Ionic probe attachment ionization mass spectrometry

A new ionization method that uses metal-complex-based ionization probes containing the 2,6-bis(oxazolinyl)pyridine (pybox) ligand is presented. This method was proven to effectively ionize large complex molecules, including biomolecules. The preparation of the charged probes and their application to the ionization of biomolecules using cold-spray ionization mass spectrometry are shown.     

Hydration effects on the reaction with an open-shell transition state: QM/MM-ER study for the dehydration reaction of alcohol in hot water

The reaction mechanism for the dehydration of 1,4-butanediol in hot water has been investigated by means of the hybrid quantum mechanical/molecular mechanical approach combined with the theory of energy representation (QM/MM-ER). We have assumed that the proton transfers along the hydrogen bonds of the water molecules catalyze the reaction, where the transition state (TS) forms a singlet biradical electronic structure. It has been revealed by the simulation that the biradical electronic state at the TS changes to zwitterionic structure in solution due to the hydration of the polar solvent. Such the electronic structure change gives rise to the substantial stabilization of the TS in hot water. As a result, the water-catalytic path becomes more favorable in aqueous solution than another possible path that proceeds without proton transfers as opposed to the reaction mechanism in the gas phase. Furthermore, the activation free energy computed by the present method is in excellent agreement with the experimental result.     

Collisional radiative model for the M1 transition spectrum of the highly-charged W54+ ions

A detailed-level collisional-radiative model for the M1 transition spectrum of the Ca-like W⁵⁴⁺ ion as observed in an electron beam ion trap (EBIT) was constructed based on atomic data calculated by the relativistic configuration interaction method and distorted wave theory. The present calculated transition energy, rate and intensity of W⁵⁴⁺ M1 transitions are compared with previous theoretical and experimental values. The results are in reasonable agreement with the available experimental and theoretical data. The synthetic spectrum explained the EBIT spectrum in the 12–20 nm region, while a new possibly strong transition has been predicted to be observable with an appropriate electron beam energy. The present work provides accurate atomic data that may be used in plasma diagnostics applications.     

Mott relation for anomalous Hall and Nernst effects in Ga1-xMnxAs ferromagnetic semiconductors

The Mott relation between the electrical and thermoelectric transport coefficients normally holds for phenomena involving scattering. However, the anomalous Hall effect (AHE) in ferromagnets may arise from intrinsic spin-orbit interaction. In this work, we have simultaneously measured AHE and the anomalous Nernst effect (ANE) in Ga1-xMnxAs ferromagnetic semiconductor films, and observed an exceptionally large ANE at zero magnetic field. We further show that AHE and ANE share a common origin and demonstrate the validity of the Mott relation for the anomalous transport phenomena.     

Structural Features and Properties of Bacterial Cellulose Produced in Agitated Culture

The structure and some properties of bacterial cellulose produced in agitated culture were studied. Scanning electron microscopy revealed that there was almost no difference between reticulated structures of bacterial cellulose fibrils produced in agitated culture and in static culture. Nevertheless, bacterial cellulose produced in agitated culture exhibited microstuctural changes, namely, a low degree of polymerization and a low crystallinity index. A CP/MAS ¹³C NMR analysis revealed that the cellulose I content of the cellulose produced in agitated culture was lower than that of the cellulose produced in static culture. The bacterial cellulose produced in agitated culture had a lower Young's modulus of sheet, a higher water holding capacity and a higher suspension viscosity in the disintegrated form than that produced in static culture.     

Regioselective boron trichloride-mediated aromatic Claisen rearrangement of resorcinol allyl ethers

The regioselective Claisen rearrangement of resorcinol allyl ethers with boron trichloride was achieved with good selectivity (ca. 13:1) to afford the 6-isomer as major product.     

AIB induced chemical reactions at surfaces detected by SIMS

Secondary ion mass spectrometry (SIMS) has been used to detect the reactions induced by active ion bombardment (AIB) of N⁺₂ on surfaces of pyrolytic graphite and a (100) Si crystal. The SIMS spectra exhibit ions of CN^?, HCN^?, H_nC₂N^?(n = 2, 3, 4), HN^?, and SiN^?, indicating that reactions take place with the graphite and silicon as well as adsorbed hydrogen on the surfaces.     

Cytotoxic and apoptosis-inducing ent-kaurane-type diterpenoids from the Japanese liverwort Jungermannia truncata NEES

Five new ent-kaurane-type diterpenoids and a new gymnomitrane (=barbatane)-type sesquiterpenoid have been isolated from the Japanese liverwort Jungermannia truncata NEES, together with twelve previously known ent-kaurane-type diterpenoids. The structures of the new compounds were elucidated by two-dimensional (2D) NMR experiments and chemical reaction. Some of the isolated compounds showed cytotoxicity against human leukemia cell lines and induced apoptosis.