liganden H3L1, welcher die geringsten sterischen Anforderungen stellt, konnten mono-, tri- und tetranukleare Koordinationsverbindungen synthetisiert werden. Dabei gelingt es dem Liganden, sich sowohl in planarer als auch in unterschiedlich stark gewinkelter Konformation um ein oder mehrere Metallzentren anzuordnen, wobei der Ligand ein N2O2- seines N2O3-Donorsets zur Koordination nutzt. Die Verbindung {[Ni7(HL1)2(L1)2(OBz)4(OMe)(H2O)]}n zeigt, dass eine Verkettung der so gestalteten dreikernigen Einheiten über das freie Propanol-Sauerstoffatomdes Ligandenrückgrats möglich ist. Mit zunehmendem sterischen Anspruch der angefügten Alkylsubstituenten nimmt die geometrische Flexibilität und somit das Potential des Liganden zur Ausbildung höhernuklearer Strukturen ab. So ist für Liganden mit mittlerem sterischen Anspruch neben mononuklearen Komplexen noch die Gestaltung dinuklearer Systeme möglich. Erhöht man den sterischen Anspruch des Liganden weiter, findet nur noch eine Reaktion zu mononuklearen Verbindungen statt.rnMit den Pyrazol-basierten Ligandensystemen H3L5A und H3L5B konnten dinukleare Kupfer- und Nickelverbindungen synthetisiert werden.rnDer zweite Teil dieser Arbeit befasst sich mit der Gestaltung von Spin-Crossover Systemen (SCO). Dazu soll ein Spinübergang innerhalb des gestalteten schaltbaren Systems an die Anwesenheit eines Signalstoffs gekoppelt werden, so dass diese SCO-Verbindung als Sensor für den Signalstoff eingesetzt werden kann. Dazu wurden zwei unterschiedliche Ansätze entwickelt und untersucht.rnDie erste Methode beruht auf der Kombination eines zum Spin-Crossover befähigten Metallzentrums, eines Capping-Liganden, eines zur Signalstofferkennung funktionalisierten Co-Liganden sowie eines entsprechenden Signalstoffs. Als Capping-Liganden wurden tetra- und pentadentateLigandensysteme eingesetzt und mit unterschiedlich Picolyl-substituierten Monoaza-[12]-krone-4-Derivaten umgesetzt, wobei die Monoazakrone zur Komplexierung des Signalstoffs,hier in Form eines Alkalimetallions, zur Verfügung steht. Nach dieser ersten Methode konnten im Zeitraum dieser Arbeit noch keine zufriedenstellenden Ergebnisse erzielt werden.rnEine vielversprechende zweite Möglichkeit beruht auf der Verwendung eines mehrzähnigen, etablierten Spin-Crossover Liganden,welcher in seiner Peripherie mit einer Bindungstasche zur Aufnahme des Signalstoffmodifiziert wird.Mit Hilfe des so gestalteten Liganden 4'-(4'''-Benzo-[15]-krone-5)-methyloxy-2,2':6',2''-terpyridin ([b15c5]-tpy) gelang die Umsetzung zu entsprechenden Eisen(II)- und Kobalt(II)komplexen der Zusammensetzung [M([b15c5]-tpy)2]2+. Alle synthetisierten Eisen(II)-Komplexe liegen aufgrund der hohen Ligandenfeldstärke des Terpyridins über einen Temperaturbereich von 300 – 400 K in ihrer diamagnetischen Low Spin Form vor. Die entsprechenden Kobalt(II)-Komplexe zeigen über einen Temperaturbereich von 2 – 350 K ein kontinuierliches, aber unvollständiges Spin-Crossover Verhalten.rnDer Einfluss von Signalstoffen auf das Spin-Crossover Verhalten der Kobalt(II)-Systeme wurde in einem ersten Versuch unter der Verwendung von Natriumionen als Signalstoff untersucht. Dabei stellte sich heraus, dass Natriumionen für dieses System zwar nicht als Auslöser eines SCO verwendet werden können, sie aber dennoch eine starke Auswirkung auf den Verlauf des Spin-Crossovers haben.

Mobile goes global: The effect of cell phones on economic growth and development

This study investigates the effect of cell phones on economic development and growth by performing an econometric analysis using data from the International Telecommunications Union and the Penn World Table. It discusses the various ways cell phones can make markets more efficient and how the diffusion of information andknowledge plays into development. Several approaches (OLS, Fixed Effects, 2SLS) were used to test over 20 econometric models. Overall, the mobile cellular subscriptions rate was found to have a positive and significant impact on countries’ level of real per capitaGDP and GDP growth rate. Furthermore, the study provides policy implications for the use of technology to promote global growth.

The Effects of Interstate Speed Limit Increases: Fatality Rates and Traffic Diversion Versus Speed Spillover

This thesis examines two panel data sets of 48 states from 1981 to 2009 and utilizes ordinary least squares (OLS) and fixed effects models to explore the relationship between rural Interstate speed limits and fatality rates and whether rural Interstate speed limits affect non-Interstate safety. Models provide evidence that rural Interstate speed limits higher than 55 MPH lead to higher fatality rates on rural Interstates though this effect is somewhat tempered by reductions in fatality rates for roads other than rural Interstates. These results provide some but not unanimous support for the traffic diversion hypothesis that rural Interstate speed limit increases lead to decreases in fatality rates of other roads. To the author’s knowledge, this paper is the first econometric study to differentiate between the effects of 70 MPH speed limits and speed limits above 70 MPH on fatality rates using a multi-state data set. Considering both rural Interstates and other roads, rural Interstate speed limit increases above 55 MPH are responsible for 39,700 net fatalities, 4.1 percent of total fatalities from 1987, the year limits were first raised, to 2009.

ELECTRICITY GENERATION MODELING AND PHOTOVOLTAIC FORECASTS IN CHINA

With the economic development of China, the demand for electricity generation is rapidly increasing. To explain electricity generation, we use gross GDP, the ratio of urban population to rural population, the average per capita income of urban residents, the electricity price for industry in Beijing, and the policy shift that took place in China. Ordinary least squares (OLS) is used to develop a model for the 1979-2009 period. During the process of designing the model, econometric methods are used to test and develop the model. The final model is used to forecast total electricity generation and assess the possible role of photovoltaic generation. Due to the high demand for resources and serious environmental problems, China is pushing to develop the photovoltaic industry. The system price of PV is falling; therefore, photovoltaics may be competitive in the future.

DiepRuR

Aufbau einer föderativen Dienstlandschaft in der Ruhr-Region auf Basis von SAML mit dem Ziel eine organisationsübergreifende Nutzung von webbasierten IT-Diensten zu ermöglichen

Tree-level contribution to B[over ¯]→X_{d}γ using fragmentation functions

We evaluate the most important tree-level contributions connected with the b→uu ¯ ¯ dγ transition to the inclusive radiative decay B ¯ ¯ ¯ →X d γ using fragmentation functions. In this framework the singularities arising from collinear photon emission from the light quarks (u , u ¯ ¯ , and d ) can be absorbed into the (bare) quark-to-photon fragmentation function. We use as input the fragmentation function extracted by the ALEPH group from the two-jet cross section measured at the large electron positron (LEP) collider, where one of the jets is required to contain a photon. To get the quark-to-photon fragmentation function at the fragmentation scale μ F ∼m b , we use the evolution equation, which we solve numerically. We then calculate the (integrated) photon energy spectrum for b→uu ¯ ¯ dγ related to the operators P u 1,2 . For comparison, we also give the corresponding results when using nonzero (constituent) masses for the light quarks.

Calculating track thrust with track functions

In e+e− event shapes studies at LEP, two different measurements were sometimes performed: a “calorimetric” measurement using both charged and neutral particles and a “track-based” measurement using just charged particles. Whereas calorimetric measurements are infrared and collinear safe, and therefore calculable in perturbative QCD, track-based measurements necessarily depend on nonperturbative hadronization effects. On the other hand, track-based measurements typically have smaller experimental uncertainties. In this paper, we present the first calculation of the event shape “track thrust” and compare to measurements performed at ALEPH and DELPHI. This calculation is made possible through the recently developed formalism of track functions, which are nonperturbative objects describing how energetic partons fragment into charged hadrons. By incorporating track functions into soft-collinear effective theory, we calculate the distribution for track thrust with next-to-leading logarithmic resummation. Due to a partial cancellation between nonperturbative parameters, the distributions for calorimeter thrust and track thrust are remarkably similar, a feature also seen in LEP data.

Microstructural, chemical and isotopic evidence for the origin of late neolithic leather recovered from an ice field in the Swiss Alps

Archaeological leather samples recovered from the ice field at the Schnidejoch Pass (altitude 2756 m amsl) in the western Swiss Alps were studied using optical, chemical molecular and isotopic (δ13C and δ15N of the bulk leather, and compound-specific δ13C analyses of the organic-solvent extracted fatty acids) methods to obtain insight into the origin of the leather and ancient tanning procedures. For comparison, leathers from modern native animals in alpine environment (red deer, goat, sheep, chamois, and calf/cow) were analyzed using the same approach. Optical and electron microscopically comparisons of Schnidejoch and modern leathers showed that the gross structure (pattern of collagen fibrils and intra-fibrils material) of archaeological leather had survived essentially intact for five millennia. The SEM studies of the hairs from the most important archaeological find, a Neolithic leather legging, show a wave structure of the hair cuticle, which is a diagnostic feature for goatskins. The variations of the bulk δ13C and δ15N values, and δ13C values of the main fatty acids are within the range expected for pre-industrial temperate C3 environment. The archaeological leather samples contain a mixture of indigenous (from the animal) and exogenous plant/animal lipids. An important amount of waxy n-alkanes, n-alkan-1-ols and phytosterols (β-sitosterol, sitostanol) in all samples, and abundant biomarker of conifers (nonacosan-10-ol) in the legging leathers clearly indicate that the Neolithic people were active in a subalpine coniferous forest, and that they used an aqueous extract of diverse plant material for tanning leather.

Geklibene šrifṭen : 1. band

L. Ṭolsṭoi. Judiš fun Peretz Hiršbain. Miṭ a forworṭ fun ...

Kozaken : a kawkazer gešichṭe

L. N. Ṭolsṭoi. Iberzeṭtzṭ fun rusiš durch Baʿal Maḥašāvôt

Oggi la storia. Geschichte(n) für ein Jahr

«Oggi, la storia» è un programma radiofonico della Radiotelevisione svizzera RSI che «mira a dare, seppur nel breve formato, profondità storico-filosofica a tematiche legate all’attualità o alle ricorrenze del calendario.» Le illustrazioni di Erik Dettwiler sono tratte dalla serie fotografica «Whiter ain't possible!» nata nel corso degli anni in diverse metropoli europee tra Roma, Bucarest e Berlino, ma anche nella città sudafricana di Johannesburg. L'amicizia tra lo storico e l'artista, sfociata in numerose successive collaborazioni, è nata negli anni 2004/2005 durante il loro soggiorno quali membri dell'Istituto Svizzero di Roma.

Identifying Individual and Group Effects in the Presence of Sorting: A Neighborhood Effects Application

Researchers have long recognized that the non-random sorting of individuals into groups generates correlation between individual and group attributes that is likely to bias naive estimates of both individual and group effects. This paper proposes a non-parametric strategy for identifying these effects in a model that allows for both individual and group unobservables, applying this strategy to the estimation of neighborhood effects on labor market outcomes. The first part of this strategy is guided by a robust feature of the equilibrium in the canonical vertical sorting model of Epple and Platt (1998), that there is a monotonic relationship between neighborhood housing prices and neighborhood quality. This implies that under certain conditions a non- parametric function of neighborhood housing prices serves as a suitable control function for the neighborhood unobservable in the labor market outcome regression. The second part of the proposed strategy uses aggregation to develop suitable instruments for both exogenous and endogenous group attributes. Instrumenting for each individual's observed neighborhood attributes with the average neighborhood attributes of a set of observationally identical individuals eliminates the portion of the variation in neighborhood attributes due to sorting on unobserved individual attributes. The neighborhood effects application is based on confidential microdata from the 1990 Decennial Census for the Boston MSA. The results imply that the direct effects of geographic proximity to jobs, neighborhood poverty rates, and average neighborhood education are substantially larger than the conditional correlations identified using OLS, although the net effect of neighborhood quality on labor market outcomes remains small. These findings are robust across a wide variety of specifications and robustness checks.

Human Capital Externalities and Private Returns to Education in Kenya

We use micro data to analyse the effect of human capital externality on earnings and private returns to education. The earnings equations are estimated using the OLS method for a sample of full-time workers. The results show that human capital has a positive effect on earnings, indicating that an increase in education benefits all workers. However, men benefit more from women's education than the women do from men's. The effects of human capital externality on private returns to schooling are shown to vary substantially between rural and urban areas and across levels of the education system.