Synthesis and Photophysical Properties of a Sc3N@C80‐Corrole Electron Donor–Acceptor Conjugate

Embedding endohdedral metallofullerenes (EMFs) into electron donor–acceptor systems is still a challenging task owing to their limited quantities and their still largely unexplored chemical properties. In this study, we have performed a 1,3‐dipolar cycloaddition reaction of a corrole‐based precursor with Sc₃N@C₈₀ to regioselectively form a [5,6]‐adduct ( 1 ). The successful attachment of the corrole moiety was confirmed by mass spectrometry. In the electronic ground state, absorption spectra suggest sizeable electronic communications between the electron acceptor and the electron donor. Moreover, the addition pattern occurring at a [5,6]‐bond junction is firmly proven by NMR spectroscopy and electrochemical investigations performed with 1 . In the electronically excited state, which is probed in photophysical assays with 1 , a fast electron‐transfer yields the radical ion pair state consisting of the one‐electron‐reduced Sc₃N@C₈₀ and of the one‐electron‐oxidized corrole upon its exclusive photoexcitation. As such, our results shed new light on the practical work utilizing EMFs as building blocks in photovoltaics.     

Synthesis and Reactivity of the First Isolated Hydrogen‐Bridged Silanol–Silanolate Anions

We report on the first examples of isolated silanol–silanolate anions, obtained by utilizing weakly coordinating phosphazenium counterions. The silanolate anions were synthesized from the recently published phosphazenium hydroxide hydrate salt with siloxanes. The silanol–silanolate anions are postulated intermediates in the hydroxide‐mediated polymerization of aryl and alkyl siloxanes. The silanolate anions are strong nucleophiles because of the weakly coordinating character of the phosphazenium cation, which is perceptible in their activity in polysiloxane depolymerization.     

PtII-Catalyzed Hydroxylation of Terminal Aliphatic C(sp3)−H Bonds with Molecular Oxygen

The practical application of Shilov-type Pt catalysis to the selective hydroxylation of terminal aliphatic C−H bonds remains a formidable challenge, due to difficulties in replacing Pt^IV with a more economically viable oxidant, particularly O₂. We report the potential of employing FeCl₂ as a suitable redox mediator to overcome the kinetic hurdles related to the direct use of O₂ in the Pt reoxidation. For the selective conversion of butyric acid to γ-hydroxybutyric acid (GHB), a significantly enhanced catalyst activity and stability (turnover numbers (TON)>30) were achieved under 20 bar O₂ in comparison to current state-of-the-art systems (TON<10). In this regard, essential reaction parameters affecting the overall activity were identified, along with specific additives to attain catalyst stability at longer reaction times. Notably, deactivation by reduction to Pt⁰ was prevented by the addition of monodentate pyridine derivatives, such as 2-fluoropyridine, but also by introducing varying partial pressures of N₂ in the gaseous atmosphere. Finally, stability tests revealed the involvement of Pt^II and FeCl₂ in catalyzing the non-selective overoxidation of GHB. Accordingly, in situ esterification with boric acid proved to be a suitable strategy to maintain enhanced selectivities at much higher conversions (TON>60). Altogether, a useful catalytic system for the selective hydroxylation of primary aliphatic C−H bonds with O₂ is presented.     

Anatomy of a gauge theory

We exhibit the role of Hochschild cohomology in quantum field theory with particular emphasis on gauge theory and Dyson–Schwinger equations, the quantum equations of motion. These equations emerge from Hopf- and Lie algebra theory and free quantum field theory only. In the course of our analysis, we exhibit an intimate relation between the Slavnov–Taylor identities for the couplings and the existence of Hopf sub-algebras defined on the sum of all graphs at a given loop order, surpassing the need to work on single diagrams.     

Mathematical Modeling, Control, Computer Simulation and Laboratory Experiments of a Spatial Servopneumatic Parallel Robot

In this paper, the special construction of a parallel robot, called spatial servopneumatic multi-axis test facility, will be discussed. The investigations include the following aspects: (i) the laboratory set-up of the robot, (ii) various results obtained in laboratory experiments, taking into account quite different control algorithms and command-input signals, (iii) a comparison of the laboratory experiments with the computer simulations of Part I of this paper, and ({vi}) a quality check of the results compared with the cost of the different controller realizations. The results of both the computer simulations and the laboratory experiments show: (i) The dynamic behavior of the parallel structure can be tremendously improved by using sophisticated nonlinear control algorithms. (ii) This improvement has to be paid by a drastically increased amount of work for deriving the model equations and control algorithms, and by augmented hardware cost of the sensing elements and controller electronics. (iii) Carefully developed model equations and identified model parameters provide theoretical models of the complex parallel structure that are very close to reality. This enables the design engineer to systematically investigate constructive alternatives of the design parameters, sensor and actuator concepts, and control strategies of the MAP prior to their hardware realization.This work has been supported by the German Science Foundation (DFG) under Contract No. Ha 1666/6-3.     

The Hopf Algebra of Rooted Trees in Epstein-Glaser Renormalization

We show how the Hopf algebra of rooted trees encodes the combinatorics of Epstein-Glaser renormalization and coordinate space renormalization in general. In particular, we prove that the Epstein-Glaser time-ordered products can be obtained from the Hopf algebra by suitable Feynman rules, mapping trees to operator-valued distributions. Twisting the antipode with a renormalization map formally solves the Epstein-Glaser recursion and provides local counterterms due to the Hochschild 1-closedness of the grafting operator B₊.submitted 29/03/04, accepted 01/06/04     

Implementation of an integrated glucose POCT system

In response to a change of the Belgian National Directives whereby hospital laboratories became responsible for all point-of-care testing (POCT) performed within hospital walls a standardized and automated POC glucose-testing system was implemented in our hospital. The system consists of 50 AccuCheck Inform instruments (Roche Diagnostics, Vilvoorde, Belgium), 50 docking stations, a DataCare Server, and connections to the medical laboratory information system (MOLIS, Sysmex, Barchon, Belgium) and to the hospital information system. Implementation involved many parties and extensive preparation and communication. Key issues were bar-coded patient and user identification, training, and responsibilities. One year after the hospital wide implementation of this system the quality of POC glucose testing has significantly increased, thereby improving patient safety. This study describes a stepwise change over involving the medical laboratory and with a focus on hands-on quality.Presented at the ninth conference on Quality in the Spotlight, 18–19 March 2004, Antwerp, Belgium.     

Laser systems specialized for laser spectroscopy at storage rings

Laser spectroscopy at storage rings often suffers from a limited resolution due to Doppler-broadened resonances. Broadening is caused by the velocity spread of the ions stored in the beam. In the following, the present status of our work on laser systems specialized on the specific needs of laser spectroscopy at storage rings is reported. Two pulsed laser systems were developed. One is a dye laser whose spectral bandwidth can be switched by inserting different Littrow-prisms into the resonator. An increase in bandwidth up to a factor of 45 was achieved. This laser was used for fast qualitative scans and high resolution measurements. The other laser system is a Nd : YAG laser pumped optical parametric oscillator. It is a tunable laser system covering the spectral range from 410 to 4000 nm. Furthermore, a continuous wave laser with a frequency shifted feedback cavity is described. It shows broadband emission with an adjustable bandwidth of up to 4.5 GHz. This laser can be advantageous for laser cooling of ion beams. This revised version was published online in August 2006 with corrections to the Cover Date.     

On cellularization for simplicial presheaves and motivic homotopy

We construct cellular homotopy theories for categories of simplicial presheaves on small Grothendieck sites and discuss applications to the motivic homotopy category of Morel and Voevodsky.