COORDINATION CHEMISTRY OF BIS(BENZYL)PHOSPHINATE

The work presented in this dissertation deals with the coordination chemistry of the bis(benzyl)phosphinate ligand with vanadium, tungsten and cobalt. The long term goal of this project was to produce and physically characterize high oxidation state transition metal oxide phosphinate compounds with potential catalytic applications. The reaction of bis(benzyl)phosphinic acid with VO(acac)2 in the presence of water or pyridine leads to the synthesis of trimeric vanadium(IV) clusters (V3(µ3-O)O2)(µ2-O2P(CH2C6H5)2)6(H2O) and (V3(µ3-O)O2)(µ2-O2P(CH2C6H5)2)6(py). In contrast, when diphenylphosphinic acid or 2-hydroxyisophosphindoline-2-oxide were reacted with VO(acac)2, insoluble polymeric compounds were produced. The trimeric clusters were characterized using FTIR, elemental analysis, single crystal diffraction, room temperature magnetic susceptibility, thermogravimetric analysis and differential scanning calorimetry. The variable-temperature, solid-state magnetic susceptibility was measured on (V3(µ3-O)O2)(µ2-O2P(CH2C6H5)2)6(py). The polymeric compounds were characterized using FTIR, powder diffraction and elemental analysis. Two different cubane clusters made of tungsten(V) and vanadium(V) were stabilized using bis(benzyl)phosphinate. The oxidation of (V3(µ3-O)O2)(µ2-O2P(CH2C6H5)2)6(H2O) with tBuOOH led to the formation of V4(µ3-O)4(µ2-O2P(Bn)2)4(O4). W4(µ3-O)4(µ2-O2P(Bn)2)4(O4) was produced by heating W(CO)6 in a 1:1 mixture of EtOH/THF at 120 ˚C. Both compounds were characterized using single crystal diffraction, FTIR, 31P-NMR, 1H-NMR and elemental analysis. W4(µ3-O)4(µ2-O2P(Bn)2)4(O4) was also characterized using UV-vis. Cobalt(II) reacted with bis(benzyl)phosphinate to produce three different dinuclear complexes. [(py)3Co(µ2-O2P(Bn)2)3Co(py)][ClO4], (py)3Co(µ2-O2P(Bn)2)3Co(Cl) and (py)(µ2-NO3)Co(µ2-O2P(Bn)2)3Co(py) were all characterized using single crystal diffraction, elemental analysis and FTIR. Room temperature magnetic susceptibility measurements were performed on [(py)3Co(µ2-O2P(Bn)2)3Co(py)][ClO4] and (py)3Co(µ2-O2P(Bn)2)3Co(Cl). The variable-temperature, solid-state magnetic susceptibility was also measured on [(py)3Co(µ2-O2P(Bn)2)3Co(py)][ClO4].

Intra- and inter-individual variation of BIS-index and Entropy during controlled sedation with midazolam/remifentanil and dexmedetomidine/remifentanil in healthy volunteers: an interventional study

INTRODUCTION: We studied intra-individual and inter-individual variability of two online sedation monitors, BIS and Entropy, in volunteers under sedation. METHODS: Ten healthy volunteers were sedated in a stepwise manner with doses of either midazolam and remifentanil or dexmedetomidine and remifentanil. One week later the procedure was repeated with the remaining drug combination. The doses were adjusted to achieve three different sedation levels (Ramsay Scores 2, 3 and 4) and controlled by a computer-driven drug-delivery system to maintain stable plasma concentrations of the drugs. At each level of sedation, BIS and Entropy (response entropy and state entropy) values were recorded for 20 minutes. Baseline recordings were obtained before the sedative medications were administered. RESULTS: Both inter-individual and intra-individual variability increased as the sedation level deepened. Entropy values showed greater variability than BIS(R) values, and the variability was greater during dexmedetomidine/remifentanil sedation than during midazolam/remifentanil sedation. CONCLUSIONS: The large intra-individual and inter-individual variability of BIS and Entropy values in sedated volunteers makes the determination of sedation levels by processed electroencephalogram (EEG) variables impossible. Reports in the literature which draw conclusions based on processed EEG variables obtained from sedated intensive care unit (ICU) patients may be inaccurate due to this variability. TRIAL REGISTRATION: clinicaltrials.gov Nr. NCT00641563.

E-Learning 2.0 in hydraulic engineering education

In this contribution the experiences with e-Learning 2.0 applications by using a Wiki for the education in hydraulic engineering are shown. Up to now important information for the students has been prepared by the instructor. For this project the students were asked to collaborate and search on their own for the information they needed. Therefore a Wiki-system was used. For the engineering practice a self dependent realisation of tasks is an important requirement which students should be prepared for. With the help of online communication there should be shown the possibilities for students for working together in an interdisciplinary team. The positive experiences as well as the results of the evaluation of this project plead for a continuation of the application of e-Learning 2.0 for education. The comparison of results of tests without using Wiki and with using Wiki shows a qualitative tendency of better marks. In this contribution we present the application of Wiki in hydraulic engineering but the results can also be used for other engineering disciplines.

Onlinestudie: Wissenschaftliches Arbeiten im Web 2.0

Das Web 2.0 eröffnet Wissenschaftlerinnen und Wissenschaftlern neue Möglichkeiten mit Wissen und Informationen umzugehen: Das Recherchieren von Informationen und Quellen, der Austausch von Wissen mit anderen, das Verwalten von Ressourcen und das Erstellen von eigenen Inhalten im Web ist einfach und kostengünstig möglich. Dieser Artikel thematisiert die Bedeutung des Web 2.0 für den Umgang mit Wissen und Informationen und zeigt auf, wie durch die Kooperation vieler Einzelner das Schaffen von neuem Wissen und von Innovationen möglich wird. Diskutiert werden der Einfluss des Web 2.0 auf die Wissenschaft und mögliche Vor- und Nachteile der Nutzung. Außerdem wird ein kurzer Überblick über Studien gegeben, die die Nutzung des Web 2.0 in der Gesamtbevölkerung untersuchen. Im empirischen Teil des Artikels werden Methode und Ergebnisse der Befragungsstudie „Wissenschaftliches Arbeiten im Web 2.0“ vorgestellt. Befragt wurden Nachwuchswissenschaftlerinnen und Nachwuchswissenschaftler in Deutschland zur Nutzung des Web 2.0 für die eigene wissenschaftliche Arbeit. Dabei zeigt sich, dass insbesondere die Wikipedia von einem Großteil der Befragten intensiv bis sehr intensiv für den Einstieg in die Recherche verwendet wird. Die aktive Nutzung des Web 2.0, z.B. durch das Schreiben eines eigenen Blogs oder dem Mitarbeiten bei der Online-Enzyklopädie Wikipedia ist bis jetzt noch gering. Viele Dienste sind unbekannt oder werden eher skeptisch beurteilt, der lokale Desktopcomputer wurde noch nicht vom Web als zentraler Speicherort abgelöst.