Conversion of Ca2+ salt of an organic compound to its Li+ salt to simplify the fast atom bombardment mass spectrum

The FAB mass spectrum of the Ca(2+) salt of RK-682 (1, MW 368), a potent protein tyrosine phosphatase inhibitor, shows a complex pattern due to Ca(2+) adduct ions with multimers of 1 and their decomposition ions. Addition of LiCl greatly simplified the FAB mass spectrum, providing a prominent Li(+) adduct ion of 1 at m/z 381 [M+2Li-H](+). The addition of LiCl also greatly simplified the FAB mass spectrum of calcium pantothenate. This approach may be generally useful for molecular weight determination of multivalent metal salts of organic compounds, or organic compounds that can form Li salts, by FAB mass spectrometry.     

An integrated strategy by absorbed component characterization,pharmacokinetics, and activity evaluation for identification of potential nephroprotective substances in Zhu-Ling decoction

An efficient strategy for the identification of potential nephroprotective substances in Zhu-Ling decoction has been established with the integration of absorbed components characterization, pharmacokinetics, and activity evaluation. A qualitative method was developed to characterize the chemical constituents absorbed components in vivo of Zhu-Ling decoction by using ultra-performance liquid chromatography-quadrupole-time-of-flight mass spectrometry. A quantitative method was established and validated for the simultaneous determination of eight compounds in rat plasma by using ultra-performance liquid chromatography-triple quadruple tandem mass spectrometry. Finally, the nephroprotective activities of absorbed components with high exposure were assessed by cell survival rate, superoxide dismutase, and malondialdehyde activities in hydrogen peroxide–induced Vero cells. As a result, 111 compounds in Zhu-Ling decoction and 36 absorbed components were identified in rat plasma and urine, and poricoic acid A, poricoic acid B, alisol A, 16-oxo-alisol A, and dehydro-tumulosic acid had high exposure levels in rat plasma. Finally, poricoic acid B, poricoic acid A, 16-oxo-alisol A, and dehydro-tumulosic acid showed remarkable nephroprotective activity against Vero cells damage induced by hydrogen peroxide. Besides, superoxide dismutase and malondialdehyde activities were obviously regulated in hydrogen peroxide–induced Vero cells by treatment with the four compounds mentioned above. Therefore, these four compounds were considered to be effective substances of Zhu-Ling decoction due to their relatively high exposure in vivo and biological activity. This study provided a chemical basis for the action mechanism of Zhu-Ling decoction in the treatment of chronic kidney diseases.     

5＇-Hydroxyzearalenol,a new β-resorcylic macrolide from Fusarium sp. 05ABR26

A new β-resorcylic macrolide, 5＇-hydroxyzearalenol （1）, was isolated from the culture broth of a marine-derived fungus Fusarium sp. 05ABR26. Three known compounds, zearalenone （2）, 8＇-hydroxyzearalenone （3） and zearalenol （4） were also isolated. The structure and relative stereochemistry of 1 were elucidated on the basis of spectroscopic data and single-crystal X-ray diffraction data. Compound 2 displayed potent inhibitory activity against Pyricularia oryzae with a MIC value of 6.25 μg/mL, while compound 3 was much less active; however, 1 and 4 showed no obvious activity.     

5′-Hydroxyzearalenol,a new β-resorcylic macrolide from Fusarium sp. 05ABR26

A new β-resorcylic macrolide,5′-hydroxyzearalenol(1),was isolated from the culture broth of a marine-derived fungus Fusarium sp.05ABR26.Three known compounds,zearalenone(2),8′-hydroxyzearalenone(3)and zearalenol(4)were also isolated.The structure and relative stereoehemistry of 1 were elucidated on the basis of spectroscopic data and single-crystal X-ray diffraction data.Compound 2 displayed potent inhibitory activity against Pyricularia oryzae with a MIC value of 6.25μg/mL, while compound 3 was much less active;however,1 and 4 showed no obvious activity.     

Single bubble growth during water electrolysis under microgravity

Single bubble evolution on a micro-electrode (Pt, φ = 0.2 mm) was observed in 0.36 M KOH solution under terrestrial (1-G) and microgravity (μ-G) environments. The bubble size during galvanostatic electrolysis (j = −2.6 × 10³ A m⁻²) was measured by CCD images, which allowed us to calculate the gas evolution efficiency, f_G, by comparison with the consumed charge. The efficiency under μ-G increased until 1 s after starting electrolysis and then reached constant value (f_G = 0.85), while, under 1-G, it showed a lower value and remarkably decreased 2 s after the beginning of the measurement. Such differences between μ-G and 1-G were explained by the mass transfer rate of the dissolved gas. Bubble-induced microconvection dominated the mass transfer under μ-G without any buoyancy force, on the other hand, the single-phase free convection (microscopic natural convection) influenced the bubble growth under 1-G.     

Platinum clusters on vacancy-type defects of nanometer-sized graphene patches

Density functional theory calculations found that spin density distributions of platinum clusters adsorbed on nanometer-size defective graphene patches with zigzag edges deviate strongly from those in the corresponding bare clusters, due to strong Pt-C interactions. In contrast, platinum clusters on the pristine patch have spin density distributions similar to the bare cases. The different spin density distributions come from whether underlying carbon atoms have radical characters or not. In the pristine patch, center carbon atoms do not have spin densities, and they cannot influence radical characters of the absorbed cluster. In contrast, radical characters appear on the defective sites, and thus spin density distributions of the adsorbed clusters are modulated by the Pt-C interactions. Consequently, characters of platinum clusters adsorbed on the sp2 surface can be changed by introducing vacancy-type defects.     

Theoretical study of NH3 adsorption on Fe(110) and Fe(111) surfaces

With the aim of understanding the nature of the interactions between organic molecules and metal surfaces, the adsorption of NH3 onto model Fe(110) and Fe(111) surfaces has been studied with use of the molecular orbital and density functional theories. B3LYP calculations have revealed that the on-top site is most suitable for adsorption of NH3 both on Fe(110) and on Fe(111). Mulliken population analysis in terms of the MO's of the two fragment systems suggested that electron delocalization from NH3 to the Fe surface should play a key role in the adsorption. Then, our transformation scheme of fragment orbitals has demonstrated that the electron delocalization is represented well only by a pair of interaction orbitals. The NH3 molecule provides the occupied interaction orbital bearing a close resemblance to the highest occupied (HO) MO, whereas the Fe surface prepares the paired unoccupied orbital that is localized at the adsorption site and overlaps in-phase with the orbital of NH3. Not only the lowest unoccupied (LU) MO but also other unoccupied MO's have been shown to participate significantly in the interaction. The reason the on-top site is the most preferable position for NH3 attack has been elucidated by investigating the interaction orbitals.     

Development of an Ultra-High Performance Multi-Turn TOF-SIMS/SNMS System “MULTUM-SIMS/SNMS”

A new system incorporating a multi-turn time-of-flight secondary ion/sputtered neutral mass spectrometer (TOF-SIMS/SNMS) with laser post-ionization was designed and constructed. This system consists of a gallium focused ion beam, femtosecond (fs) laser for post-ionization, and multi-turn TOF mass spectrometer. When laser post-ionization was used, the secondary ion signal strengths for several metals increased by up to 650 times, and were greater than the values obtained in conventional TOF-SIMS experiments. Use of the multi-turn mass spectrometer resulted in an increase in mass resolving power with increase in the total TOF. The mass resolving power reached to 23,000 after 800 multi-turn cycles, corresponding to a flight path length of 1040 m. These results indicated that this system is very effective for the analysis of valuable materials such as space samples with high sensitivity, high mass resolving power, and high lateral resolution.      

Extractability of dioxins from suspended substances in distributed water

The extractability of dioxins from suspended substances (SS) in distributed water was evaluated. Dioxins adsorbed on the collected SS were extracted by pressurized liquid extraction with various solvents. High-polarity solvents (acetone, alcohols) extracted considerably higher amounts of some lower-chlorinated dibenzo-p-dioxins (LoCDDs) than did low-polarity solvents (dichloromethane, toluene), whereas the extracted amounts of higher-chlorinated dibenzo-p-dioxins (HiCDDs) were roughly the same, regardless of the solvent. The extractability of the LoCDDs depended on the isomer. Daily variations in quantities for PCDDs, organic matter (OM), and iron in the SS were examined, and the results suggested that in the SS, LoCDDs and HiCDDs were associated, respectively, with raw water-derived organic matter and microparticles sequestered in iron oxy(hydr)oxide floc. It was also suggested that the low extractability of certain congeners was not attributable to the enormously coexisting ferric compounds but was probably attributable to OM with which they strongly associate.