A quantum chemical study of interchain hopping model of negatively charged solitons in polyacetylene

Phonon-assisted interchain hopping of negatively charged solitons in polyacetylene has been studied using a local chemical reaction model CH + CH₄ → CH₄ + CH. Quantum chemical characteristics of the electron transfer process have been analyzed in terms of the dynamic electron density and the mutual polarization moment. The CH stretching vibrational motion of CH₄, which is a local model of the sp³ defect, has been found to play a significant role for the electron transfer. The excitation of the corresponding vibrational mode of the sp³ defect would promote the interchain hopping of the charged soliton. The electron transfer process has also been studied in terms of the “regional” density functional theory. It has been shown that the driving force of the electron transfer is represented by the regional chemical potentials.     

Progress toward the total synthesis of ciguatoxins: a convergent synthesis of the FGHIJKLM ring fragment

[structure: see text] A highly convergent synthetic route to the FGHIJKLM ring fragment of ciguatoxins has been developed, which relied on extensive use of the B-alkyl Suzuki-Miyaura coupling reaction.     

Dynamic stability of carbonyl ylides

The non- and fluorine-substituted singlet carbonyl ylides are studied by using ab initio MCSCF calculations. The thermodynamic stability of the carbonyl ylides and the intramolecular stability to isomerization or fragmentation reaction coordinates is demonstrated in terms of the topological structure of the ab initio potential energy surfaces. The allylic resonance is found to be dynamically unstable, considering out-of-plane vibrational mode. The instability is studied by the symmetries of the low-lying excitations out of the MCSCF wave function.     

Direct measurements of HOx radicals in the marine boundary layer: testing the current tropospheric chemistry mechanism

OH and HO(2) radicals, atmospheric detergents, and the reservoir thereof, play central roles in tropospheric chemistry. In spite of their importance, we had no choice but to trust their concentrations predicted by modeling studies based on known chemical processes. However, recent direct measurements of these radicals have enabled us to test and revise our knowledge of the processes by comparing the predicted and observed values of the radical concentrations. We developed a laser-induced fluorescence (LIF) instrument and successfully observed OH and HO(2) at three remote islands of Japan (Oki Island, Okinawa Island, and Rishiri Island). At Okinawa Island, the observed daytime level of HO(2) agreed closely with the model estimates, suggesting that the photochemistry at Okinawa is well described by the current chemistry mechanism. At Rishiri Island, in contrast, the observed daytime level of HO(2) was consistently much lower than the calculated values. We proposed that iodine chemistry, usually not incorporated into the mechanism, is at least partly responsible for the discrepancy in the results. At night, HO(2) was detected at levels greater than 1 pptv at all three islands, suggesting the presence of processes in the dark that produce radicals. We showed that ozone reactions with unsaturated hydrocarbons, including monoterpenes, could significantly contribute to radical production.     

Design and synthesis of novel type somatostatin analogs with antiproliferative activities on A431 tumor cells

It was reported that the somatostatin analog TT-232, d-Phe-c(Cys-Tyr-d-Trp-Lys-Cys)-Thr-NH₂, exhibited a highly potent antitumor activity in vitro and in vivo. Using pyrazinone analogs and aliphatic amino acids instead of the disulfide bond, we prepared novel type somatostatin analogs including the sequence essential for antitumor activities, Tyr-d-Trp-Lys. These analogs exhibited antiproliferative effect on A431 tumor cells.     

Markers of bone pain in hemodialysis patients with renal insufficiency

The patients receiving maintenance hemodialysis were divided into two groups in the absence and the presence of bone pain and investigated the markers of bone pain in these patients. These results suggested that the duration of receiving hemodialysis, serum concentrations of alkaline phosphatase, osteocalcin and parathyroid hormone became to be the markers of bone pain.