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.

     

Notiz über Parachloraldehyd

Ohne Zusammenfassung     

Experimental characterization of hexatic smectic phases through electro-optic studies and dielectric relaxation spectroscopy

The electro-optic and complex dielectric behaviour of an antiferroelectric liquid crystal 4-(1-methylheptyloxycarbonyl)phenyl 4'-(n-butanoyloxyprop-1-oxy)biphenyl-4-carboxylate, having chiral SmC_A* and hexatic smectic phases, have been investigated. Complex dielectric permittivities were measured as a function of frequency, d.c. bias field and temperature. Spontaneous polarization was measured by the current reversal technique; tilt angle was measured under a polarizing microscope using a low frequency electric field. The electro-optic properties and dielectric behaviour of the material are compared with results obtained by DSC and polarizing optical microscopy. Dielectric relaxation processes in SmC_A* and hexatic smectic phases were determined. The dielectric strength at the SmC_A* to hexatic smectic phase transition is discussed in terms of coupling between the long range bond orientational order and smectic C director. It seems from the results of spontaneous polarization and dielectric relaxation spectroscopy that the material might possess an additional phase between the SmC_A* and hexatic smectic I* phases.     

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.     

Synthesis and Characterization of Silica@Copper Core–Shell Nanoparticles: Application for Conjugate Addition Reactions

Silica@copper (SiO₂@Cu) core–shell nanoparticles were synthesized and well characterized by XRD, TEM, AFM, XPS, UV/Vis, TGA–MS, and ICP–AES techniques. The synthesized SiO₂@Cu core–shell nanoparticles were employed as catalysts for the conjugate addition of amines to α,β‐unsaturated compounds in water to obtain β‐amino carbonyl compounds in excellent yields in shorter reaction times. Furthermore, the catalyst works well for hetero‐Michael addition reactions of heteroatom nucleophiles such as thiols to α,β‐unsaturated compounds. As the reaction is performed in water, it allows for easy recycling of the catalyst with consistent activity.     

Non-protein amino acids in peptide design

An overview of the use of non-protein amino acids in the design of conformationally well-defined peptides, based on work from the author’s laboratory, is discussed. The crystal structures of several designed oligopeptides illustrate the useα-aminoisobutyric acid (Aib) in the construction of helices, D-amino acids in the design of helix termination segments and^DPro-Xxx segments for nucleating ofβ-hairpin structures.β- andγ-amino acid residues have been used to expand the range of designed polypeptide structures. Dedicated to Professor C N R Rao on his 70th birthday     

Bargaining over the division of a shrinking pie: An axiomatic approach

The Bargaining Problem paradigm is extended to time-consuming conflict situations. Such a situation can be represented by a chain of bargaining domains, each representing the conflict at a different point in time. The solution function selects a point in the union of all these domains. We characterize a solution function which satisfies several requirements and explore its properties. One of the results is that an extension of the Adding requirement (Thomson-Myerson 1980) is enough, under some conditions, to yield a solution point, so there is no need to extend the stronger requirements of Independence of Irrelevant Alternatives (Nash 1950) or Monotonicity (Kalai-Smorodinsky 1975).