Formulation for XPS spectral change of oxides by ion bombardment as a function of sputtering time

XPS measurement revealed that the original state of TiO₂ was changed to Ti₂O₃ and TiO by ion bombardment. TiO₂ decreased and Ti₂O₃ increased at the initial stage. TiO increased at a later stage than Ti₂O₃. Each of them saturated after enough sputtering time.A formulation was proposed in order to explain the change of XPS spectra for oxides as a function of ion sputtering time. This formulation was based on reaction equations that contain two reduction processes (from TiO₂ to Ti₂O₃ and from Ti₂O₃ to TiO), and sputtering effects. Using four fitting parameters (two reduction coefficients, sputtering yield and information depth), the present formula was fitted to the experimental results. The fitting results agree satisfactorily with the experimental results. The calculation shows that the reduction coefficient from TiO₂ to Ti₂O₃ is about ten times larger than that from Ti₂O₃ to TiO. This calculation predicts that surface composition of an oxide that is changed by ion bombardment will reach a different value depending on its bulk composition. Moreover, the present formulation can determine the chemical states of compounds changed by ion bombardment.     

Enhancement effect of iron addition for the decomposition of organic mercury as studied by continuous flow analysis with cold vapor atomic absorption spectrometric detection

Summary A continuous flow analysis is described for the determination of total mercury by cold vapor atomic absorption spectrometry. Organic mercury compounds such as methylmercury(II) chloride, ethylmercury(II) chloride and phenylmercury(II) chloride were decomposed by potassium peroxodisulphate with addition of ferric chloride as catalytic reagent. The reducing reagent used was tin(II) chloride in sodium hydroxide solution. With 1,000 mg Fe/l added in the decomposition process, we found that methylmercury(II) chloride and ethylmercury(II) chloride gave response signals similar to those of mercury(II) chloride. The proposed method was applied to the analysis of total mercury in waste water. Permanent address: Department of Chemistry, Faculty of Mathematics and Natural Sciences, Andalas University, Padang, West Sumatra, Indonesia     

Successive phase transitions of [(PyO)(H/D)][AuCl4] (PyO=C5H5NO)

³⁵Cl NQR as well as heat capacity measurements of [(PyO)H][AuCl₄] and its deuterated analog [(PyO)D][AuCl₄] revealed successive phase transitions at 70.5 and 62.5 K, and at 71 and 63 K, respectively. The NQR frequency varied continuously through the upper transition point while discontinuously through the lower transition point. In the intermediate-temperature phase a remarkable decrease in the signal intensity was observed. These NQR observations as well as the feature of the heat capacity anomaly in which a broad peak is succeeded by a sharp peak with decreasing temperature suggest a possibility of normal-incommensurate-commensurate phase sequence.     

The first total synthesis of (±)-annosqualine by means of oxidative enamide-phenol coupling: pronounced effect of phenoxide formation on the phenol oxidation mechanism

The first total synthesis of a spiro-isoquinoline alkaloid, (±)-annosqualine, was established by employing an enamide-phenol coupling of a 1-methylene-1,2,3,4-tetrahydroisoquinoline derivative with a hypervalent iodine reagent, where the formation of the phenoxide was recognized to be an essential step for the reaction of the phenolic hydroxyl group with the hypervalent iodine reagent leading to the formation of the desired product.     

Martin Boundaries of Elliptic Skew Products, Semismall Perturbations, and Fundamental Solutions of Parabolic Equations

We consider positive solutions of elliptic partial differential equations on non-compact domains of Riemannian manifolds. We explicitly determine Martin boundaries and Martin kernels for a class of elliptic equations in skew product form by exploiting and developing perturbation theory for elliptic equations and short/long-time estimates for fundamental solutions of parabolic equations.     

Synthesis of endogenous sperm-activating and attracting factor isolated from ascidian Ciona intestinalis

A chemoattractant candidate named sperm-activating and attracting factor (SAAF) from the eggs of ascidian Ciona intestinalis, was synthesized from chenodeoxycholic acid in 16 steps. The present synthesis led to the unambiguous structure determination of SAAF to be (3R,4R,7R,25S)-3,4,7,26-tetrahydroxycholestane-3,26-disulfate. The synthetic pure specimen was also used to confirm the dual sperm-activating and attracting activity.     

Major-to-ultratrace elements in bone-marrow fluid as determined by ICP-AES and ICP-MS.

The major-to-ultratrace elements in human bone-marrow fluid were determined by ICP-AES (inductively coupled plasma atomic emission spectrometry), and ICP-MS (inductively coupled plasma mass spectrometry). The bone-marrow fluid sample was centrifuged prior to acid digestion to exclude the bone piece from bone marrow, and then digested with nitric acid. As a result, 20 elements could be determined over the concentration range from 1610 microg g(-1) for Na to 0.00043 microg g(-1) for W. It was found that Fe, Zn and Sb were enriched by ca. 264-, 7- and 15-fold, respectively, in bone-marrow fluid, compared to those in human blood serum. Alkali metals (K, Rb, Cs), except for Na, were also significantly enriched in bone-marrow fluid. Furthermore, the concentrations of various elements, such as Fe, P, Al, Zn, Cu, Se, Zr, Sn, Ag and W, were significantly higher than those in open seawater.