Diatomic interactions in momentum space. The effect of polarization and floating functions

The method of momentum density for interatomic interactions is used to investigate the pictures and roles of the polarization and floating functions in momentum (p-) space. Referring to the previous results from the minimal LCAO (Finkelstein-Horowitz) momentum density, we quantitatively discuss the effect of these functions for the bonding process in the ground state of H ₂ ⁺ system. The essence of the polarization and floating effects is found to be a modulation of the oscillation in the two-center part of the momentum density. The polarization function introduces a term with a phase and the floating function enlarges the period of the oscillation. An increased migration of the density from the one-center to the two-center part is also important. As a result, both the functions contribute to emphasize the contraction and expansion of momentum density observed previously. However, the floating function disturbs the density distribution in high momentum region, reflecting the destruction of cusps in position (r-) space. We point out an error in the pioneer work of Duncanson.     

Simultaneous derivatization/preconcentration of volatile aldehydes with a miniaturized fiber-packed sample preparation device designed for gas chromatographic analysis

A novel in-needle sample preparation device has been developed for the determination of volatile aldehydes in gaseous samples. The needle device is designed for the gas chromatographic (GC) analysis of aldehydes and ketones commonly found in typical in-house environments. In order to prepare the extraction device, a bundle of polymer-coated filaments was longitudinally packed into a specially designed needle. Derivatization reactions were prompted by 2,4-dinitrophenylhydrazine (NDPH) included in the needle, and so the aldehydes and ketones were derivatized to the corresponding hydrazones and extracted with the extraction needle. A reproducible extraction needle preparation process was established, along with a repeatable derivatization/extraction process that ensures the successful determination of aldehydes. The storage performance of the extraction needle was also evaluated at room temperature for three days. The results demonstrate the successful application of the fiber-packed extraction device to the preparation of a gaseous sample of aldehydes, and the future possibility of applying the extraction device to the analysis of in-house environments.     

First measurement of inclusive B→Xsη decays

We report a first measurement of inclusive B→Xsη decays, where Xs is a charmless state with unit strangeness. The measurement is based on a pseudoinclusive reconstruction technique and uses a sample of 657×10(6)BB pairs accumulated with the Belle detector at the KEKB e+e- collider. For MXs < 2.6 GeV/c2, we measure a branching fraction of [26.1±3.0(stat)-2.1+1.9(syst)-7.1+4.0(model)]×10(-5) and a direct CP asymmetry of ACP=-0.13±0.04-0.03+0.02. Over half of the signal occurs in the range MXs > 1.8 GeV/c2.     

Dibenzoarsepins: Planarization of 8π‐Electron System in the Lowest Singlet Excited State

Dibenzo[b,f]arsepins possessing severely distorted cores compared to those of other heteropins were synthesized. These derivatives exhibited dual photoluminescence in the green‐to‐red region (500–700 nm) and the near‐ultraviolet region (<380 nm), which could be attributed to the planarization of the arsepin core in the lowest singlet excited (S₁) state. The computational approach for the assessment of the aromatic indices revealed that the dibenzoarsepins studied show aromaticity (8π system) in the S₁ states in line with Baird's rule. The lone pair electrons of the arsenic atoms play a crucial role in the aromaticity in the S₁ states.     

Coexistence of Spin–Lattice Relaxation and Phonon-Bottleneck Processes in GdIII–Phthlocyaninato Triple-Decker Complexes under Highly Diluted Conditions

Gd³⁺ complexes have been shown to undergo unusual slow magnetic relaxation processes similar to those of single-molecule magnets (SMMs), even though Gd³⁺ does not exhibit strong magnetic anisotropy. To reveal the origin of the slow magnetic relaxation of Gd³⁺ complexes, we have investigated the magnetic properties and heat capacities of two Gd³⁺-phthalocyaninato triple-decker complexes, one of which has intramolecular Gd³⁺–Gd³⁺ interactions and the other does not. It was found that the Gd³⁺–Gd³⁺ interactions accelerate the magnetic relaxation processes. In addition, magnetically diluted samples, prepared by doping a small amount of the Gd³⁺ complexes into a large amount of diamagnetic Y³⁺ complexes, underwent dual magnetic relaxation processes. A detailed dynamic magnetic analysis revealed that the coexistence of spin–lattice relaxation and phonon-bottleneck processes is the origin of the dual magnetic relaxation processes.     

A novel electrosynthetic system for anodic substitution reactions by using parallel laminar flow in a microflow reactor

We have developed a novel electrosynthetic system for anodic substitution reactions by using parallel laminar flow in a microflow reactor. This system enables nucleophilic reactions to overcome the restraint, such as the oxidation potential of nucleophiles and the stability of cationic intermediates, by the combined use of ionic liquids as reaction media and the parallel laminar flow in the microflow reactor. By using this novel electrosynthetic system, the anodic substitution reaction of carbamates, especially of cyclic carbamates, with allyltrimethylsilane were carried out to provide the corresponding products in moderate to good conversion yields in a single flow-through operation at ambient temperature (without the need for low-temperature conditions).     

Synthesis of 3-substituted isocoumarins and their inhibitory effects on degranulation of RBL-2H3 cells induced by antigen

Eleven 3-substituted isocoumarins and a benzylidenephthalide were synthesized through thermal cyclization reaction of delta- and gamma-ketoamides, respectively. Subsequent deprotection of the hydroxyl groups of the resulting isocoumarin and benzylidenephthalide compounds afforded thunberginols A, B, and F, respectively, which originated from the processed leaves of Hydrangea macrophylla SERINGE var. thunbergii MAKINO. The synthesized isocoumarins and thunberginols were evaluated for their anti-allergic activity, in which thunberginol B exhibited the highest inhibitory potency on the degranulation of RBL-2H3 cells induced by antigen. Structure-activity relationship studies were carried out to determine the necessary substituents on the 3-phenylisocoumarin skeleton for inhibitory activity.