Identification of Al(III) species in a solution containing equimolar concentrations of Al(III) and citric acid using varying-temperature 27Al NMR spectrometry.

27Al NMR spectra of an equimolar (10 mM) Al(III)-citrate system were obtained at different temperatures. The linewidths of the signals decreased in the spectra recorded at elevated temperatures, which enabled us to unequivocally identify the resonance lines. From the spectrum recorded at 65 approximately C, a mononuclear Al(III)-citrate complex was identified at a solution pH of 3.0 in addition to trinuclear Al(III)-citrate complex, which dominated at pH 4.0.     

Towards the selective formation of specific isomers of fullerenes: T - and p-dependence in the yield of various isomers of fullerenes C60–C84

Systematic fractional change in the yield of various isomers of fullerenes was revealed to strongly depend on temperature of a buffer gas. A new kinetic consideration is proposed for understanding the observed temperature- and pressure-dependence of yield of fullerenes. The model consists of three competitive reactions in consideration of plausible behaviors of a precursor, (1) decomposition into smaller fragments, (2) isomerization leading to formation of a stable fullerene cage, and (3) growth into a larger carbon cluster. Arrhenius activation energy of formation of stable fullerenes was determined to be 0.8 eV for both C₆₀ and C₇₀, while a higher energy of 2.0?3.3 eV for seven different isomers of higher fullerenes ranging from C₇₆ to C₈₄. Correlation in the activation energy is noted for a series of higher fullerenes with different sizes, suggesting the existence of a specific precursor in their formation processes.     

Sensitive measurement of methylene blue active substances by attenuated total reflection spectrometry with a trimethylsilane-modified glass slab optical waveguide

Attenuated total reflection spectrometry with a slab optical waveguide (SOWG) was explored for the simple, rapid and sensitive measurement of total anionic surfactants by the methylene blue active substance (MBAS) method. A fused-silica sheet used as a guiding layer was modified with trimethylsilane (TMS) to extract and concentrate the MBASs on the SOWG surface. Based on preliminary studies of the adsorption behavior and visible ATR spectrum of MB on the modified silica surface, a detection wavelength of 600 nm was chosen for the sensitive measurement of anionic surfactants. When the concentration of MB was set at 10 microM in the final measurement solution, the calibration curve for a typical anionic surfactant (sodium dodecylbenzenesulfonate) was linear up to 0.6 microM and the detection limit was 0.07 microM. The proposed method was applied to the determination of total anionic surfactants in river water.     

Fluorinated monomer–styrene copolymer latex particles: I. kinetic studies in a soap-free aqueous medium

Soap-free emulsion copolymerization of 2, 2, 2-trifluoroethyl acrylate (3FEA) with styrene was carried out by using potassium persulfate as an initiator, and the effects of the weight fraction of 3FEA in the monomer feed on the kinetics and the particle size were investigated. Monomer conversions were followed by a gravimetric method, revealing that the overall polymerization rate increased exponentially with an increase in the weight fraction of 3FEA. According to dynamic light scattering measurement, the final particle size was found to decrease with an increase in the weight fraction of 3FEA. The number of particles for 3FEA homopolymerization was roughly twice as large as that at the fraction of 0.9, although both fractions had the almost same polymerization rates. These results indicate that soap-free emulsion homopolymerization of 3FEA would proceed not only inside the polymer particles but also in the aqueous phase throughout the polymerization.     

Speciation of mercury in salmon egg cell cytoplasm in relation with metallomics research

Speciation of mercury in salmon egg cell cytoplasm was investigated by surfactant-mediated high-performance liquid chromatography/inductively coupled plasma mass spectrometry (HPLC/ICP-MS), where an ODS (octadecylsilica) column coated with a bile acid derivative, CHAPS (3-[(3-cholamidopropyl)-dimethylammonio]-1-propane sulfonate), was used for species separation. Prior to the speciation analysis, total Hg in the cell cytoplasm was determined by ICP-MS at m/z 202 in a flow injection mode. For the precise measurement, salmon egg cell cytoplasm was diluted five-fold with 0.1 M Tris (Tris(hydroxymethyl)aminomethane)-HNO₃ buffer solution, and the standard addition method was employed. Thus, the total concentration of Hg in cell cytoplasm was estimated to be 12.4 ng g⁻¹ on the wet weight basis. Next, the cell cytoplasm diluted five-fold with 0.1 M Tris-HNO₃ buffer solution was analyzed by surfactant-mediated HPLC with the dual detection system of a UV absorption detector and an ICP-MS instrument. Two peaks corresponding to some proteins and small molecules were mainly observed in those chromatograms. When salmon egg cell cytoplasm was diluted five-fold with 0.01 M Tris buffer solution or pure water, some precipitates appeared probably because of precipitation of hydrophobic proteins in cytoplasm. After the precipitates were eliminated with a membrane filter, the filtrate was subjected to the analysis by surfactant-mediated HPLC/UV/ICP-MS. As a result, the peaks for small molecular species of Hg were clearly observed at the retention time near 4.0 min (corresponding to low-molecular weight zone) in the chromatograms with UV absorption detection as well as with Hg- and S-specific ICP-MS detections. The small molecule bound with Hg was identified as cysteine through the cysteine-spiked experiment. In addition, the protein fraction on the chromatogram obtained by using the CHAPS-coated ODS column was further analyzed by SEC (size exclusion chromatography). Consequently, several protein peaks with molecular weight of 300, 50 and 12 kDa were observed in all the detections of UV absorption, Hg and Se, although two peaks among them were coincident in the case of S. These results indicate that Hg in salmon egg cell cytoplasm binds with proteins containing selenocysteine and/or cysteine residues in proteins.     

Ground-state α-decay of N = 128 isotones 216Ra, 217Ac and 218Th

The α-decay properties of very short-lived N = 128 isotones, ²¹⁶Ra, ²¹⁷Ac and ²¹⁸Th, were investigated by the pulsed-beam method. Alpha emitters of interest were produced in the bombardment of ²⁰⁸Pb or ²⁰⁹Bi with 65–96 MeV ¹²C or ¹⁴N ions and α-decays were measured between natural beam bursts of the cyclotron. The results obtained are _Eα = 9.349±0.008 MeVand $\text{t}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{= 182±10}\text{ns for}{}^{216}\text{Ra}\text{, 9.650±0.010}\text{MeV}$ and $\text{111±7}\text{ns for}{}^{217}\text{Ac}\text{, 9.665±0.010}\text{MeV}$ and $\text{96±7}\text{ns for}{}^{218}\text{Th}$. The experimental reduced α-widths of N = 128 isotones from ²¹²Po to ²¹⁸Th are shown to agree well with the simple shell model calculation.     

A density-functional study for the liquid-vapor coexistence curve of nitrogen fluid

We have used a density-functional theory based on the interaction site model to predict the liquid-vapor coexistence curve of nitrogen fluid. The pressure and chemical potential were calculated from thermodynamic integrations. The different paths of thermodynamic integration provide slightly different predictions for the liquid-vapor coexistence curve. However, these critical points and coexistence curves evaluated by the theory are in qualitative agreement with the experimental data. The theoretical coexistence curves scaled to critical constants agree with the experimental data quantitatively.     

Penetration of ammonia molecule into ice film; activation energy analysis using Xe molecular beam irradiation

We have investigated the barrier energy for an ammonia molecule to penetrate into ice film by the use of infrared spectroscopy and Xe supersonic beam. After the ice film on a Pt(1 1 1) surface is exposed to ammonia molecules, an umbrella mode of ammonia molecules adsorbed on the ice film has been observed in infrared spectra. After the irradiation of accelerated Xe beam, we observed an energy shift of the mode of ammonia. The shifted mode is assigned to that of ammonia molecules at the interface between the ice film and the Pt(1 1 1) surface. This indicates that the collision with Xe beam induced the penetration of an ammonia molecule to the interface through the ice film. Using this feature, we estimate a barrier for penetration as 0.28 ± 0.03 eV which is much smaller than the one previously reported for bulk ice.     

Fixed point theory for a class of generalized nonexpansive mappings

In this paper we introduce two new classes of generalized nonexpansive mapping and we study both the existence of fixed points and their asymptotic behavior.     

Perturbation method for determining the group of invariance of hierarchical models

We propose a perturbation method for determining the (largest) group of invariance of a toric ideal defined in [S. Aoki, A. Takemura, The largest group of invariance for Markov bases and toric ideals, J. Symbolic Comput. 43 (5) (2008) 342–358]. In the perturbation method, we investigate how a generic element in the row space of the configuration defining a toric ideal is mapped by a permutation of the indeterminates. Compared to the proof by Aoki and Takemura which was based on stabilizers of a subset of indeterminates, the perturbation method gives a much simpler proof of the group of invariance. In particular, we determine the group of invariance for a general hierarchical model of contingency tables in statistics, under the assumption that the numbers of the levels of the factors are generic. We prove that it is a wreath product indexed by a poset related to the intersection poset of the maximal interaction effects of the model.