Control of single molecular nanodot patterns of phenyl azomethine dendrimers by statistical simulation

Precisely synthesized subnanometer particles of metals or metal oxides can be prepared using dendritic polyphenyl azomethines as the template. With a goal of their arrays to a surface using a simple and quick process, such as spin-casting, statistical analyses were applied to a nanodot array of the dendrimers to obtain the relationship between the experimental condition and the results such as size, spacing, or its standard deviations. The dot patterns of a single molecular dendrimer on a substrate were able to be predicted with numerical values of the experimental parameters associated with the spin coat (concentration of the dendrimer, physical properties of solvent, the spin coating recipe, temperature of the solution, relative humidity (RH)) as the inputs for the statistical analysis.     

On two expressions of the MLE for a special case of the extended growth curve models

An algebraic proof is given on the equivalence between two solutions of MLEs for a special case of the extended growth curve models called the Banken model. One solution given by Verbyla and Venables is an iterative solution in the general case but reduces to a non-iterative one in the case of the Banken model. The other solution given by von Rosen is a closed-form solution specifically targeted at the Banken model. The proof has turned out to be quite challenging yet intriguing as it touches on many aspects of intricate matrix theory involving projection matrices.     

Distribution of lattice-strain on partly nitrogen-covered Cu(0 0 1) surfaces

In-plane elastic lattice strain on the Cu(0 0 1)-c(2 × 2)N surfaces is investigated by scanning tunneling microscopy on the surface where nitrogen-adsorbed patches with average size of 5 × 5 nm² (c(2 × 2)N patches) are well separated by wide clean Cu surface. The lattice distortion on clean Cu surface is recognized in the vicinity of the boundary to a c(2 × 2)N patch. The positions of the protrusions observed on the c(2 × 2)N patch are compared with the surrounding undistorted (1 × 1) lattice of the clean Cu surface. Most of the protrusions on the c(2 × 2)N patches locate on the fourfold hollow sites of the undistorted Cu lattice. The lattice distortion is significant only near the boundary to the surrounding clean Cu surface.     

Raman-Nath diffraction by microparticles in water

In Raman-Nath diffraction by water, the intensities of even order light beams are selectively enhanced by suspension of microparticles. The diffracted beams remain for several seconds even after the ultrasonic oscillation stops. These phenomena are elucidated by assuming the laminar arrangement of micropaticles due to the ultrasonic wave.     

Synthetic approaches to fused heteroaromatic compounds by the condensation reactions of functional pyrroles

Condensation reactions ol the “functionalized” pyrroles which were obtained by one pot synthesis of aziridines and acetylenic dipolarophiles were discussed. On treatments of 3,4-di- and 2,3,4-tribenzoylpyrroles with hydrazine hydrate and phosphorus pentasulfide, the several pyrrolo-pyridazine derivatives and fused thiophenes, respectively, were prepared. The structure proofs for the products of the reaction of the 2,3,4-tribenzoylpyrrole ( 9a ) with hydrazine hydrate were based on the ¹³C FT-nmr spectrum of the corresponding ¹³C-enriched compounds.     

Cocrystallization of Two Different Pseudorotamers of Monocyclic Phosphorane Bearing Two Martin Ligands

Solution and crystal structures of monocyclic pentacoordinate phosphoranes bearing two Martin ligands and two carbon substituents are described. When the two carbon substituents are different, relative apicophilicity of the two monodentate carbon substituents could be determined based on the equilibrium ratio of the pseudorotamers. In some cases, x-ray structural analysis could be carried out and the crystallized structure from CH 3 CN is consistent with the major pseudorotamer in solution (CD 3 CN). Furthermore, when the equilibrium ratio of pseudorotamers is almost unity, novel cocrystallization of two pseudorotamers in a single crystal was observed.     

Investigation of a molecular morphology effect on polyphenylazomethine dendrimers; physical properties and metal-assembling processes

A series of novel dendritic polyphenylazomethines (DPA) with asymmetric morphologies was synthesized. Their physical properties, such as encapsulating effect, molecular dynamics, and metal assembly, are strongly dependent on the entire conformation of the molecules. The most important property is layer-by-layer metal assembly in the dendrimer structure from the core to the outside. Bis- and tris-substituted DPAs of the fourth generation also act as frameworks for stepwise assembly of a metal component (SnCl2), like the fully substituted symmetric DPA. However, extensive investigation of metal assembly in specific DPAs revealed that they do not follow the stepwise process. The molecular density calculated from the experimental hydrodynamic volume indicated that bis- and tris-substituted DPAs with asymmetric morphology still retain a free space similar to that of fully substituted symmetric DPA. The monosubstituted DPA, however, displayed a slightly higher density (smaller space) than the other DPAs. The experimental results suggest a bent conformation of the dendrimer in which the core moiety is folded into the dendron structure. In addition, the molecular dynamics were probed by means of the 1H NMR signals of the porphyrin core. It was demonstrated that the conformation is not fixed at room temperature in solvated DPAs, especially in monosubstituted DPA. A similar observation was for the smaller DPAs (third generations) with asymmetric morphologies. These dendrimers do not follow the stepwise complexation process. The structures of bis- and tris-substituted dendrimers which accurately follow the stepwise process are fixed. These observations provide a new insight into the finely controlled metal-assembly chemistry of dendritic macromolecules, and a rigid and fixed conformation is one of important factors for their unique properties.     

Static magnetic-field-induced phase lag in the magnetization response of tris(dipicolinato)lanthanides

Alternating-current (ac) magnetic susceptibility measurements for tris(dipicolinato) complexes with a trivalent heavy lanthanide ion, [N(C2H5)4]3[Ln(dipic)(3)] x nH2O (dipic = pyridine-2,6-dicarboxylate; Ln = Tb, Dy, Ho, Er, Tm, or Yb) are reported. While none of the six complexes showed a magnetization lag from the ac magnetic field of 10-10(3) Hz above 1.8 K, the Dy, Er, and Yb complexes with odd numbers of 4f electrons exhibited the magnetization lag in a static magnetic field. This phenomenon is explained to be caused by the elimination of a fast relaxation path, which is only effective for the Kramers doublet ground states in near zero field. At higher static fields, the remaining paths such as Orbach and/or direct processes govern the dynamics of the two-level systems comprised of spin-up and spin-down states. The non-Kramers complexes were found to have a nondegenerate ground state with large energy gaps from higher states, which is consistent with their fast magnetization relaxation.     

Total synthesis of (R)-telomestatin

We have achieved a total synthesis of telomestatin, and its absolute configuration was determined to be (R). Coupling of cysteine-containing trisoxazole amine and serine-containing trisoxazole carboxylic acid, followed by macrocyclization, provided a 24-membered diamide. The seventh oxazole ring was formed by a Shin's procedure via dehydroamide. Cyclodehydration of a modified (R)-cysteine-(S-(t)Bu) moiety using Kelly's method (PPh3(O)-Tf2O) with anisole furnished (R)-telomestatin, whose CD spectrum was in good agreement with that of the natural product.