The Role of Radical Bridges in Polynuclear Single-Molecule Magnets

Employing radical bridges between anisotropic metal ions has been a viable route to achieve high-performance single-molecule magnets (SMMs). While the bridges have been mainly considered for their ability to promote exchange interactions, the crystal-field effect arising from them has not been taken into account explicitly. This lack of consideration may distort the understanding and limit the development of the entire family. To shed light on this aspect, herein we report a theoretical investigation of a series of N -radical-bridged diterbium complexes. It is found that while promoting strong exchange coupling between the terbium ions, the N -radical induces a crystal field that interferes destructively with that of the outer ligands, and thus reduces the overall SMM behavior. Based on the theoretical results, we conclude that the SMM behavior in this series could be further maximized if the crystal field of the outer ligands is designed to be collinear with that of the radical bridge. This conclusion can be generalized to all exchange-coupled SMMs.     

Wechselnde Bindungen in einem Zweikörpersystem mit trockener Reibung

Übersicht Betrachtet wird ein zwangserregtes Zweikörpersystem mit wechselnden Bindungen infolge trockener Reibung. Stationäre Bewegungen werden als Grenzfall instationärer Einschwingvorgänge berechnet. Abhängig von den Systemparametern ergeben sich drei typische Bewegungsformen. Ihnen entsprechen dauernde Haftzustände, wechselnde Haft-Gleitzustände oder dauernde Gleitzustände an der Berührfläche beider Körper.

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Intermittant constraints in a two-body-system with dry friction

Summary An externally excited two-body-system with intermittant constraints due to dry friction is considered. Stationary motions are calculated as limit cases of instationary transients. Depending on the parameters of the system, three typical modes are of interest. These correspond to permanent sticking, slipstick behaviour, or to permanent slipping in the contact surface of the bodies, respectively.

     

Selective Propargylation of Carbonyl Compounds and Imines with Barium Reagents

A Barbier‐type regioselective propargylation of aldehydes and ketones with (3‐bromobut‐1‐ynyl)trimethylsilane has been achieved using reactive barium as a low‐valent metal in THF. Especially in the case of ketones, the corresponding homopropargylic alcohols form almost exclusively. In the reaction of α,β‐unsaturated carbonyl compounds, only 1,2‐adducts have been observed. This method is also applicable to propargylation of imines, and the corresponding homopropargylic amines are obtained regiospecifically in good yields with diastereomeric ratios of up to 87:13.     

Hindered motions in a ketonea-urea inclusion compound. An ESR and ENDOR study

We have studied by ESR and ENDOR spectroscopy the free radicals produced in γ-irradiated inclusion compound formed between the ketone 10-nonadecanone and urea. Only one type of long lived radical is formed by the removal of an α-proton from the ketone. The hyperfine (hf) coupling constants of the α- and β-protons of the radicals have been measured by ESR at different temperatures in the range 110–292 K and at different orientations of the crystals. The hf coupling of the γ-protons of the radical and of the urea protons have been studied by ENDOR. The temperature and angular dependences of the coupling constants have been analyzed in terms of the internal and overall motions of the radical inside the hexagonal channels formed by the urea molecules. It has been found that the radical cannot perform complete reorientations around the long molecular axis, but it undergoes restricted rotational diffusion. This process is explained by assuming a coupling between the rotational and translational degrees of freedom of the radical inside the urea channels.     

Medicinal Organometallic Chemistry: Designing Metal Arene Complexes as Anticancer Agents

The field of medicinal inorganic chemistry is rapidly advancing. In particular organometallic complexes have much potential as therapeutic and diagnostic agents. The carbon‐bound and other ligands allow the thermodynamic and kinetic reactivity of the metal ion to be controlled and also provide a scaffold for functionalization. The establishment of structure–activity relationships and elucidation of the speciation of complexes under conditions relevant to drug testing and formulation are crucial for the further development of promising medicinal applications of organometallic complexes. Specific examples involving the design of ruthenium and osmium arene complexes as anticancer agents are discussed.     

Genetically Encoded Bioluminescent Indicator for ERK2 Dimer in Living Cells

In this study, a genetically encoded bioluminescent indicator for ERK2 dimer was developed with the split Renilla luciferase complementation method, in which the formation of ERK2 dimer induces a spontaneous emission of bioluminescence in living cells. In response to extracellular stimuli, such as epidermal growth factor (EGF) or 17β‐estradiol (E2), extracellular signal‐regulated kinase 2 (ERK2) is phosphorylated by its upstream kinase MEK, and also phosphorylates its substrates in various regions of the cell, including the nucleus. Phosphorylated ERK2 is led to form its dimer, thereby transporting itself into the nucleus. We demonstrated with the indicator that stimulation with EGF or E2 induces the formation of ERK2 dimer in living MCF‐7 cells. The dynamics of this dimer formation was examined and discussed.     

Prädikatives und funktionales Denken in der Wahrscheinlichkeitsrechnung

In order to emphasize functional thinking in mathematical education, arguments are brought forward for an early and frequent use of tree diagrams in teaching stochastics. Since set and tree diagrams can be regarded as two sides of the same matter, Bayes’ theorem, which is strongly associated with predicative set diagrams, need not be dealt with explicitly any longer. Set diagrams are replaced by tree diagrams that are labelled in detail and by tree inversion as a functional instrument of dealing with conditioned probabilities. This technique is demonstrated by three typical problems in the context of conditioned probability. Finally, two letters by Pascal to Fermat are analysed in order to illustrate that predicative and functional approaches were already pursued in the early stages of probability calculus in the 17^th century.     

Gasdynamische Untersuchung des Jouleschen Überströmversuches

Zusammenfassung Es wird die zeitabhängige Strömung beim Ausgleichsvorgang zwischen zwei endlichen Behältern untersucht. Den Überlegungen wird eine eindimensionale, reibungsfreie und quasistationäre Strömung zugrunde gelegt. Während bei überkritischer Strömung eine analytische Lösung möglich ist, wird das Problem bei unterkritischer Strömung numerisch gelöst.Dem Druckausgleich zwischen den beiden Behältern folgt ein isobarer Wärme- und Massenaustausch, bis sich das thermodynamische Gleichgewicht eingestellt hat.

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Gasdynamical investigation of Joule's overflow experiment

The time-dependent flow of an exchange process between two big insulated tanks is considered. The problem is treated on the basis of a one-dimensional, inviscid and quasi-steady flow. An analytical solution is obtained for supercritical flow, while for subcritical flow the problem is solved numerically.After the pressure-equilibrium between the two-tanks an isobar heat and mass exchange follows, until the thermodynamic equilibrium is reached.

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Formelzeichen a Schallgechwindigkeit - A engster Querschnitt - c Geschwindigkeit - c _p spezifische Wärme bei konstantem Druck - c _v spezifische Wärme bei konstantem Volumen - e innere Energie - i Enthalpie - m Masse - M Machzahl - p Druck - spezielle Gaskonstante - s Stromlinie, spezifische Entropie - t dimensionsbehaftete Zeit - T Temperatur - V Volumen - Konstante - Abkürzung - Volumenverhältnis - Verhältnis der spezifischen Wärmen - Dichte - dimensionslose Zeit Indizes 0 Zustand zur Zeitt=0 - 1 Zustand im Überdruckbehälter - 2 Zustand im Überströmbehälter - * Zustand im engsten Querschnitt - K kritisch - M Zustand bei Druckausgleich - E Endzustand bei Temperaturausgleich Herrn Prof. Dr. B. Schmidt in Dankbarkeit zum 60. Geburtstag gewidmet