Distribution and cycle of arsenic compounds in the ocean

In order to understand the distribution and the cycle of arsenic compounds in the marine environment, the horizontal distributions of arsenic(V) [As(V)], arsenic(III) [As(III)], monomethylarsonic acid (MMAA) and dimethylarsinic acid (DMAA) in the Indian Pacific Oceanic surface waters have been investigated. This took place during cruises of the boat Shirase from Tokyo to the Syowa Station (15 November–19 December 1990), of the tanker Japan Violet from Sakai to Fujayrah (28 July–17 August 1991) and of the boat Hakuho-maru from Tokyo to Auckland (19 September–27 October 1992). Vertical distributions of arsenic in the west Pacific Ocean have also been investigated. The concentration of As(V) was found to be relatively higher in the Antarctic than in the other areas. Its concentration varied from 340 ng dm^?3 (China Sea) to 1045 ng dm^?3 (Antarctic). On the other hand, the concentrations of the biologically produced species, MMAA and DMAA, were extremely low in the Antarctic and southwest Pacific waters. Their concentrations in Antarctic waters were 8 ng dm^?3 and 22 ng dm^?3 and those in the southwest Pacific were 12 ng dm^?3 and 25 ng dm^?3. In the other regions the concentration varied from 16 ng dm^?3 (China Sea) to 36 ng dm^?3 (north Indian Ocean) for MMAA and from 50 ng dm^?3 (east Indian Ocean) to 172 ng dm^?3 (north Indian Ocean) for DMAA. As a result, with the exception of Antarctic and southwest Pacific waters, the percentages of each arsenic species in the surface waters were very similar and varied from 52% (east Indian Ocean) to 63% (northwest Pacific Ocean) for As(V), from 22% (northwest Pacific Ocean) to 27% (east Indian Ocean) for As(III) and from 15% (northwest Pacific Ocean) to 21% (north and east Indian Oceans) for the methylated arsenics (MMAA+DMAA). These percentages in Antarctic waters were 97%, 0.2% and 2.8%, respectively, and those in the southwest Pacific Ocean were 97% for As(V)+As(III) and 3% for MMAA+DMAA. The very low concentrations of the biologically produced species in Antarctic waters and that of methylated arsenic in southwest Pacific waters indicated that the microorganism communities in these oceans was dominated by microorganisms having a low affinity towards arsenic. Furthermore, microorganism activity in the Antarctic was also limited due to the much lower temperature of the seawater there. The vertical profile of inorganic arsenic was 1350 ng dm^?3 in surface waters, 1500 ng dm^?3 in bottom waters with a maximum value of 1700 ng dm^?3 at a depth of about 2000 m in west Pacific waters. This fact suggested the uptake of arsenic by microorganisms in the surface waters and the co-precipitation of arsenic with hydrated heavy-metal oxides in bottom waters. The suggested uptake of inorganic arsenic and subsequent methylation was also supported by the profile of DMAA, with a high concentration of about 26 ng dm^?3 in surface water and a significant decrease to a value of 9 ng dm^?3 at a depth of 1000 m.     

Synthesis of 3-cyano-2-methylpyridines substituted with heteroaromatics

A series of title compounds were easily prepared by the sonication of α,β-unsaturated carbonyl compound in acetonitrile in the presence of potassium t-butoxide.     

Measurement of the polarization for the reactions K+n → K+n and K0p at 1.06, 1.28, 1.39 and 1.49 GeV/c

The polarization for the K⁺n elastic and charge-exchange reactions was measured at the momenta of 1.06, 1.28, 1.39 and 1.49 GeV/c. It was found to be negative for the K⁺n elastic process and generally positive for the charge-exchange process. The present results are compared with the predictions of phase shift analyses.     

Crystal structures of heptakis(2,3,6-tri-O-methyl)-β-cyclodextrin complexes with (R)- and (S)-Flurbiprofen

Hepatakis(2,3,6-tri-O-methyl)--cyclodextrin (TM--CDx) forms crystalline complexes with (R)-Flubiprofen (R-FP), C₆₃H₁₁₂O₃₅C₁₅H₁₃O₂F·H₂O, and (S)-Flurbiprofen (S-FP), C₆₃H₁₁₂O₃₅C₁₅H₁₃O₂F. The crystal structures were determined by X-ray analysis. Crystals of both compounds are orthorhombic and the space group isP2₁2₁2₁ with cell dimensions:a=15.092(2),b=21.714(3), andc=28.269(4) Å for theR-FP complex, anda=15.271(2),b=21.451(3) andc=27.895(3) Å for theS-FP complex. The macrocyclic ring of TM--CDx is markedly distorted because of the inability to form intramolecular hydrogen bonds and the steric hindrance involving methyl groups. In both complexes, the phenyl group is inserted into the host cavity from the O(2), O(3) side, which is wider than the O(6) side. The biphenyl moiety ofR-FP is fixed in theR-configuration within the host cavity. The phenyl group ofS-FP is disordered, andR-andS-configurations are statistically distributed with equal probability. TM--CDx molecules are stacked along theb axis to form a column structure. The TM--CDx molecule is laterally shifted with respect to the column axis, and a half of the guest molecule protrudes outside from the crevis of the column. The carboxyl group ofR-FP forms a hydrogen bond with water located outside the host cavity, while the carboxyl group ofS-FP is hydrogen-bonded to an oxygen atom of an adjacent TM--CDx. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82064 (24 pages).     

X-ray compressibility measurements of the graphite intercalates KC8 and KC24

The isothermal compressibilities of pristine graphite and stages 1 and 2 potassium-graphite have been measured at room temperature. Diamond anvil X-ray diffraction techniques were employed to determine the c-axis lattice constant as a function of hydrostatic pressure up to 12 kbar. The compressibilities $\text{k}{}_{\mathrm{c}}\text{?}\text{1}\text{C}{}_{33}$ were found to be (2.73±0.09)×10^-12, (2.13±0.09)×10^-12, (5.3±0.8)×10^-12 and $\text{(1.6±0.2)×10}{}^{-12}\text{cm}{}^2\text{dyn}$ for graphite, KC₈, stage 2 KC₂₄ and stage 3 KC₂₄, respectively. The compressibility of KC₈ was comparable to that of RbC₈ deduced from neutron scattering experiments.     

Effects of polymerization and hydrolysis degrees of poly(vinyl alcohol) (PVA) on the efficiency of the PVA-solid substrate for room-temperature phosphorimetry.

Several kinds of poly(vinyl alcohols) (PVAs) having different degrees of polymerization and hydrolysis were tested as a material of a solid substrate for room-temperature phosphorimetry (RTP). Effects of these differences on the efficiency of the solid substrate were investigated. Completely hydrolyzed PVAs acquired a luminescence property in the grinding process of substrate preparation, but partially hydrolyzed PVAs did not acquire this property. When the completely hydrolyzed PVA substrates were prepared by drying their aqueous solutions, their luminescence property almost disappeared. However, very weak background emission remained on the surface of a completely dried substrate which had been treated with an analyte aqueous solution. This residual background affected the spectrum of the analyte, especially at low concentrations. Stability of the phosphorescence intensity with the passage of time was superior on the partially hydrolyzed PVAs than on the completely hydrolyzed PVAs. On the other hand, the RTP intensity and reproducibility were superior on the completely hydrolyzed PVAs. Practically, partially hydrolyzed PVAs were more suitable as a material of the substrate because of the stability of its RTP intensity and the weakness of its background emission. The linear dynamic range of the analytical curve for p-aminobenzoic acid on the substrate of partially hydrolyzed PVA having a degree of polymerization of 3,500 was 5-2,000 pmol/spot (20 microL) and its correlation coefficient was 0.963 for 30 data points.     

Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS): comparison of different internal standardization methods using laser-induced plasma (LIP) emission and LA-ICP-MS signals.

The source of signal variations that governs the analytical performance of laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was investigated in this study. In order to specify the source of signal variations of LA-ICP-MS, laser-induced plasma (LIP) Fe emission, LA-ICP-MS Fe+ and LA-ICP-MS Ni+ signals were used as internal standards for the determination of trace elements in low-alloy steel certified reference materials (BS 50D and JSS 1005-1008). Fe 1373.5 nm emission signals from LIP were measured, while trace element LA-ICP-MS signals were collected. After that, the LIP emission signals, LA-ICP-MS Fe+ and LA-ICP-MS Ni+ signals were used as internal standards, and the analytical performance was evaluated by the RSDs and the correlation coefficients (r) of the calibration curves. The improvement factors were dependent on the internal standardization methods. Analytical precisions (RSDs) of trace element LA-ICP-MS signals were improved by factors of 1.5-3.3 using LIP Fe emission signals as an internal standard. The improvement factors of 2.5 - 5.9 and 4.1 - 17 were obtained by using LA-ICP-MS Fe+ and LA-ICP-MS Ni+ signals as internal standards, respectively. Better correlation coefficients (r) were also obtained using the LA-ICP-MS signal compensation (0.9985 by LA-ICP-MS Fe+ and 0.9996 by LA-ICP-MS Ni+) rather than the LIP Fe emission compensation (0.9932). In this paper we compare and discuss the analytical performance achieved by LA-ICP-MS using LIP Fe emission, LA-ICP-MS Fe+ and LA-ICP-MS Ni+ signals as internal standards.