Multielement monitoring for dissolved and acid-soluble concentrations of trace metals in surface seawater along the ferry track between Osaka and Okinawa as investigated by ICP-MS.

Multielement monitoring of the concentrations of trace metals dissolved in surface seawater collected at sampling stations along the ferry track between Osaka and Okinawa was performed by ICP-MS (inductively coupled plasma mass spectrometry). The surface seawater samples were collected by an automated sampling system for on-board sampling, which was installed on the bottom of a ferryboat. A part of each seawater sample was filtered with a membrane filter (pore size of 0.45 microm) immediately after sampling. Both filtered and non-filtered seawater samples were acidified to pH ca. 1 by adding conc. HNO3, and were subjected to chelating resin preconcentration for the determination of trace metals by ICP-MS, where the concentrations of analyte metals in the filtered and non-filtered seawater samples were referred to as the dissolved and total concentrations, respectively. According to the thus-obtained results, it was found that most trace metals, especially below the 0.01 microg l(-1) as the dissolved and total concentrations, sensitively reflected the environmental pollution in the Osaka Bay and Seto Inland Sea area, as well as near to the Bungo Canal and the outlet of Kagoshima Bay.     

Difference of solute-solvent interactions of cis- and trans-1,2-dichloroethylene in supercritical CO2 investigated by raman spectroscopy

Vibrational Raman spectra of CC stretching modes of both cis- and trans-1,2-dichloroethylene (C2H2Cl2) were measured as a function of density in supercritical carbon dioxide (CO2). Measurements were performed with solute mole fraction of 0.01 at an isotherm of T r = T/ T c = 1.02. As the density of CO2 increased, peak frequencies of the CC stretching modes shifted toward the low energy side. By analyzing these density dependences using perturbed hard-sphere theory, we decomposed the shifted amounts into attractive and repulsive components. The amounts of repulsive shifts were almost equivalent, whereas those of the attractive shifts of trans-C2H2Cl 2 were larger than those of cis-C2H2Cl2 at all densities. This means that the nonpolar solute, trans-C2H2Cl2, shows stronger solute-solvent interactions than those of the polar solute cis-C2H2Cl2. The difference of attractive interactions between these isomers is the greatest at a density where local density enhancement of supercritical CO2 reaches the maximum.     

Colloidal crystallization of colloidal silica modified with ferrocenyl group-contained polymers in organic solvents

Surface modification of colloidal silica with ferrocenyl-grafted polymer and colloidal crystallization of the particles in organic solvent were studied. Poly(methyl methacrylate-co-vinylferrocene)-grafted silica never formed colloidal crystals in polar solvent, such as acetone, acetonitrile, ethanol and N,N-dimethylformamide (DMF), while poly(methyl methacrylate-co-ferrocenyl acrylate)-grafted silica gave colloidal crystallization in DMF. The particles prepared by grafting of poly(N,N-dimethylacrylamide-co-vinylferrocene), with vinylferrocene (Vfc) mole fraction of 1/13 and 1/23, were observed to give the crystallization in ethanol and DMF over particle volume fraction of 0.058. Further, silica modified with copolymer of Vfc and N-vinyl-2-pyrrolidone, N-vinylcarbazole or N-isopropylacrylamide formed colloidal crystals in ethanol and DMF. Especially, poly(N-isopropylacrylamide-co-Vfc)-grafted silica, which was composed of the highest mole fraction of vinylferrocene, 1/3, afforded colloidal crystallization in ethanol over particle volume fraction of 0.053. Relatively high polar vinylferrocene copolymer grafting of silica resulted in colloidal polymerization in organic solvents.     

Formation of N-heterocyclic, donor-stabilized borenium ions

Cationic and zwitterionic boryl bromide species and a borenium-boryl bromide cation have been synthesised which represent new N-donor stabilised cationic boron compounds with β-diketiminate ligands. The unexpected borenium-boryl bromide results from a head-to-tail dimerisation of the corresponding zwitterionic boryl bromide accompanied by proton migration. The electronic nature of these new species was studied by DFT calculations.     

Magnetic Susceptibility of Deintercalated Tunnel Compound of KxCr5Se8 and Mössbauer Spectra of Kx(Cr0.95 57Fe0.05)5Se8

Abstract

KCr₅Se₈ has a TIV₅S₈-type structure, containing K ions in one-dimensional tunnels. Deintercalated samples of K_xCr₅Se₈ (0.32 ≤ x ≤ 0.93) were prepared by leaching method using Alc₃/FeCl₃ aqueous solution. These samples showed a broad peak of magnetic susceptibility at ca. 130 K. ⁵⁷Fe-Mössbauer spectra of K_x(Cr_0.95 ⁵⁷Fe_0.05)₅Se₈ (x = 1.0, 0.49) showed a quadrupole doublet at 300 K. Magnetic sextets appeared at 4.2 K in both samples, indicative of magnetic ordering. The observed isomer shift indicated that the charge of Fe is +3 in both samples. It was proposed that Se^2- was partially oxidized by the deintercalation.     

Molecularly imprinted solid-phase extraction for the selective determination of methamphetamine, amphetamine, and methylenedioxyphenylalkylamine designer drugs in human whole blood by gas chromatography-mass spectrometry

A novel method is described for the extraction of methamphetamine, amphetamine, and methylenedioxyphenylalkylamine designer drugs, such as 3,4-methylenedioxy-methamphetamine, 3,4-methylenedioxyamphetamine, 3,4-methylenedioxyethylamphetamine, N-methyl-1-(3,4-methylenedioxyphenyl)-2-butanamine, and 3,4-(methylenedioxyphenyl)-2-butanamine, from human whole blood using molecularly imprinted solid-phase extraction as highly selective sample clean-up technique. Whole blood samples were diluted with 10 mmol/L ammonium acetate (pH 8.6) and applied to a SupelMIP-Amphetamine molecularly imprinted solid-phase extraction cartridge. The cartridge was then washed to eliminate interferences, and the amphetamines of interest were eluted with formic acid/methanol (1:100, v/v). After derivatization with trifluoroacetic anhydride, the analytes were quantified using gas chromatography-mass spectrometry. Recoveries of the seven amphetamines spiked into whole blood were 89.1-102%. The limits of quantification for each compound in 200 μL of whole blood were between 0.25 and 1.0 ng. The maximum intra- and inter-day coefficients of variation were 9.96 and 13.8%, respectively. The results show that methamphetamine, amphetamine, and methylenedioxyphenylalkyl-amine designer drugs can be efficiently extracted from crude biological samples such as whole blood by molecularly imprinted solid-phase extraction with good reproducibility. This extraction method will be useful for the pretreatment of human samples before gas chromatography-mass spectrometry.