Synergic extraction of lanthanoids by mixtures of LIX 54 (high molecular weight beta-diketone) and bidentate neutral amines.

The synergic extraction of lanthanoids has been investigated using mixtures of high molecular weight beta-diketone, LIX 54 (HA; major component, 1-phenyl-3-isoheptyl-1,3-propanedion) and bidentate neutral ligands (S) in toluene. The distribution behavior of bidentate amines (2,2'-bipyridine (bpy), 1,10-phenanthroline (phen) and 2,9-dimethyl-1,10-phenanthroline (dmp)) was investigated and their related equilibrium constants were evaluated. The synergic effect is produced by the formation of such adduct complexes as MA3 x S. The extraction constants with LIX 54 alone and those in the presence of bidentate ligands were determined for lanthanoid-series elements.     

Modular synthesis of the ClickFerrophos ligand family and their use in rhodium- and ruthenium-catalyzed asymmetric hydrogenation

A series of diphosphine ClickFerrophos ligands (CF), based on a triazoleferrocene backbone, was synthesized in a four-step sequence via click chemistry methodology. In addition to the four previously synthesized ligands CF1, CF4, CF7 and CF10, six novel CF ligands CF2–3 and CF5–8 were prepared. Hydrogenation reactions of alkenes and ketones were significantly improved upon by using CF ligands as rhodium- or ruthenium-complexes in which the % ee values can be optimized by choosing the appropriate CF ligand depending on the substrate.     

Surface plasmon resonance study on binding interactions of multivalent cyclophane hosts with immobilized guests

Guest‐binding affinities of water‐soluble cyclophane heptadecamer (1) and pentamer (2) with immobilized guests such as 1‐pyrenylmethylamine (PMA) and 2‐(1‐ naphthyl)ethylamine (NEA) were investigated by surface plasmon resonance (SPR) measurements. As a typical example, the binding constants (K) for 1 and 2 with the immobilized PMA as a guest were evaluated to be 2.5 × 10⁷ and 2.7 × 10⁶ M^?1, respectively, and were much larger than that of a monocyclic reference cyclophane (K, 2.5 × 10⁴ M^?1). Interestingly, in the complexation of 1 and 2 with the immobilized guests, more favorable association and dissociation rate constant values (k_a and k_d, respectively) were observed in comparison with those for the monocyclic cyclophane, reflecting multivalent effects in macrocycles. The multivalent effects in macrocycles as well as molecular recognition abilities of the cyclophane oligomers were confirmed even when the guest molecules were immobilized on SPR sensor chip surfaces. Copyright © 2009 John Wiley & Sons, Ltd.     

Intermolecular π‐stacking and F...F interactions of fluorine‐substituted meso‐alkynylporphyrin

Two C2‐symmetric meso‐alkynylporphyrins, namely 5,15‐bis[(4‐butyl‐2,3,5,6‐tetrafluorophenyl)ethynyl]‐10,20‐dipropylporphyrin, C₅₀H₄₂F₈N₄, (I), and 5,15‐bis[(4‐butylphenyl)ethynyl]‐10,20‐dipropylporphyrin, C₅₀H₅₀N₄, (II), show remarkable π–π stacking that forms columns of porphyrin centers. The tetrafluorophenylene moieties in (I) show intermolecular interactions with each other through the F atoms, forming one‐dimensional ribbons. No significant π–π interactions are observed in the plane of the phenylene and tetrafluorophenylene moieties in either (I) or (II). The molecules of both compounds lie about inversion centers.     

Fabrication of marker area to align TEM tomographic tilt series of rod-shaped specimens

In this study, we present a new method for placing markers for alignment of tomographic tilt-series of rod-shaped specimen before 3D reconstructions. By this method, markers (gold nanoparticles) were placed only on the carbon layer (referred to as the "marker area") deposited for protecting the specimen surface against ion beam irradiation; this placement was achieved by vacuum evaporation of gold with the help of a mask fabricated adjacent to the specimen. Experimental results showed that the use of the proposed method facilitates the identification of the markers in the alignment process, because the image of the marker area consists of simple high-contrast images of the gold nanoparticles on the carbon layer. The performance of the proposed method was successfully verified experimentally by applying it to a high-density Au/SiO? nanocomposite material as a test specimen.     

Sensitivity analysis incorporating fuzzy evaluation for scaling constants of multiattribute utility functions

A multiattribute utility function can be represented by a function of single-attribute utility functions if the decision maker’s preference satisfies additive independence or mutually utility independence. Additive independence is a preference condition stronger than mutually utility independence, and the multiattribute utility function is in the additive form if the former condition is satisfied, otherwise it is in the multiplicative form. In this paper, we propose a method for sensitivity analysis of multiattribute utility functions in multiplicative form, taking into account the imprecision of the decision maker’s judgment in the procedures for determining scaling constants (attribute weights).