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.     

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.     

Facilitated sulfate transfer across the nitrobenzene-water interface as mediated by hydrogen-bonding ionophores.

Facilitated SO4(2-) transfers by hydrogen bond-forming ionophores are investigated across the nitrobenzene (NB)-water interface by using polarography with a dropping electrolyte electrode. Bis-thiourea 1, alpha,alpha'-bis(N'-p-nitrophenylthioureylene)-m-xylene, is found to significantly facilitate the transfer of the highly hydrophilic SO4(2-) whereas its counterpart, N-(p-nitrophenyl)-N'-propylthiourea (ionophore 2), cannot. In contrast to the predominant formation of a 1:1 complex with SO4(2-) in the bulk NB phase, the SO4(2-) transfer assisted by 1 is indeed based on the formation of a 1:2 complex between SO4(2-) and ionophore, even under the condition of [SO4(2-)]aq > [1]org. Such an exclusive formation of the 1:2 (SO4(2-) to ionophore) complex at the NB-water interface is not observed with structurally similar bis-thiourea 3, alpha,alpha'-bis(N'-phenylthioureylene)-m-xylene, where p-nitrophenyl moietes of bis-thiourea 1 are simply replaced by phenyl groups. The facilitated transfer of SO4(2-) with bis-thiourea 1 is further compared to that of HPO4(2-) and H2PO4- across the NB-water interface, which was previously shown to be assisted by 1 through the formation of the 1:1 and 2:1 (anion to ionophore) complexes, respectively. On the basis of these examinations, unique binding behaviors of hydrogen bond-forming ionophores at the NB-water interface are discussed, with a view towards development of ionophore-based anion-selective chemical sensors.     

Ring‐opening grafting polymerization of cyclic monomers onto human hair

Natural human hair was successfully modified by the graft polymerization of trimethylene carbonate, β‐propiolactone, ε‐caprolactone, glycidol, ε‐caprolactam, and 5,5‐dimethyl‐1,3‐dioxane‐2‐thione. In contrast, we could not modify natural human hair by the graft polymerization of oxetane under similar conditions. The model reaction suggested that the main initiating species in these polymerizations were the amino, thiol, and hydroxyl groups in hair, which could induce ring‐opening polymerization. Among the tested monomers, β‐propiolactone was most effective for hair modification with its graft polymer, whose concentration was as high as 0.5 g/g of hair though polymerization under mild conditions. The effects of the hair pretreatment and polymerization temperature on the weight ratio of the grafted polymers were also investigated. Hair modified by grafted polymers was characterized with scanning electron microscopy and Fourier transform infrared measurements. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 736–744, 2007     

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.     

Synthesis and characterization of norbornene–ethylene–styrene terpolymers with a substituted ansa‐fluorenylamidodimethyltitanium‐based catalyst

This article reports a synthetic method for a norbornene–ethylene–styrene (N‐E‐S) terpolymer, which has not been well investigated so far, via incorporation of styrene (S) into vinyl‐type norbornene–ethylene (N‐E) copolymers catalyzed by a substituted ansa‐fluorenylamidodimethyltitanium [Me₂Si(3,6‐tBu₂Flu)(tBuN)]TiMe₂ catalyst ( I ) activated with a [Ph₃C][B(C₆F₅)₄]/Al(iBu)₃ cocatalyst at room temperature in toluene. The resulting terpolymerization product contained the targeted N‐E‐S terpolymer and the contaminated homopolymers, which were then able to be completely removed by solvent fractionation techniques. While homopolystyrene was easily extracted by fractionation with methylethylketone as a soluble part, homopolyethylene and a trace amount of homopolynorbornene could be perfectly separated by fractionation with chloroform as insoluble parts. The detail characterizations of a chloroform‐soluble polymer with gel permeation chromatography, nuclear magnetic resonance, and differential scanning calorimetry analyses proved that it contained a true N‐E‐S terpolymer with long N‐E sequences incorporated with isolated or short styrene sequences. The homogeneity of the morphology together with a single glass transition temperature that proportionally decreased with the increase of the styrene contents indicated that the N‐E‐S terpolymer obtained in this work is a random polymer with an amorphous structure. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2765–2773, 2007