Stable but Reactive Perfluoroalkylzinc Reagents: Application in Ligand‐Free Copper‐Catalyzed Perfluoroalkylation of Aryl Iodides

The aromatic perfluoroalkylation catalyzed by a copper(I) salt with bis(perfluoroalkyl)zinc reagents Zn(R_F)₂(DMPU)₂, which were prepared and then isolated as a stable white powder from perfluoroalkyl iodide and diethylzinc, was accomplished to provide the perfluoroalkylated products in good‐to‐excellent yields. The advantages of this reliable and practical catalytic reaction are 1) air‐stable and easy‐to‐handle bis(perfluoroalkyl)zinc reagents can be utilized, 2) the reagent is reactive and hence the operation without activators and ligands is simple, and 3) not only trifluoromethylation but also perfluoroalkylation can be attained.     

Visible light-emitting and temperature-sensitive copolymer gel/ZnO nanocomposites loaded with surface-modified ZnO nanoparticles having polyethylene glycol chains

New visible light-emitting and temperature-sensitive poly(VCL-co-SA)/ZnO gel nanocompsites (GNs) 4 loaded with surface-modified ZnO nanoparticles NPs 3 with polyethylene glycol (PEG) chains were successfully prepared by the cross-linking of N-vinylcaprolactam (VCL), sodium acrylate (SA) and tetraethylene glycol dimethacrylate (TEGDM) in the presence of NPs 3. The NPs 3 having nanostructured size were prepared from ZnO NPs 2 with 2-bromo-2-methylpropionyl linkages on the surface, and sodium alcoholate of polyethylene glycol monomethyl ether (PEGME). The NPs 3 and the GNs 4 were characterized by FTIR, UV–vis absorption and photoluminescent (PL) spectroscopies, X-ray analysis measurements, TEM and SEM observations and dynamic light scattering (DLS) measurements. The measurements indicated that the GNs 4 with wurtzite crystal structures based on the ZnO NPs show absorptions and yellow light-emitting properties arising from the NPs 3, except for the GNs 4 containing a high weight % of NPs 3. The size of the GNs 4 drastically decreased with increasing temperature in the range of 20–35 °C, probably because of the induction of steric hindrance and enhancement of hydrophilic PEG chain concentrations inside the GN networks 4.     

Sensitivity of minimaxity and admissibility in the estimation of a positive normal mean

On the problem of estimating a positive normal mean with known variance, it is well known that one minimax admissible estimator is the generalized Bayes one with respect to the non-informative prior measure, the Lebesgue measure, restricted on the positive half-line. When the true variance is misspecified, however, it is shown that this estimator does not always retain minimaxity and admisssibility. In particular, it is almost surely inadmissible in the misspecification case.     

Genetically-increased taste cell population with Gα-gustducin-coupled sweet receptors is associated with increase of gurmarin-sensitive taste nerve fibers in mice

Background  

The peptide gurmarin is a selective sweet response inhibitor for rodents. In mice, gurmarin sensitivity differs among strains with gurmarin-sensitive C57BL and gurmarin-poorly-sensitive BALB strains. In C57BL mice, sweet-responsive fibers of the chorda tympani (CT) nerve can be divided into two distinct populations, gurmarin-sensitive (GS) and gurmarin-insensitive (GI) types, suggesting the existence of two distinct reception pathways for sweet taste responses. By using the dpa congenic strain (dpa CG) whose genetic background is identical to BALB except that the gene(s) controlling gurmarin sensitivity are derived from C57BL, we previously found that genetically-elevated gurmarin sensitivity in dpa CG mice, confirmed by using behavioral response and whole CT nerve response analyses, was linked to a greater taste cell population co-expressing sweet taste receptors and a Gα protein, Gα-gustducin. However, the formation of neural pathways from the increased taste cell population to nerve fibers has not yet been examined.     

The decomposition and measurement of the interdependency between second-order stationary processes

Summary For a given pair of multivariate stationary processes, the process of one-way effect is extracted from each of the processes. Each process is decomposed into two orthogonal processes, namely, into the process generated by the one-way effect of the other process and the process orthogonal to it. Based on the decomposition, three measures characterizing the interdependency of the pair of processes are introduced. They are the measure of association, the measure of one-way effect and the measure of reciprocity. Each of the measures is defined as overall as well as frequencywise measure. The paper shows that the measure of association is equal to the sum of the others. It discusses the relationships of those measures to the ones proposed by Gel'fand-Yaglom and by Geweke.This paper is partially supported by the Japanese Ministry of Education Grant for Scientific Research No. C02630010     

Calculation of stacking geometries by a modified MM2 method

The MM2 method has been modified using a three‐center charge model aimed at determining stacking geometries. The stacking interactions for the benzene dimer, porphine dimer, and bis(4,5‐diazafluoren‐9‐one thiosemicarbazonato)palladium(II) have been assessed with both the three‐center charge model and the conventional single‐center charge model using the MM2 method. The modified MM2 method always gave better results than the conventional method, and the obtained structures by the former method are in good agreement with the proposed structures from those theoretical and experimental results. The possible advantages of using the three‐center charge model for complex systems are also discussed. © 2001 John Wiley & Sons, Inc. J Comput Chem 22: 835–845, 2001     

Aromatic substitution of olefins. Arylation with anilines via the C-N bond cleavage in the presence of palladium(II) acetate

A new aromatic substitution reaction of styrene by arylamines such as aniline, (unp)-toluidine, (unp)-anisidine, (unp)-chloroaniline, and (unp)-nitroaniline in the presence of palladium(II) acetate has been found to give (E)-stilbene, (E)-(unp)-methylstilbene, (E)-(unp)-methoxystilbene, (E)-(unp)-chlorostilbene, and (E)-(unp)-nitrostilbene, respectively, in modest yields.     

Shape modeling of mineral dust particles for light-scattering calculations using the spatial Poisson-Voronoi tessellation

We present a shape model of mineral dust particles for use in light-scattering calculations. A spatial Poisson-Voronoi tessellation was applied to simulate the aggregate structure and, therefore, the rough surface of the mineral particles. To develop the shape model, we took into account statistics of shape parameters derived from the cross-sectional areas, maximum dimensions, and perimeters of field-collected dust particles. Light-scattering properties of the modeled Voronoi aggregates were examined by the finite-difference time-domain (FDTD) method. The results of randomly oriented scattering properties agreed with previously reported laboratory measurements of mineral dust particles.     

An unexpected chelate conformation in trans‐[(R)‐N,N′‐bis(α‐phenyl­salicyl­idene)­propane‐1,2‐diaminato(2–)]­bis(1‐methyl‐1H‐imidazole‐κN3)­cobalt(III) perchlorate

The title compound, [Co(C₂₉H₂₄N₂O₂)(C₄H₆N₂)₂]ClO₄, contains an optically active tetradentate Schiff base ligand in an equatorial plane and two 1‐methyl­imidazole ligands at apical positions. The central N—C—C—N chelate ring of the Schiff base ligand has an envelope structure with a λ conformation, which is different from the solution structure predicted from circular dichroism and ¹H NMR spectra.