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     

Argon sorption and partial molar volume in poly(ethyl methacrylate) above and below the glass transition temperature

Sorption and dilation isotherms for argon in poly(ethyl methacrylate) (PEMA) are reported for pressures up to 50 atm over the temperature range 5–85°C. At temperatures below the glass transition (T_g=61°C), sorption isotherms are well described by the dual-mode sorption model; and isotherms above T_g follow Henry's law. However, isotherms for dilation due to sorption are linear in pressure at all temperatures over the range investigated. Partial molar volumes of Ar in PEMA are obtained from these isotherms. The volumes are approximately constant above T_g (about 40 cm³/mol), whereas the volumes below T_g are smaller and dependent on both temperature and concentration (19–26 cm³/mol). By analyzing the experimental data according to the dual-mode sorption and dilation model, the volume occupied by a dissolved Ar molecule and the mean size of microvoid in the glass are estimated to be 67 129 ų, respectively. The cohesive energy density of the polymer is also estimated as 61 cal/cm³ from the temperature dependence of the dual-mode parameters.     

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.     

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.     

Reduction of dislocation density and improvement of optical quality in ZnO layers by MgO-buffer annealing

Optical properties of ZnO thin films with/without MgO-buffer annealing were investigated by low and room temperature photoluminescence measurements. The ZnO films were grown on c-sapphire substrates by plasma-assisted molecular-beam epitaxy employing a thin MgO-buffer layer. Dislocation density of ZnO layer was reduced from 5.3 × 10⁹ to 1.9 × 10⁹ cm⁻² by annealing MgO-buffer prior to the growth of ZnO. The intensity of free exciton emission from the sample with MgO-buffer annealing was almost twice of that from the sample without annealing, while the deep level emission from the sample with MgO-buffer annealing was about 1/3 of that without annealing. The MgO-buffer annealing improves optical quality of overgrown ZnO films.     

Complex genetic evolution of artificial self‐replicators in cellular automata

It is widely believed that evolutionary dynamics of artificial self‐replicators realized in cellular automata (CA) are limited in diversity and adaptation. Contrary to this view, we show that complex genetic evolution may occur within simple CA. The evolving self‐replicating loops (“evoloops”) we investigate exhibit significant diversity in macro‐scale morphologies and mutational biases, undergoing nontrivial genetic adaptation by maximizing colony density and enhancing sustainability against other species. Nonmutable subsequences enable genetic operations that alter fitness differentials and promote long‐term evolutionary exploration. These results demonstrate a unique example of genetic evolution hierarchically emerging from local interactions between elements much smaller than individual replicators. © 2004 Wiley Periodicals, Inc. Complexity 10: 33–39, 2004