Electrochemical, Computational, And Reactivity Studies Of Strongly Stabilized Cerium(iv) Hydroxylaminato Coordination Complexes And Pyrroloquinoline Quinone Cofactor Surrogates

A series of electron rich, air-stable hydroxylamine ligands and their strongly stabilized cerium(IV) hydroxylaminato complexes are described. Monotopic, ditopic, and tetratopic hydroxylaminato ligands are described. The synthesis and characterization of HLNOx, H2ODiNOx, H2PhNDiNOx, and H4TetraNOx were accomplished through modified literature procedures from their parent aryl bromides. The cerium(IV) complexes Ce(LNOx)4, Ce(ODiNOx)2 were synthesized by protonolysis reactions, crystallized, and characterized electrochemically and computationally. The cerium(IV) complexes exhibited significant stabilization of the Ce(III/IV) couple as observed in their cyclic voltammetry data. The pyrroloquinoline quinone (PQQ) is an important cofactor that shuttles redox equivalents in diverse metalloproteins. Quinoline 7,8-quinones have been synthesized and characterized as surrogates for PQQ to elucidate redox energetics within metalloenzyme active sites. The quinoline 7,8-quinones were synthesized, and the compounds were evaluated using solution electrochemistry. Together with a family of quinones, the products were evaluated computationally and used to generate a predictive correlation between a computed ΔG and the experimental reduction potentials. The methoxy substituted derivative exhibited catalytic activity in the dehydrogenation of benzylamines. The stoichiometric dehydrogenation of benzyl alcohols was also achieved with irradiation

Is the equity premium puzzle just a lack of foresight? The impact of targeting on myopic loss a aversion

Imagine an individual facing three identical investment decisions in a row. Each time she decides on how much to invest in a risky asset or save. Also, imagine the same individual deciding about three consecutive investments at once. Equal for rational investors, when suffering Myopic Loss Aversion, the latter scenario is perceived differently though: More is invested when payoffs are evaluated over a greater time horizon. Based on the theory of reference points I proposed a novel method – investment targets – to shift attention to longer-term goals. I find that exogenously proposed targets eliminate Myopic Loss Aversion in an experiment

Diener vieler Herren. Die Reichs-Agenten am Kaiserhof (1550-1740)

Working at the Imperial Court in Vienna and Prague, respectively, the “Imperial Agents” were an important functionary elite in the Holy Roman Empire of the German Nation. They served as representatives of the princes and estates of the Empire, who usually lived several hundred kilometers from the Imperial Court. One of the agents’ central tasks was, for example, to conduct trials before the Imperial Supreme Court, to carry out diplomatic missions, and to gather information. The essay analyzes the activity spectrum of the agents and thus contributes to a better understanding of the mode of operation of both the Imperial Court and the empire. At the same time it proves the thesis that the emperor also benefited from the activities of the “Imperial Agents”.Die am Kaiserhof in Wien bzw. Prag tätigen „Reichs-Agenten“ waren eine wichtige Funktionselite im Heiligen Römischen Reich deutscher Nation. Sie fungierten als Interessenvertreter der Fürsten und Stände des Reiches, die in der Regel mehrere hundert Kilometer vom Kaiserhof entfernt lebten: Zu den zentralen Aufgaben der Agenten gehörte es beispielsweise, Prozesse vor dem kaiserlichen Höchstgericht zu führen, diplomatische Aufträge zu erledigen sowie Informationen zu sammeln. Der Aufsatz analysiert das Tätigkeitsspektrum der Agenten und trägt somit zum besseren Verständnis der Funktionsweise des Kaiserhofs sowie des Reiches bei. Zugleich wird die These belegt, dass auch der Kaiser von der Tätigkeit der „Reichs-Agenten“ profitierte

Can we use it? On the utility of de novo and reference-based assembly of Nanopore data for plant plastome sequencing

The chloroplast genome harbors plenty of valuable information for phylogenetic research. Illumina short-read data is generally used for de novo assembly of whole plastomes. PacBio or Oxford Nanopore long reads are additionally employed in hybrid approaches to enable assembly across the highly similar inverted repeats of a chloroplast genome. Unlike for PacBio, plastome assemblies based solely on Nanopore reads are rarely found, due to their high error rate and non-random error profile. However, the actual quality decline connected to their use has rarely been quantified. Furthermore, no study has employed reference-based assembly using Nanopore reads, which is common with Illumina data. Using Leucanthemum Mill. as an example, we compared the sequence quality of seven chloroplast genome assemblies of the same species, using combinations of two sequencing platforms and three analysis pipelines. In addition, we assessed the factors which might influence Nanopore assembly quality during sequence generation and bioinformatic processing. The consensus sequence derived from de novo assembly of Nanopore data had a sequence identity of 99.59% compared to Illumina short-read de novo assembly. Most of the errors detected were indels (81.5%), and a large majority of them is part of homopolymer regions. The quality of reference-based assembly is heavily dependent upon the choice of a close-enough reference. When using a reference with 0.83% sequence divergence from the studied species, mapping of Nanopore reads results in a consensus comparable to that from Nanopore de novo assembly, and of only slightly inferior quality compared to a reference-based assembly with Illumina data. For optimal de novo assembly of Nanopore data, appropriate filtering of contaminants and chimeric sequences, as well as employing moderate read coverage, is essential. Based on these results, we conclude that Nanopore long reads are a suitable alternative to Illumina short reads in plastome phylogenomics. Few errors remain in the finalized assembly, which can be easily masked in phylogenetic analyses without loss in analytical accuracy. The easily applicable and cost-effective technology might warrant more attention by researchers dealing with plant chloroplast genomes