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.     

Electrochemical determination of serotonin and the competitive adsorption with dopamine at 5,5-ditetradecyl-2-(2-trimethylammonioethyl)-1,3-dioxane bromide lipid film modified by glassy carbon electrode.

A novel and effective approach to sensitively determine serotonin, known as 5-hydroxytryptamine (5-HT), has been proposed based on a 5,5-ditetradecyl-2-(2-trimethylammonioethyl)-1,3-dioxane bromide (DTDB) self-assembled lipid bilayer membrane modified glassy carbon electrode (DTDB/GCE). A DTDB/GCE shows the strong electrocatalysis for the oxidation of 5-HT, with the peak potential shifted to less positive value of 0.376 V vs. SCE, and effectively eliminates the interference from ascorbic acid (AA), even in the presence of 100-fold concentration of AA. Differential pulse voltammetry (DPV) gave a linear current for 5-HT from 2.0 x 10(-7) to 1.0 x 10(-5) M. At the DTDB/GCE, the oxidation of 5-HT was controlled by the adsorption process; for 5-HT coexisting with DA, the competitive adsorption was observed.     

Shape transition from InAs quantum dash to quantum dot on InP(3 1 1)A

We report on the shape transition from InAs quantum dashes to quantum dots (QDs) on lattice-matched GaInAsP on InP(3 1 1)A substrates. InAs quantum dashes develop during chemical-beam epitaxy of 3.2 monolayers InAs, which transform into round InAs QDs by introducing a growth interruption without arsenic flux after InAs deposition. The shape transition is solely attributed to surface properties, i.e., increase of the surface energy and symmetry under arsenic deficient conditions. The round QD shape is maintained during subsequent GaInAsP overgrowth because the reversed shape transition from dot to dash is kinetically hindered by the decreased ad-atom diffusion under arsenic flux.     

Thickness decrease of a grafted polyelectrolyte membrane exposed to shear flow

The effect of the shear flow on the thickness change of a polyelectrolyte membrane grafted onto a glass substrate was directly investigated with a flow cell combined with a confocal laser scanning microscope. The membrane thickness decreased proportionally to an increase in the shear stress of the flow when the shear rate exceeded a critical value of 1 s^?1. The higher the ionic strength was of the fluid, the greater the thinning effect was. The correlation between the critical shear rate and the relaxation of the polymer in the gel membrane was examined. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2808–2815, 2003     

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.