Derivate von m- und p- Oligophenylenen und deren Anwendungen

Die vorliegende Dissertation untergliedert sich in die Thematik der meta- und para-Phenylene als 1,2-Dithiine und der azobenzol¬hal¬tigen meta-Phenylenpolymere. Die 1,2-Dithiine kann man per Redox¬reaktion über die enthaltene Disulfidbrücke öffnen und schließen. Während die azobenzol¬enthal¬tenden meta-Phenylene mittels UV/Vis cis/trans-isomerisiert und folglich ebenfalls zwischen zwei Zuständen hin und her schaltbar sind. In Kapitel 3 wurden 1,2-Dithiinoligomere in Form von meta- und para-Phenylenen dargestellt und auf ihre kristallbildenden, chemischen und optischen Eigenschaften hin analysiert. Die Auswirkung der Schwefelsubstitution in der 1- und 1´-Position auf die Rotations¬barriere der Biphenylbindung wurde berechnet. Da diese nicht ausreicht, um das Ziel stabiler schaltbarer Helicene zu erreichen wurde im Falle der meta-Phenylen-1,2-Dithiine die End-zu-End-Überlappung durch Naphthalenreste verstärkt. Dies war notwendig, da mit zunehmendem Schwefelanteil im Molekül dieser extrudiert wurde, um eine stabilere Benzothiophen-Subeinheit anstelle eines antiaromatischen 1,2-Dithiins zu bilden. Folglich konnte somit die Ausweitung und damit die Inversions¬barriere des Helixkörpers nicht durch Erhöhung der Anzahl der 1,2-Dithiin-Einheiten im Molekül erreicht werden. Da 1,2-Dithiine Disulfidbrücken enthalten, wurde ihre Anwendungsmöglichkeit als Kathodenmaterialien in Lithium-Schwefel-Batterien untersucht. Zusätzlich dazu wurde die chemische Reaktivität der 1,2-Dithiine analysiert, wozu neben der Oxidation des 1,2-Dithiins auch die Schwefelextrusion zur selektiven Darstellung von Benzothiophenderivaten gehört. In Kapitel 4 wurden die Synthesemöglichkeiten der meta-Phenylen-1,2-dithiin-polymere und die der entsprechenden 1,2-Dithiin-Makrocyklen in Anlehnung an das [6]Cyclo-meta-phenylen untersucht. Hier konnte Suzuki-vermittelt der Vorläufer des meta-Phenylen-1,2-dithiinpolymers dargestellt werden. Alle weiteren Synthese-versuche scheiterten: beim Polymer infolge der in Kapitel 3 besprochenen Schwefelextrusion und beim Makrocylus wegen zu hoher Sterik oder unvollständiger Substitution. In Kapitel 5 ging es um Poly-meta-phenylene an der Wasser-Luft-Grenzfläche die in ihrer Seitenkette befindliche Azobenzoleinheiten infolge eines Lichtpulses cis/trans-isomerisieren lassen sollen, um an der Oberfläche eine Geschwindigkeitsverände¬rung zu induzieren. Nach der Synthese diverser Polymere dieses Typs wurde dann zunächst die freie Schaltbarkeit der Azobenzoleinheiten mittels UV/Vis-Spektrum und Bestrahlung im jeweiliegen cis- bzw. trans-Konfigurationsmaximum untersucht. Zusätzlich wurde mittels Langmuir-Trog die Bildung von Monolagen an der Wasser¬oberfläche und mittels transienter SFG-Spektroskopie (Sum-Frequency-Generation-Spektroskopy) der Einfluss der Azobenzole auf die umliegenden Wassermoleküle beobachtet. Im letzten Schritt galt es per FCS (Fluoreszenz korrelations¬spektros¬kopie) zu schauen, ob sich der anhängte Farbstoff (ein PMI) in Folge der Bestrahlung im Vergleich zur Brown´schen Molekularbewegung verändert bewegt.The present dissertation is subdivided into the topic of meta- and para-phenylenes as 1,2-dithiines and the azobenzene-containing meta-phenylene polymers. The 1,2-dithiine can be opened and closed by redox reaction via the contained disulfide bridge. While the azobenzene-containing meta-phenylenes are UV-Vis cis / trans-isomerized and is thus between two states back and forth switchable. In Chapter 3, 1,2-dithiine oligomers in the form of meta- and para-phenylenes were prepared and analyzed for their crystal-forming and optical properties. The effect of the thiomethyl-substitution in the 1- and 1'-positions on the rotational barrier of biphenyl bond was calculated. Since this is insufficient to achieve the goal of stable switchable helicenes, in the case of the meta-phenylene-1,2-dithiine, the end-to-end overlap was enhanced by naphthalene residues. This was necessary because with increasing 1,2-dithiine subunits in the molecule sulfur was extruded to form a more stable benzothiophene subunit instead of an antiaromatic 1,2-dithiine. Consequently, the expansion and thus the inversion barrier of the helical body could not be achieved by increasing the number of 1,2-dithiine units in the molecule. Since 1,2-dithiines contain disulfide bridges, their application as cathode materials in lithium-sulfur batteries has been investigated. In addition, the chemical reactivity of the 1,2-dithiines was analyzed, which included not only the oxidation of 1,2-dithiine, but also sulfur extrusion for the selective preparation of benzothiophene derivatives. In Chapter 4, the synthetic possibilities of the meta-phenylene-1,2-dithiine polymers and of the corresponding 1,2-dithiine macrocycles based on [6] cyclo-meta-phenyl-ene were investigated. Here, Suzuki-mediated precursor of the meta-phe¬nylene-1,2-dithiine polymer was synthesized. Due to the loss of sulfur to form more stable benzothiophenes – as already mentioned in chapter 3 – a bigger 1,2-dithiin-polymer was not reached. In case of the macrocycles, the extreme steric hindrance or incomplete reactions blocked their synthesis. Chapter 5 focused on poly-meta-phenylenes at the water-air interface, where the azobenzene moieties in their side chains should be cis/trans-isomerized. This happens due to a light pulse with the aim to induce a change in the movement of the polymer at the surface. After the synthesis of various polymers of this type, the free switch ability of the azobenzene units by UV/Vis spectrum and irradiation in the respective cis- or trans-configuration maximum was first investigated. By Langmuir trough technique we observed the formation of monolayers at the water surface. The in¬fluence of the azobenzene-isomerization on the surrounding water molecules were checked by transient SFG spectroscopy (sum-frequency generation spectroscopy). The final step was to use FCS (Fluorescence Correlation Spectroscopy) to see, if the attached dye (a PMI) changes its speed because of irradiation compared to Brownian molecular motion only

Virtopsy post-mortem multi-slice computed tomograhy (MSCT) and magnetic resonance imaging (MRI) demonstrating descending tonsillar herniation: comparison to clinical studies

Descending cerebellar tonsillar herniation is a serious and common complication of intracranial mass lesions. We documented three cases of fatal blunt head injury using post-mortem multi-slice computed tomography (MSCT) and magnetic resonance imaging (MRI). The results showed massive bone and soft-tissue injuries of the head and signs of high intracranial pressure with herniation of the cerebellar tonsils. The diagnosis of tonsillar herniation by post-mortem radiological examination was performed prior to autopsy. This paper describes the detailed retrospective evaluation of the position of the cerebellar tonsils in post-mortem imaging in comparison to clinical studie

Energy Informatics - Current and Future Research Directions

Due to the increasing importance of producing and consuming energy more sustainably, Energy Informatics (EI) has evolved into a thriving research area within the CS/IS community. The arti- cle attempts to characterize this young and dynamic field of research by de- scribing current EI research topics and methods and provides an outlook of how the field might evolve in the fu- ture. It is shown that two general re- search questions have received the most attention so far and are likely to dominate the EI research agenda in the coming years: How to leverage infor- mation and communication technol- ogy (ICT) to (1) improve energy effi- ciency, and (2) to integrate decentral- ized renewable energy sources into the power grid. Selected EI streams are reviewed, highlighting how the re- spective research questions are broken down into specific research projects and how EI researchers have made con- tributions based on their individual academic background

Virtopsy post-mortem multi-slice computed tomography (MSCT) and magnetic resonance imaging (MRI) demonstrating descending tonsillar herniation: comparison to clinical studies.

Descending cerebellar tonsillar herniation is a serious and common complication of intracranial mass lesions. We documented three cases of fatal blunt head injury using post-mortem multi-slice computed tomography (MSCT) and magnetic resonance imaging (MRI). The results showed massive bone and soft-tissue injuries of the head and signs of high intracranial pressure with herniation of the cerebellar tonsils. The diagnosis of tonsillar herniation by post-mortem radiological examination was performed prior to autopsy. This paper describes the detailed retrospective evaluation of the position of the cerebellar tonsils in post-mortem imaging in comparison to clinical studies

Third International Consensus Conference on lesions of uncertain malignant potential in the breast (B3 lesions)

The heterogeneous group of B3 lesions in the breast harbors lesions with different malignant potential and progression risk. As several studies about B3 lesions have been published since the last Consensus in 2018, the 3rd International Consensus Conference discussed the six most relevant B3 lesions (atypical ductal hyperplasia (ADH), flat epithelial atypia (FEA), classical lobular neoplasia (LN), radial scar (RS), papillary lesions (PL) without atypia, and phyllodes tumors (PT)) and made recommendations for diagnostic and therapeutic approaches. Following a presentation of current data of each B3 lesion, the international and interdisciplinary panel of 33 specialists and key opinion leaders voted on the recommendations for further management after core-needle biopsy (CNB) and vacuum-assisted biopsy (VAB). In case of B3 lesion diagnosis on CNB, OE was recommended in ADH and PT, whereas in the other B3 lesions, vacuum-assisted excision was considered an equivalent alternative to OE. In ADH, most panelists (76%) recommended an open excision (OE) after diagnosis on VAB, whereas observation after a complete VAB-removal on imaging was accepted by 34%. In LN, the majority of the panel (90%) preferred observation following complete VAB-removal. Results were similar in RS (82%), PL (100%), and FEA (100%). In benign PT, a slim majority (55%) also recommended an observation after a complete VAB-removal. VAB with subsequent active surveillance can replace an open surgical intervention for most B3 lesions (RS, FEA, PL, PT, and LN). Compared to previous recommendations, there is an increasing trend to a de-escalating strategy in classical LN. Due to the higher risk of upgrade into malignancy, OE remains the preferred approach after the diagnosis of ADH

Differential cross section measurements for the production of a W boson in association with jets in proton–proton collisions at √s = 7 TeV

Measurements are reported of differential cross sections for the production of a W boson, which decays into a muon and a neutrino, in association with jets, as a function of several variables, including the transverse momenta (pT) and pseudorapidities of the four leading jets, the scalar sum of jet transverse momenta (HT), and the difference in azimuthal angle between the directions of each jet and the muon. The data sample of pp collisions at a centre-of-mass energy of 7 TeV was collected with the CMS detector at the LHC and corresponds to an integrated luminosity of 5.0 fb[superscript −1]. The measured cross sections are compared to predictions from Monte Carlo generators, MadGraph + pythia and sherpa, and to next-to-leading-order calculations from BlackHat + sherpa. The differential cross sections are found to be in agreement with the predictions, apart from the pT distributions of the leading jets at high pT values, the distributions of the HT at high-HT and low jet multiplicity, and the distribution of the difference in azimuthal angle between the leading jet and the muon at low values.United States. Dept. of EnergyNational Science Foundation (U.S.)Alfred P. Sloan Foundatio

Penilaian Kinerja Keuangan Koperasi di Kabupaten Pelalawan

This paper describe development and financial performance of cooperative in District Pelalawan among 2007 - 2008. Studies on primary and secondary cooperative in 12 sub-districts. Method in this stady use performance measuring of productivity, efficiency, growth, liquidity, and solvability of cooperative. Productivity of cooperative in Pelalawan was highly but efficiency still low. Profit and income were highly, even liquidity of cooperative very high, and solvability was good

Juxtaposing BTE and ATE – on the role of the European insurance industry in funding civil litigation

One of the ways in which legal services are financed, and indeed shaped, is through private insurance arrangement. Two contrasting types of legal expenses insurance contracts (LEI) seem to dominate in Europe: before the event (BTE) and after the event (ATE) legal expenses insurance. Notwithstanding institutional differences between different legal systems, BTE and ATE insurance arrangements may be instrumental if government policy is geared towards strengthening a market-oriented system of financing access to justice for individuals and business. At the same time, emphasizing the role of a private industry as a keeper of the gates to justice raises issues of accountability and transparency, not readily reconcilable with demands of competition. Moreover, multiple actors (clients, lawyers, courts, insurers) are involved, causing behavioural dynamics which are not easily predicted or influenced. Against this background, this paper looks into BTE and ATE arrangements by analysing the particularities of BTE and ATE arrangements currently available in some European jurisdictions and by painting a picture of their respective markets and legal contexts. This allows for some reflection on the performance of BTE and ATE providers as both financiers and keepers. Two issues emerge from the analysis that are worthy of some further reflection. Firstly, there is the problematic long-term sustainability of some ATE products. Secondly, the challenges faced by policymakers that would like to nudge consumers into voluntarily taking out BTE LEI

Search for stop and higgsino production using diphoton Higgs boson decays

Results are presented of a search for a "natural" supersymmetry scenario with gauge mediated symmetry breaking. It is assumed that only the supersymmetric partners of the top-quark (stop) and the Higgs boson (higgsino) are accessible. Events are examined in which there are two photons forming a Higgs boson candidate, and at least two b-quark jets. In 19.7 inverse femtobarns of proton-proton collision data at sqrt(s) = 8 TeV, recorded in the CMS experiment, no evidence of a signal is found and lower limits at the 95% confidence level are set, excluding the stop mass below 360 to 410 GeV, depending on the higgsino mass

Impacts of the Tropical Pacific/Indian Oceans on the Seasonal Cycle of the West African Monsoon

The current consensus is that drought has developed in the Sahel during the second half of the twentieth century as a result of remote effects of oceanic anomalies amplified by local land–atmosphere interactions. This paper focuses on the impacts of oceanic anomalies upon West African climate and specifically aims to identify those from SST anomalies in the Pacific/Indian Oceans during spring and summer seasons, when they were significant. Idealized sensitivity experiments are performed with four atmospheric general circulation models (AGCMs). The prescribed SST patterns used in the AGCMs are based on the leading mode of covariability between SST anomalies over the Pacific/Indian Oceans and summer rainfall over West Africa. The results show that such oceanic anomalies in the Pacific/Indian Ocean lead to a northward shift of an anomalous dry belt from the Gulf of Guinea to the Sahel as the season advances. In the Sahel, the magnitude of rainfall anomalies is comparable to that obtained by other authors using SST anomalies confined to the proximity of the Atlantic Ocean. The mechanism connecting the Pacific/Indian SST anomalies with West African rainfall has a strong seasonal cycle. In spring (May and June), anomalous subsidence develops over both the Maritime Continent and the equatorial Atlantic in response to the enhanced equatorial heating. Precipitation increases over continental West Africa in association with stronger zonal convergence of moisture. In addition, precipitation decreases over the Gulf of Guinea. During the monsoon peak (July and August), the SST anomalies move westward over the equatorial Pacific and the two regions where subsidence occurred earlier in the seasons merge over West Africa. The monsoon weakens and rainfall decreases over the Sahel, especially in August.Peer reviewe