Reaction behavior of iron and copper complexes towards dioxygen

To provide a better understanding of the reactions of iron and copper proteins with dioxygen, the corresponding reactions of small molecule model complexes with dioxygen were analysed using spectroscopic and kinetic methods. Special attention focused upon the binding and activation of dioxygen by iron proteins such as hemerythrin (Hr) and protocatechuat-3,4-dioxygenase (3,4-PCD) and by copper proteins like hemocyanin (Hc) and tyrosinase. Iron complexes of the ligand tmpa (tmpa = tris[(2-pyridyl)methyl]amine, also known as tpa in literature) were synthesised and modifications of the tmpa ligand were made. Increasing as well as decreasing chelate ring sizes in the highly active complex [Fe(tmpa)(dbc)]B(C6H5)4 (dbc = 3,5-di-tert-butylcatecholate dianion), only resulted in decreased reactivity of the investigated compounds. A detailed low-temperature stopped-flow investigation of the reaction of dioxygen with [Fe(tmpa)(dbc)]B(C6H5)4 was performed and activation parameters of Delta H# = 23 +- 1 kJ mol-1 and Delta S# = -199 +- 4 J mol-1 K-1 were obtained. Crystal structures of bromo-(tetrachlorocatecholato-O,O\u27)(bis((2-pyridyl)methyl)-2-pyridylamine-N,N\u27,N\u27\u27)-iron(III) (2), (mu-oxo)-bis(bromo)(bis((2-pyridyl)methyl)-2-pyridylamine-N,N\u27,N\u27\u27,N\u27\u27\u27)-diiron(III) (3), dichloro-((2-(2-pyridyl)ethyl)bis((2-pyridyl)methyl)amine-N,N\u27,N\u27\u27,N\u27\u27\u27)-iron(III) (4) and (tetrabromocatecholato-O,O\u27)((2-(2-pyridyl)ethyl)bis((2-pyridyl)methyl)amine-N,N\u27,N\u27\u27,N\u27\u27\u27)-iron(III) (5) are reported (Chapter 2). Besides altering the chelate ring size the influence of the donor atoms of the ligand on catechol dioxygenase reactivity was investigated. Two derivatives of the tmpa ligand (uns-penp and acetyl-uns-penp) were synthesised, where one aromatic nitrogen donor was replaced by an aliphatic nitrogen donor. The iron(III) complexes of the tripodal ligands N\u27,N\u27-bis[(2-pyridyl)methyl]ethylenediamine (uns-penp), [Fe(uns-penp)Cl2]ClO4 x CH3CN, [{Fe(uns-penp)Cl}2O](ClO4)2 x 2CH3CN and the amide derivative N-Acetyl-N\u27,N\u27-bis[(2-pyridyl)methyl]ethylenediamine (acetyl-uns-penp), [Fe2(acetyl-uns-penp)2O](ClO4)2 x H2O, [Fe(acetyl-uns-penp)(tcc)Br] x (C2H5)2O and [{Fe(acetyl-uns-penp)(tcc)}2O] x (C2H5)2O x CH3OH were synthesised and characterised. Catechol dioxygenase reactivity of in situ prepared complex solutions only showed slower reactions in comparison with the iron tmpa system (Chapter 3). Corresponding ligand system variations in the small molecule model complexes of copper proteins were made and analysed with respect to dioxygen reactivity. Intramolecular ligand hydroxylation was observed during the reactions of dioxygen with the dicopper(I) complexes of the ligands L3 (L3 = alpha,alpha\u27-bis[(2-pyridylethyl)amino]-m-xylene) and L5 (L5 = alpha,alpha\u27-bis[N-(2-pyridylethyl)-N-(2-pyridylmethyl)-amino]-m-xylene). The dinuclear copper(I) complex [Cu2L5](ClO4)2 and the dicopper(II) complex [Cu2(L3-O)(OH)(ClO4)]ClO4 were characterised by single-crystal X-ray structure analysis. Furthermore, phenolate-bridged complexes were synthesised with the ligand L4-OH and Me-L5-OH (structurally characterised: [Cu2(L4-O)Cl3] with L4 = alpha,alpha\u27-bis[N-methyl-N-(2-pyridylethyl)amino]-m-xylene and [Cu2(Me-L5-O)(mu-X)](ClO4)2 x nH2O with Me-L5-OH = 2,6-bis[N-(2-pyridylethyl)-N-(2-pyridylmethyl)amino]-4-methylphenol and X = C3H3N2- (prz), MeCO2- and N3-). Temperature-dependent magnetic studies revealed the antiferromagnetic coupling of the copper ions of these complexes (Chapter 4). The reactions of dioxygen with copper(I) complexes of the tridentate ligands 1,1,4,7,7-pentamethyldiethylethylenetriamine (Me5dien), 1,1,4,7,7-pentaethyldiethylethylenetriamine (Et5dien), N-methyl-[bis(2-pyridyl)methyl]amine (Me-bpa) and N-methyl-[(2-pyridyl)ethyl(2-pyridyl)methyl]amine (MeL) have been investigated using low-temperature stopped-flow techniques. The formation of a bis(mu-oxo) copper complex as a reactive intermediate could only be detected spectroscopically at low temperatures for [Cu(Me5dien)(CH3CN)]ClO4 and allowed a quantitative kinetic analysis to be performed. Crystal structures of the copper(II) complexes [(Me-bpa)Cu(Cl)2], [{(Me-bpa)Cu(Cl)(ClO4)}2], [{(MeL)Cu(Cl)(ClO4)}2] and [(MeL)Cu(NCS)2] are reported. (Chapter 5)Zum besseren Verständnis der Reaktionen von Eisen- und Kupferproteinen mit elementarem Sauerstoff wurden im Rahmen dieser Arbeit für Eisen- und Kupferproteine Modellkomplexe mit geringer Molekularmasse mit spektroskopischen oder kinetischen Methoden untersucht. Besondere Aufmerksamkeit wurde hierbei der Bindung und der Aktivierung von elementarem Sauerstoff durch die Eisenproteine, wie z. B. Hämerythrin (Hr) und Protocatechuat-3,4-dioxygenase (3,4-PCD), und die Kupferproteine, wie z. B. Hämocyanin (Hc) und Tyrosinase, gewidmet. Bezüglich der Modelle für Eisenenzyme wurde der Ligand tmpa (tmpa = tris[(2-pyridyl)methyl]amin; in der Literatur auch mit tpa abgekürzt) untersucht und systematisch variiert. Die Vergrößerung und Verkleinerung der Chelatringgröße im hochreaktiven Komplex [Fe(tmpa)(dbc)]B(C6H5)4 (dbc = 3,5-Di-tert-butylcatecholat Dianion) führte nur zu einer verringerten Reaktivität der untersuchten Verbindungen. Die Reaktion von elementaren Sauerstoff mit [Fe(tmpa)(dbc)]B(C6H5)4 wurde mittels der Tieftemperatur-\u27stopped-flow\u27-Technik untersucht und ergab die Aktivierungsparameter Delta H# = 23 +- 1 kJ mol-1 und Delta S# = -199 +- 4 J mol-1 K-1. Weiterhin wurden die Kristallstrukturanalysen der Verbindungen bromo-(tetra-chlorocatecholato-O,O\u27)(bis((2-pyridyl)methyl)-2-pyridylamine-N,N\u27,N\u27\u27)-eisen(III) (2), (mü-oxo)-bis(bromo)(bis((2-pyridyl)methyl)-2-pyridylamine-N,N\u27,N\u27\u27,N\u27\u27\u27)-dieisen (III) (3), dichloro-((2-(2-pyridyl)ethyl)bis((2-pyridyl)methyl)amine-N,N\u27,N\u27\u27,N\u27\u27\u27)-eisen (III) (4) und (tetrabromocatecholato-O,O\u27)((2-(2-pyridyl)ethyl)bis((2-pyridyl)methyl) amine-N,N\u27,N\u27\u27,N\u27\u27\u27)-eisen (III) (5) beschrieben (Kapitel 2). Neben der Änderung der Chelatringgröße wurde auch der Einfluss der Donoratome des Liganden untersucht. Dazu wurden abgeleitet vom tmpa zwei Liganden (uns-penp und acteyl-uns-penp) synthetisiert, bei denen ein aromatischer Stickstoff durch einen aliphatischen Stickstoff ersetzt wurde. Die Eisen(III)-Komplexe mit den tripodalen Liganden N\u27,N\u27-bis[(2-pyridyl)methyl]ethylenediamin (uns-penp), [Fe(uns-penp)Cl2]ClO4 x CH3CN, [{Fe(uns-penp)Cl}2O](ClO4)2 x 2CH3CN und dem Amidderivat N-Acetyl-N\u27,N\u27-bis[(2-pyridyl)methyl]ethylenediamin (acetyl-uns-penp), [Fe2(acetyl-uns-penp)2O](ClO4)2 x H2O, [Fe(acetyl-uns-penp)(tcc)Br] x (C2H5)2O und [{Fe(acetyl-uns-penp)(tcc)}2O] x (C2H5)2O x CH3OH wurden synthetisiert und charakterisiert. Untersuchungen zur Catecholdioxygenasereaktivität der in situ dargestellten Komplexlösungen zeigten nur langsamere Reaktionen im Vergleich zu dem Eisen-tmpa-System (Kapitel 3) Die Ligandensysteme für Modelle von Kupferproteinen wurden nach denselben Gesichtspunkten verändert wie bei den Modellen für die Eisenproteine. Intramolekulare Hydroxylierung des Liganden war bei der Reaktion von elementaren Sauerstoff mit Dikupfer(I)-Komplexen der Liganden L3 (L3 = alpha,alpha\u27-bis[(2-pyridylethyl)amino]-m-xylol) und L5 (L5 = alpha,alpha\u27-bis[N-(2-pyridylethyl)-N-(2-pyridylmethyl)-amino]-m-xylol) zu beobachten. Der dinukleare Kupfer(I)-Komplex [Cu2L5](ClO4)2 und der Dikupfer(II)-Komplex [Cu2(L3-O)(OH)(ClO4)]ClO4 konnten durch Einkristallröntgenstrukturanalyse charakterisiert werden. Zusätzlich wurden Phenolatverbrückte Komplexe mit den Liganden L4-OH und Me-L5-OH synthetisiert (Strukturlösungen für [Cu2(L4-O)Cl3] mit L4 = alpha,alpha\u27-bis[N-methyl-N-(2-pyridylethyl)amino]-m-xylol und [Cu2(Me-L5-O)(mü-X)](ClO4)2 x nH2O (Me-L5-OH = 2,6-bis[N-(2-pyridylethyl)-N-(2-pyridylmethyl)amino]-4-methylphenol und X = C3H3N2- (prz), MeCO2- und N3-). Temperaturabhängige magnetische Untersuchungen zeigten antiferromagnetische Kopplung der Kupferionen in diesen Komplexen (Kapitel 4). Die Reaktionen von elementaren Sauerstoff mit Kupfer(I)-Komplexen der dreizähnigen Liganden 1,1,4,7,7-pentamethyldiethylethylenetriamin (Me5dien), 1,1,4,7,7-pentaethyldiethylethylenetriamin (Et5dien), N-methyl-[bis(2-pyridyl) methyl]amin (Me-bpa) und N-methyl-[(2-pyridyl)ethyl(2-pyridyl)methyl]amin (MeL) mit Hilfe der Tieftemperatur-\u27stopped-flow\u27-Technik untersucht. Die Bildung eines bis(mü-oxo)-Kupferkomplexes konnte dabei bei tiefen Temperaturen nur für den Komplex [Cu(Me5dien)(CH3CN)]ClO4 spektroskopisch beobachtet und quantitativ kinetisch analysiert werden. Die Komplexe [(Me-bpa)Cu(Cl)2], [{(Me-bpa)Cu(Cl)(ClO4)}2], [{(MeL)Cu(Cl)(ClO4)}2] und [(MeL)Cu(NCS)2] konnten kristallographisch charakterisiert werden. (Kapitel 5

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Abstract Quality management is an important function for viable production networks. In order to qualify decision makers to understand the fundamental principles of quality management in production networks, a game-based simulation and learning environment is developed, which can furthermore be used to understand how human factors influence the quality of decisions in complex production networks. Previous studies have shown that underlying factors must exist, which predict the players' performance. It is currently unexplored, which factors are contributing to high performance. To deeper investigate which human factors are critical for supply chain success and to further refine the quality management game a series of studies were examined. As expected, expertise had a great impact on performance, however contrary to the expectations cognitive skills had none. The refined decision dashboard, with seamlessly integrated self-adapting visualizations on key performance indicators, had a significant positive impact on game performance. The studies suggest that the developed game is a valuable contribution for the qualification of quality managers, as the quality of decision increased

Identification of regulatory variants associated with genetic susceptibility to meningococcal disease.

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Although electric drives can locally reduce the environmental impact of traffic, the penetration rates of battery electric vehicles (BEV) are far below expectations, not least because the charging infrastructure network is still considered insufficient by potential users. Therefore, the planning of charging infrastructure that considers both needs and user requirements is essential to remove an important barrier to widespread adaptation of e-vehicles, but it is also a challenge. A better understanding of the charging behavior and the underlying usage motivation is therefore needed. A frequently mentioned factor is the so-called range stress. While there are many studies on this subject with new BEV users, there is a lack of approaches that also include experienced e-vehicle users and at the same time allow a comparison with drivers of cars with internal combustion engines (ICE). In this paper, this is realized with the help of a questionnaire study ( n = 204 ). The results show that ICE and BEV users at different experience levels hardly differ regarding the perceived range stress; BEV users even perceive less stress. BEV users also showed more trust in the vehicle and in the tank/battery indicators, while this trust depends only marginally on the type of information provided by the car. Furthermore, there is a correlation between users’ technology commitment and risk-taking, on the one hand, and range stress, on the other. However, for the prediction of range stress, gender, experience with e-cars, and the question of whether cars are privately owned, or car-sharing is used, are more relevant

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