Kinetic and thermodynamic effects on intramolecular aromatic substitution in meta and para substituted benzalacetones

meta and para substituted benzalacetones lose the substituents after electron impact in a multi-step intramolecular aromatic substitution. The differences in the relative abundances of the benzopyrylium ions thus formed are not determined by the activation energies for the substituent losses but depend on a delicate balance between the thermodynamic stability of the intermediates involved and the rates of several H-shifts within the intermediates (kinetic stability). The consequences for the analytical utility of intramolecular aromatic substitution are discussed briefly.     

Single-qubit optical quantum fingerprinting

We analyze and demonstrate the feasibility and superiority of linear optical single-qubit fingerprinting over its classical counterpart. For one-qubit fingerprinting of two-bit messages, we prepare "tetrahedral" qubit states experimentally and show that they meet the requirements for quantum fingerprinting to exceed the classical capability. We prove that shared entanglement permits 100% reliable quantum fingerprinting, which will outperform classical fingerprinting even with arbitrary amounts of shared randomness.     

Investigation and design of an impact actuated micro shift valve

New concepts for an impact actuated micro shift valve are presented which are useful, e.g. as implant for the hydrocephalus disease. Such an implant must fulfil requirements, such as using biocompatible materials, a separation of the actuator from the fluid, MRT safety and low-energy consumption in order to allow a battery-powered system. The concepts are based on the impacts that transmit an impulse into the interior of the valve through the casing, switching the valve. In order to predict the energy transmitted into the valve, an elastic multibody model is created, verified with full finite element simulations and experiments on scaled-up models. Using this model, the most important effects and parameters are discussed. Also, fluid effects are included into the elastic multibody model for a qualitative assessment of its influence on the efficiency. The simulations are compared to experiments performed with a scaled model for two different cases. Two designs of a shift valve based on impact actuation are built as prototypes and tested.     

UV-laser ablation of ionic liquid matrices

Ionic liquid matrices are a new class of matrices used in MALDI mass spectrometry. The ablation process of several ionic liquid matrices was studied by determining the velocity distribution of ablated neutral matrix molecules. This was done by a postionization approach, where the neutrals were ionized in the ablation plume by a second laser pulse. It was found that a second, time-delayed ablation event occurs consisting completely of neutral molecules. To explain this, the reflected-shockwave model is used, which assumes that the shockwave emerging from the laser ablation is reflected at the sample holder surface. When the shockwave arrives at the sample surface it causes a second ablation.     

Supramolecular clusters between carbohydrates and concave pyridines. Detection in the gas phase by resonance-enhanced multi-photon ionization reflectron time-of-flight mass spectrometer

For the first time the formation of supramolecular clusters between concave pyridines and different carbohydrates could be observed in the gas phase. The different clusters have been investigated by means of laser desorption into a supersonic beam followed by resonant multi photon excitation yielding mass spectra with high intensity of the different cluster. These preliminary results open a way for the investigations of the hydrogen bonds in these compounds.     

Multiple hydrogen bonds. Mass spectra of hydrogen bonded heterodimers. A comparison of ESI- and REMPI-ReTOF-MS

Resonance enhanced multi-photon ionization-reflectron time of flight mass spectrometry is the analytical method of choice to observe hydrogen bonded supramolecules in the gas phase when protonation of basic centers competes with cluster formation.     

Die eindeutige Bestimmung einer Klasse von offenen,vollständigen Flächen durch die Metrik

Ohne ZusammenfassungHerrnWilhelm Süss zum 60. Geburtstag am 7. März 1955 gewidmet.     

Mimicking Elementary Reactions of Manganese Lipoxygenase Using Mn-hydroxo and Mn-alkylperoxo Complexes

Manganese lipoxygenase (MnLOX) is an enzyme that converts polyunsaturated fatty acids to alkyl hydroperoxides. In proposed mechanisms for this enzyme, the transfer of a hydrogen atom from a substrate C-H bond to an active-site Mn^III-hydroxo center initiates substrate oxidation. In some proposed mechanisms, the active-site Mn^III-hydroxo complex is regenerated by the reaction of a Mn^III-alkylperoxo intermediate with water by a ligand substitution reaction. In a recent study, we described a pair of Mn^III-hydroxo and Mn^III-alkylperoxo complexes supported by the same amide-containing pentadentate ligand (^6Medpaq). In this present work, we describe the reaction of the Mn^III-hydroxo unit in C-H and O-H bond oxidation processes, thus mimicking one of the elementary reactions of the MnLOX enzyme. An analysis of kinetic data shows that the Mn^III-hydroxo complex [Mn^III(OH)(^6Medpaq)]⁺ oxidizes TEMPOH (2,2′-6,6′-tetramethylpiperidine-1-ol) faster than the majority of previously reported Mn^III-hydroxo complexes. Using a combination of cyclic voltammetry and electronic structure computations, we demonstrate that the weak Mn^III-N(pyridine) bonds lead to a higher Mn^III/II reduction potential, increasing the driving force for substrate oxidation reactions and accounting for the faster reaction rate. In addition, we demonstrate that the Mn^III-alkylperoxo complex [Mn^III(OO^tBu)(^6Medpaq)]⁺ reacts with water to obtain the corresponding Mn^III-hydroxo species, thus mimicking the ligand substitution step proposed for MnLOX.