ESR studies on calcite encrustation on Fili neotectonic fault, Greece

Electron spin resonance (ESR) study was done on calcite encrustation on Fili neotectonic fault surface, Greece. Normally such calcite encrustations on fault surfaces are not observed. Significantly, the ESR study has detected the presence of nitrate NO₃²⁻ radical in this calcite encrustation, havingg _⊥=2.0063±0.0001 and hyperfine coupling constantA _⊥=3.44 mT, the second such detection of nitrate NO₃²⁻ radical following a sample from Scott Glacier, Antarctica. From isochronal thermal annealing measurement the NO₃²⁻ radical was found to be quite stable, only fully annealed at 475°C. This study also shows that the ESR, as a tool, can be suitably applied to date the age of formation of the calcite encrustation with SO₃⁻ as an ESR dating signal by additive γ-ray irradiation. A preliminary estimation indicates the age of formation of calcite precipitation at Fili fault, Greece to be about 5600 years.     

Spatial distribution and formation of nitrate radical NO<Stack><Subscript>3</Subscript><Superscript>2−</Superscript></Stack> in Antarctic calcitic evaporates

Nitrate radical NO₃²⁻ in calcitic evaporate was discovered in Antarctica. The distribution and formation of nitrate radical NO₃²⁻ in the calcite have been studied by pulse and continuous-wave electron spin resonance. In samples that had been annealed to destroy the NO₃²⁻, regeneration of the radical by γ-rays or UV light indicated that the radical was formed by UV light (with wavelengths less than 340 nm) from solar rays, not by environmental radiation. The nonuniform spatial distribution of the nitrate radical, which was deduced from high ratios of local spin density to total spin density, suggests that the nitrate impurity was introduced into the calcium carbonate after carbonate grain formation. Formation of the carbonate-containing nitrate requires the presence of high amounts of nitrate and a dry climate. Formation of the nitrate radical requires sample exposure to UV light. These conditions are satisfied in the environment of Antarctica.     

Preparation and condensation reactions of a new light-fluorous Mukaiyama reagent: reliable purification with fluorous solid phase extraction for esters and amides

A modified light-fluorous Mukaiyama reagent bearing a C₈F₁₇ tag was prepared and examined in ester and amide forming condensation reactions. Following the reactions, the desired product was effectively separated from the fluorous pyridone by-product using a simple fluorous solid phase extraction.     

Complexation of a hydrophobic thiazorylazophenol with Ni2+ at sodium dodecylsulfate micellar surface

Complexation of thiazorylazododecylphenol (TADP) with Ni2+ at the surface of sodium dodecylsulfate (SDS) micelles has been spectrophotometrically studied. Complicated spectral changes are analyzed by a factor and multivariate analysis, which implies the formation of [TDAP(OH-)Ni]0 as well as a simple 1:1 complex of Ni2+ with TDAP at the micellar interface. All of the equilibrium constants required to describe this system are substantially affected by electrolyte concentrations. Coexistent electrolytes vary the surface potential of the micelle, and in turn influence the equilibria taking place on the micellar surface. The electrostatic potential estimated based on the equilibrium shifts is more negative than that calculated according to Poisson-Boltzmann theory, which simply involves electrostatic effects. This disagreement is possibly caused by different aqueous environments around the micelle from bulk solution, which also facilitate the formation of unusual complex such as [TDAP(OH-)Ni]0.     

Electron spin resonance imaging of mouse B16 melanoma

An X-band electron spin resonance (ESR) imaging apparatus with a pin-hole TE102 mode cavity and a rapid scan coil was constructed. Using this apparatus, ESR imaging of melanin in mouse B16 melanoma was observed for the first time. The ESR spectrum of B16 melanoma is similar to that of natural melanin extracted from sepia officinalis in microwave power dependence.     

Synthesis of the proposed structure of plakevulin A: revised structure of plakevulin A

A total synthesis of the proposed structure of plakevulin A was accomplished. However, the NMR spectral data of the synthetic plakevulin A were not identical of those of the reported compound. We next converted the synthetic plakevulin A into 1-dihydrountenone A. The ¹H and ¹³C NMR spectral data of 1-dihydrountenone A were identical with those of reported plakevulin A except for the peaks derived from levulinic acid. Thus, we repurified sample of the natural product and confirmed that the natural sample contained 1-dihydrountenone A and levulinic acid in the ratio of one to one. We also found that not plakevulin A but 1-dihydountenone A possessed the inhibitory activity against mammalian DNA polymerases α and β.     

An ESR study of NH 3 + , al center and HO2 · radical in alkali feldspars

Paramagnetic centers of NH ₃ ⁺ , Al, and HO₂ · have been observed in alkali feldspars from Aichi prefecture, Japan. The quartet signal has been tentatively ascribed to NH ₃ ⁺ rather than to ·CH₃, although the hyperfine splitting by¹⁴N (I=1) was not observed. The averageg- andA-valuesg _av=2.0033 andA _av ^H =2.45 mT, respectively, were attributed to hydrogen. The powder spectra of Al centers stable up to 400 K were simulated by the anisotropicg factors ofg _zz =2.060,g _xx =2.0014,g _yy=2.0021 andA=0.9 mT. Newly discovered HO₂ · is stable up to 570 K. The intensities of the spectra from NH ₃ ⁺ and Al centers were enhanced by gamma-ray irradiation, while that of HO₂ · was not enhanced. Production efficiency,G-value (radical/100 eV) of NH ₃ ⁺ has been obtained to beG=0.01. These results suggest that ESR dating of feldspars is possible.     

Studies on the metabolism of gomisin A (TJN-101). II. Structure determination of biliary and urinary metabolites in rat

After oral administration of gomisin A (1) to rats, the bile and urine were collected and treated with beta-glucuronidase and arylsulfatase. Seven metabolites, met B (2), met A-III (3), met E (4), met D (5), met F (6), met G (7), and met H (8) were isolated from the bile treated with the enzymes. Eight metabolites 2-8, and met A-II (9) were isolated from the urine treated with the enzymes. A major metabolite 2, and two minor metabolites 3 and 9 were identified as met B, met A-III, and met A-II, respectively, which are oxidative products of 1 formed by rat liver S9 mix. The structures of five new metabolites 4-7, and 8 were determined on the basis of chemical and spectral studies.     

SINGLE AND DOUBLE EDGE INTERFACE CRACK SOLUTIONS FOR ARBITRARY FORMS OF MATERIAL COMBINATION

In this paper interfacial edge crack problems are considered by the application of the finite element method. The stress intensity factors are accurately determined from the ratio of crack-tip-stress value between the target given unknown and reference problems. The reference problem is chosen to produce the singular stress fields proportional to those of the given unknown problem. Here the original proportional method is improved through utilizing very refined meshes and post-processing technique of linear extrapolation. The results for a double-edge interface crack in a bonded strip are newly obtained and compared with those of a single-edge interface crack for different forms of combination of material. It is found that the stress intensity factors should be compared in the three different zones of relative crack lengths. Different from the case of a cracked homogeneous strip, the results for the double edge interface cracks are found to possibly be bigger than those for a single edge interface crack under the same relative crack length.