Peripheral Modifications of meso-Hydroxyporphyrins: Formation of π-Electronic Anions and Ion-Pairing Assemblies

Phenyl groups were introduced at the β-positions proximal to the meso-hydroxy moiety in hydroxyporphyrin Ni^II complexes by oxidized BINAP Pd^II complexes. Ion-pairing assemblies of deprotonated π-electronic anions, anionic site of which was stabilized by the introduced phenyl moieties with a bulky cation, were formed. They showed charge-by-charge assemblies, assembly modes of which were modulated by the anionic building units.     

Preparation of free‐standing silicone particles in aqueous heterogeneous system

To prepare cross‐linked silicone (silicone rubber) particles in an aqueous medium, we investigated two synthesis methods involving a miniemulsion system. The first method was based on cationic ring‐opening polymerization of cyclic siloxane, which is a common synthetic route for linear silicone oil and uses octamethylcyclotetrasiloxane (D₄) as the monomer and dimeric D₄ (bis‐D₄) as the cross‐linker. Although this method produces silicone particles, the particles do not remain in the particulate state after drying because of low cross‐linking density. The polymerization mechanism of this method was also investigated, which proceeds under the ring‐opening reaction of D₄ in monomer droplets and upon polycondensation of hydrolyzed D₄, which occurs in the water phase (ie, outside the monomer droplets). This mechanism implied that introducing the cross‐linking structure into particles is difficult because of the low solubility of bis‐D₄ in water. To overcome these difficulties, we demonstrated a second method of preparing silicone particles based on the thiol‐Michael addition reaction between thiol‐terminated silicone oil and triacrylate in miniemulsion systems. Transmission electron microscopy images indicated that the silicone particles obtained in the particulate state upon drying and the aggregates of these particles showed elasticity.     

N-Doping of Polyaromatic Capsules: Small Cavity Modification Leads to Large Change in Host–Guest Interactions

To gain insight into the host functions of a nanocavity encircled by both polyaromatic panels and heteroatoms, nitrogen-doped polyaromatic capsules were successfully synthesized from metal ions and pyridine-embedded, bent anthracene-based ligands. The new capsules display unique host–guest interactions in the isolated cavities, which are distinct from those of the undoped analogues. Besides the inclusion of Ag⁺ ions, the large absorption change of fullerene C₆₀ and altered emission of a BODIPY dimer are observed upon encapsulation by the present hosts. Moreover, the N-doped capsule exhibits specific binding ability toward progesterone and methyltestosterone, known as a natural female and synthetic male hormone, respectively, in water.     

Which Stereoinductor Is Better for Asymmetric Functionalization of α-Amino Acids in a Nickel(II) Coordination Environment? Experimental and DFT Considerations

The results of extended comparative investigation of nickel(II) Schiff base complexes (containing various auxiliary chiral moieties) commonly used as a methodological platform for the asymmetric synthesis of tailor-made α-amino acids are provided. The following issues are addressed: 1) redox activity (determining the possibility for electrochemically induced reactions); 2) quantitative estimation of the reactivity of deprotonated complexes towards electrophiles; and 3) quantum-chemical estimation of noncovalent interactions in the metal coordination environment (which shed light on the origin of the stereochemical outcome observed for different stereoinductors). Possible mechanisms that determine the relationship between the stereochemical configuration of a molecule and its electronic structure are discussed. The DFT-calculated HOMO–LUMO energies and localization, as well as relative energies for the (S)- and (R)-alanine derivatives, that determine the stereoinduction efficiency in thermodynamically controlled reactions in nickel(II) coordination are provided. The computational data are supported by experimental results on the monobenzylation of glycine derivatives.     

Measurements of velocity distributions with a laser doppler imaging system

A laser Doppler imaging system with a TV camera has been constructed and velocity distributions of fluid flow in cross sections of a rectangular channel have been measured. Consequently, it has been found that the system has some advantages in comparison with usual laser Doppler velocimeters, for example, the visualization of flow can be easily achieved.     

Hausdorff measures and packing measures of limit sets of CIFSs of generalized complex continued fractions

ABSTRACT

We consider a certain family of CIFSs of the generalized complex continued fractions with a complex parameter space. We show that for each CIFS of the family, the Hausdorff measure of the limit set of the CIFS with respect to the Hausdorff dimension is zero and the packing measure of the limit set of the CIFS with respect to the Hausdorff dimension is positive (main result). This is a new phenomenon of infinite CIFSs which cannot hold in finite CIFSs. We prove the main result by showing some estimates for the unique conformal measure of each CIFS of the family and by using some geometric observations.     

Polarization-maintaining photonic crystal fibers with near-zero flattened dispersion in 1.06 μm waveband for medical applications

In this paper we present the design of a modified hexagonal photonic crystal fiber (PCF) having high birefringence and a near-zero flattened dispersion. Using the finite-difference method (FDM), it is shown that the proposed multiple Gedoped core hexagonal PCF exhibits a high birefringence of order 10⁻³ and a nearly zero flattened dispersion in the optical coherence tomography (OCT) waveband. In addition, the proposed PCF has a confinement loss of less than 10⁻⁸ dB/m at 1.06 μm. PCFs with such properties are considered suitable for both endoscopic OCT and other experimental setups employing 1.06 μm lasers.     

Dependence of tracking error characteristics on objective lens shift for in-line-type differential push-pull methods using segmented gratings

In this paper, we present the validity of in-line-type differential push-pull methods using segmented gratings with respect to the radial shift of an objective lens by numerical calculation for the first time. In these differential push-pull methods, the segmented gratings for generating sub spots are divided into two to four regions each with a specific phase value and a width. Tracking error signals are calculated with respect to the objective lens shift under parameter conditions of the widths of the segmented regions. The obtained results show that the grating of the simpler configuration with two regions reveals good compatibility between DVD-R and DVD-RAM compared with those with three or four regions