Use of transition elements to enhance sensitivity for selenium determination by graphite-furnace atomic-absorption spectrophotometry combined with solvent extraction with the APDC-MIBK system

A microanalytical method for the measurement of selenium in waters and biological materials by a flameless atomic-absorption technique has been developed. The ammonium pyrrolidinedithiocarbamate-methyl isobutyl ketone extraction system is used for separation from interfering materials such as large amounts of alkali and alkaline earth metal salts and mineral acids. The atomic-absorption sensitivity for selenium is found to be enhanced to a large extent by co-extraction of some transition metal ions. Copper(II) has been used successfully as such an additive to diminish the volatility of selenium in the graphite furnace during the ashing step of the atomization cycle. When the aqueous phase/organic solvent volume ratio is 5 and the volume injected into the graphite furnace is 20 mul, the sensitivity for selenium is 0.3 ng/ml for 1% absorption. The relative standard deviation is ca. 2%. Interference by other metal ions is prevented by masking with EDTA. The method has been applied satisfactorily for the determination of minute amounts of selenium in waters and various biological materials.     

Radioisotopes of thirteen elements in intertidal coastal and estuarine sediments in the Irish Sea

A survey has been carried out of⁴⁰K,⁶⁰Co,⁹⁹Tc,¹⁰⁶Ru,¹²⁵Sb,¹²⁹I,¹³⁴Cs,¹³⁷Cs,¹⁵⁴Eu,²²⁶Ra,²²⁸Ra,²³⁷Np,²³⁸Pu,^239,240Pu,²⁴¹Pu,²⁴¹Am,²⁴²Cm, and^243,244Cm activities in sediments from the Irish Sea. Several of these radionuclides were measured independently at two separate laboratories to enable the intercomparison of the results produced. The comprehensive data set generated allows the present spatial distributions of these radionuclides in coastal sediments to be examined in relation to sediment textural characteristics and by comparison with earlier survey, enables the temporal trends in their activities to be determined. In general all artificial radionuclides showed lower activities in sediments in response to falling discharges from Sellafield and relationships with either grain size, distance from Sellafield or both. Isotope ratios were similar to cumulative weighted activity ratios rather than present day values due to sediment mixing. Pu levels supplied evidence for the lag in response of sediment deposits with increasing distance from Sellafield due to sediment transport.     

Determination of environmental actinide nuclides and210Pb(210Po) by low-energy photon spectrometry with alpha-spectrometry

Low-energy photon spectrometry with -spectrometry was used to determine the environmental concentrations of low-level actinides and other nuclides, especially²¹⁰Pb and²¹⁰Po. The isotopic ratio of²⁴⁰Pu/²³⁹Pu was successfully determined by measuring L_x-ray/-ray counting ratio. A reliable method has been developed for the determination of extremely low-level²³⁷Np global fallout in environmental samples. The non-destructive determination by Ge-LEPS for natural²¹⁰Pb in various samples (tobacco leaves, commercially available tobacco, etc.) was also carried out with the determination of²¹⁰Po by -spectrometry using²⁰⁹Po as a yield tracer.     

Catalytic, highly enantio- and diastereoselective pinacol coupling reaction with a new tethered bis(8-quinolinolato) ligand

A new class of chiral ligand, tethered bis(8-quinolinol) (TBOxH), is developed. Its chromium complex, TBOxCrCl (3 mol %), effectively catalyzes the pinacol coupling reaction of aromatic aldehydes at room temperature with high yield (up to 94%), high diastereoselectivity (up to dl:meso = 98:2), and high enantioselectivity (up to 98%). The scope of the present method turns out not to be limited to aromatic aldehyde derivatives, as cyclohexanecarboxaldehyde undergoes pinacolization as well (44% yield, dl:meso = 93:7, 84% ee). The method provides an efficient access to enantioenriched 1,2-diols.     

Ideal nonideality in adsorption of 2-aminoethanethiol and 2-mercaptoethane sulfonic acid to form electrostatically stabilized binary self-assembled monolayers on Au(111)

In formation of binary self-assembled monolayers (SAMs) composed of 2-aminoethanethiol (AET) and 2-mercaptoethane sulfonic acid (MES) by adsorption from an ethanol solution on Au(111), the adsorption shows nearly ideal nonideality in that the surface ratio of MES to AET in the SAM is unity and does not depend on the mixing ratio of MES to AET in the bathing ethanol solution used for preparing SAMs, chi(soln)MES, over the wide range of chi(soln)MES between 0.01 and 0.95. X-ray photoelectron spectroscopy confirms that at least 80% of AET molecules adsorbed are protonated in this range of chi(soln)MES, indicating that the electrostatic interaction between positively charged AET and negatively charged MES is responsible to the observed nonideality. Correspondingly, there appears only one cathodic peak in a linear-sweep voltammogram of the reductive desorption of the SAM, having a narrow full width at half-maximum of about 20 mV. This suggests the presence of strong lateral attractive interaction between the adsorbed thiolates.     

Determination of Low-Level Ethylenediaminetetraacetic Acid in Water Samples by Ion Chromatography with Ultraviolet Detection

A convenient and sensitive ion chromatographic (IC) method for the analysis of ethylenediaminetetraacetic acid (EDTA) in water samples was proposed. Using a fast reversible reaction of free EDTA and metal–EDTA complexes into Fe(III)–EDTA complex in the presence of Fe(III) ions, sample solutions were applied to an ion-exchange column using a mobile phase (pH 2.3), which was composed of 100 μM Fe(III) chloride and 5 mM methanesulfonic acid. The addition of Fe(III) solution (100 μL) containing 10 mM Fe(III) chloride and 0.5 M methanesulfonic acid to the sample solution (10 mL) permitted the injection of a large volume (400 μL) of sample, which allowed for greater sensitivity. The proposed IC method gave a highly linear (r ² > 0.999) calibration curve ranging 0.005–1.0 μM EDTA and had a limit of detection of 1.5 nM. High repeatability (RSD < 2.1%) and recoveries (88–108%) were also obtained. With this method, total EDTA level in raw and drinking waters were analyzed successfully.     

Photoinduced ionic polymerization. VII. Cationic polymerization of cyclohexene oxide in solid state

Photopolymerization of cyclohexene oxide in the presence of electron acceptors was studied in a bulk system (in liquid as well as in solid states). The polymerization was proved to proceed by a cationic mechanism in both states by the effect of inhibitors. In a liquid phase the light intensity dependence of the rate of polymerization and the molecular weight distribution showed a contribution of a free ionic polymerization. Any discontinuous phenomenon in the rate as well as in the molecular weight was not discerned between liquid(above ?36°C) and plastic crystal (between ?36 and ?81°C) phases. A quantum yield of monomer consumption as high as 8 × 10³ was observed in the plastic crystal phase. Below ?81°C in the normal crystal phase the rate as well as the molecular weight was remarkably suppressed.     

Ligand-exchange ion chromatographic determination of malic acid enantiomers in apple juice with photometric detection.

An ion chromatographic separation with photometric detection using a chiral copper(II) complex as the eluent has been developed for the resolution of enantiomers of malic acid in commercially available apple juices. The results obtained by this method were in good agreement with those by an enzymatic method with separation by high-performance liquid chromatography.     

High pressure and high temperature investigations in the system MgOSiO2H2O

The system MgOSiO₂H₂O was investigated at pressures between 40 and 95 kbar and at temperatures between 500 and 1400°C. The reaction products were examined by X-ray, optical and thermal analysis techniques and the density of phase A discovered by Ringwood and Major was also measured. It was found that phase A was hydrated and its chemical formula was H₆Mg₇Si₂O₁₄. When the $\text{Mg}\text{Si}$ ratio of the system is 2, phase A + clinoenstatite, and forsterite are stable at temperatures lower and higher than a boundary curve T (°C) = 10P (kbar), respectively. When the $\text{Mg}\text{Si}$ ratio of the system is 3, phase A + phase D (which is completely different from the phases, A, B and C discovered by Ringwood and Major, and any other known phases of magnesium silicate) and phase D + brucite are stable at temperatures lower and higher than a boundary curve T(°C) = 10P (kbar) + 200. Phase A has approximately an hexagonal symmetry and the space group and the lattice parameters are determined as P6₃ or $\text{P6}{}_3\text{m}$ and a = 7.866(2) Å and c = 9.600(3) Å, respectively. The measured density is 2.96 ± 0.02 g/cm³. The optical observations show that phase A is biaxial positive crystal with refractive indices α = 1.638 ± 0.001, β = 1.640 ± 0.002, and γ = 1.649 ± 0.001. Some interpretation is given on the inconsistency between the symmetry determined by the X-ray diffraction and the optical observation. The new phase D belongs to the space group $\text{P2}{}_1\text{c}$ with lattice parameters a = 7.914(2)Å, b = 4.752(1) Å, c = 10.350(2) Å and β = 108.71(5)° and is a biaxial crystal with refractive indices α = 1.630 ± 0.002, β = 1.642 ± 0.002 and γ = 1.658 ± 0.001.     

Photoreaction of anthracenyl phosphine oxides: Usual reversible photo- and heat-induced emission switching,and unusual oxidative PC bond cleavage

Anthracenyl(diphenyl)phosphine oxide and dianthracenylphenylphosphine oxide as photoactive compounds have been synthesized. Anthracenyl group of these compounds indicate the multi-functional roles such as an emission component, a photodimerization component, and a leaving group. When the light irradiation was performed under an oxygen atmosphere, photo-oxidative PC bond cleavage to leave the antharacenyl group was observed. Moreover, phosphonyl radical was produced and then PP bond formation to form diphosphane was observed.