Comparisons of elemental concentrations in hair of the inhabitants of heavy metal polluted areas with those of normal Japanese

Human hair collected from the mercury, arsenic and cadmium polluted areas has been analysed by instrumental neutron activation method. The concentrations of 27 elements were compared with those of normal Japanese. Correlation coefficients of logarithmic concentrations between the elements were calculated and their significance levels were determined. Factor contribution and factor loadings of the elements were calculated for each factor by making use of principal component analysis. The factor score of each sample was also calculated for each factor to examine the effects of the contamination by heavy metals on individuals.     

Early-stage flocculation kinetics of polystyrene latex particles with polyelectrolytes studied in the standardized mixing: Contrast of excess and moderate polyelectrolyte dosage

Standardized mixing procedure was applied to the analysis of flocculation of polystyrene latex (PSL) particles with polyelectrolytes. After confirming the initial enhancement of flocculation rate in the very beginning followed by abrupt stop with excess dosage, attention was shifted to the system of moderate dosage. In the former, effects of ionic strength were further analyzed to find the consistency with adsorption isotherm. In the latter, flocculation started slowly in the beginning, sometime slower than salt-induced rapid coagulation, however, the rate gradually increases in the middle stage. Often, the increased rate exceeds that of salt-induced rapid coagulation. This behavior emerged more clearly in the case of lower ionic strength. This is the indication that the rate of relaxation of polymer on the colloidal surface is a function of surface coverage and ionic strength. The ultimate degree of flocculation is usually higher than that observed for excess dosage. The size distribution of flocs was also examined, however, no clear difference between different experimental conditions was confirmed for the same degree of flocculation.     

Inorganic-organic hybrids of the p,p′-diphenylmethylenediphosphinate ligand with bivalent metals: a new 2D-layered phenylphosphinate zinc(II) complex

By reaction of Zn(CH₃COO)₂ with p,p′-diphenylmethylenediphosphinic acid in water a new inorganic-organic polymeric hybrid of formula [Zn(CH₂(P(Ph)O₂)₂)] has been synthesized and completely characterized. The X-ray analysis established that the structure consists of 2D-layered polymeric array, the 2D-sheets being built up through strong covalent linkages between the zinc metal and the oxygen donors of the phenylphosphinate ligand. The 2D-layers, which are featuring a mesh-net fashion, present voids of various dimensionality, up to 24-membered rings. The organic parts of the hybrid ligand, namely the phenyl rings, are shielding the inorganic skeleton of the layers, preventing the propagation of the polymer in the third dimension. No water molecules are present in the lattice, both of coordination and crystallization. Crystal data are: monoclinic, P2₁/c, a=11.840(2), b=9.646(9), c=12.516(5) Å, β=95.03(2), V=1423.9(15) Å³, Z=4. The solid material has been characterized by ³¹P MAS NMR spectroscopy and thermogravimetric analysis.     

Passivation of the calcite surface with malonate ion

Samples of polycrystalline calcite were impregnated with solutions of malonic acid of three concentrations (5 x 10(-2), 5 x 10(-3) , and 5 x 10(-4) M) and different pH values (6.00, 7.00, and 8.00). The impregnation was carried out at room temperature to evaluate the adsorption of malonate ion in the calcite surface to optimize the conditions for possible application on limestone and marble in cultural heritage materials. The affinity of the malonate ion was determined through the potentiometric measurement of the surface charge and the corresponding adsorbed amounts by titration, Raman spectroscopy, and small-angle X-ray scattering (SAXS). The results indicate effective adsorption of the malonate ion on the surface at a pH value close to the point of zero charge (pHpzc approximately 8.20) and changes in some surface morphological properties such as the pore shape and the pore size distribution. The presence of a malonate adsorptive layer on calcite generates an interface interaction potential that may influence the reaction and transport mechanisms within the medium.     

Synthesis of [1,3]dithiole and spiro[1,3]dithiole thiopyran derivatives of the [1,2]dithiolo[1,4]thiazine ring system

We report the synthesis of some new polysulfur-nitrogen heterocycles by cycloaddition reactions to readily available tricyclic condensed 1,2-dithiole-3-thiones. Thus, treatment of bis[1,2]dithiolopyrrole ketothione 1 with diacyl acetylenes gave the bis-aducts 2a-d. On the other hand, cycloaddition of bis[1,2]dithiolo[1,4]thiazine ketothione 3 with 1 equiv of acyl or diacyl acetylenes gave [1,3]dithiolylidenyl[1,2]dithiolo[1,4]thiazines 4a-f in fair to high yields. Catalysis by scandium triflate was used in the reactions that implied the less reactive dipolarophiles. Treatment of 3 with 2 equiv of DBA gave the bis-aduct 5a, and reaction of 4c with DMAD gave the mixed bis-adduct 5b. Cyclic voltammetry of selected examples showed irreversible processes that were influenced by the electrochemical activity of peripheral groups bonded to the heterocyclic system.     

Lipase from a Brazilian StrainPenicillium citrinum Cultured in a Simple and Inexpensive Medium st]Heat-Denaturation, Kinetics, and pH Stability

This work is a study of lipase production by a Brazilian strain ofPenicillium citrinum using an inexpensive and simple medium without organic nitrogen sources and of some important industrial properties, including thermostability in relation to ionic strength. The maximal lipase activity (1585 U/L) was obtained whenPenicillium citrinum was cultured on 0.75% ammonium sulfate complemented with minerals salts instead of yeast extract. Although this activity was about 55% lower than that produced in medium with yeast extract (2850 U/L), the specific activity (7.8 U/mg proteins) was higher than that obtained with the yeast extract (4.9 U/mg proteins). The morphology of fungus changed totally, with yeast extract there are smooth, solid, and spherical pellets whereas on ammonium sulfate there are small “hairy” pellets uniformly suspended in the medium. The effect of ferrous (Fe⁺⁺) ions was carried out using medium MA with and without Fe⁺⁺ ions. Lipase production byPenicillium citrinum in medium MA requires Fe⁺⁺ ions, the absence of which caused a decreased of about 50% in the specific activity (3.5 U/mg proteins). The utilization of commercial, locally available oils as carbon sources, such as soybean oil (236 U/L) and corn oil (74 U/L) resulted in lower activity compared to olive oil, showing that lipase production byPenicillium citrinum is specifically induced by olive oil. Potassium concentration in the medium can effects the production of lipase (1 mM (1585 U/L), 10 mM (1290 U/L), and 30 mM (1238 U/L), 50 mM (195 U/L), and 100 mM (2 U/L). The crude culture filtered was susceptable to thermal deactivation. It was stable at pH 6.0, but was not stable at the optimum pH (8.0-8.5) at 50 mM. At the low ionic concentration (1-25 mM) this lipase was stable at low pH (3.5-4.0). The activation energy was 22.4 ±2.2 Kcal. mol 1.     

Theoretical study of ribonucleotide reductase mechanism-based inhibition by 2'-azido-2'-deoxyribonucleoside 5'-diphosphates

2'-azido-2'-deoxyribonucleoside 5'-diphosphates are mechanism-based inhibitors of Ribonucleotide Reductase. Considerable effort has been made to elucidate their mechanism of inhibition, which is still controversial and not fully understood. Previous studies have detected the formation of a radical intermediate when the inhibitors interact with the enzyme, and several authors have proposed possible structures for this radical. We have conducted a theoretical study of the possible reactions involved, which allowed us to identify the structure of the new radical among the several proposals. A new reactional path is also proposed that is the most kinetically favored to yield this radical and ultimately inactivate the enzyme. The energetic involved in this mechanism, both for radical formation and radical decay, as well as the calculated Hyperfine Coupling Constants for the radical intermediate, are in agreement with the correspondent experimental values. This mechanistic alternative is fully coherent with remaining experimental data.     

Evaluation and application of bismuth as an internal standard for the determination of lead in wines by simultaneous electrothermal atomic absorption spectrometry

A method for the direct determination of Pb in wines by simultaneous multi-element atomic absorption spectrometry (SIMAAS) using a transversely heated graphite atomizer, Zeeman-effect background corrector and internal standardization is proposed. Bismuth was used as an internal standard and Pd(NO3)2 plus Mg(NO3)2 as chemical modifier to stabilize both the analyte and the internal standard. The implementation of two pyrolysis steps avoided any build-up of carbonaceous residues on the graphite platform. All diluted samples (1 + 1 v/v) in 0.2% v/v HNO3 and reference solutions (5.0-50 microg l(-1) Pb in 0.2% v/v HNO3) were spiked with 25 microg l(-1) Bi. For a 20 microl aliquot dispensed into the graphite tube, a good correlation (r = 0.9997) was obtained between the ratio of the analyte signal to the internal standard signal and the analyte concentration of the reference solutions. The electrothermal behaviour of Pb and Bi in red, white and rosé wines were compared. In addition, absorbance variations due to changes in experimental conditions, such as atomizer temperature, integration time, injected sample volume, radiation beam intensity, graphite tube surface, dilution and sample composition, were minimized by using Bi as internal standard. Relative standard deviations of measurements based on integrated absorbance varied from 0.1 to 3.4% and from 0.5 to 7.3% (n = 12) with and without internal standard correction, respectively. Good recoveries (91-104%) for Pb spikes were obtained. The characteristic mass was 45 pg Pb and the limit of detection based on integrated absorbance was 0.9 microg l(-1) Pb. Internal standardization increased the lifetime of the tube by 25%. Direct determinations of Pb in wines with and without internal standardization approaches were in agreement at the 95% confidence level. The repeatability and the tube lifetime were improved when using Bi as internal standard. The improvement in accuracy using an internal standard was only observed when the analytical results were affected by errors.     

The study of electron beam flue gas treatment for coal-fired thermal plant in Japan

The fundamental research work with simulated coal-fired flue gas was performed in JAERI to get basic data for electron beam treatment of flue gas from thermal power plants in Japan. The standard condition of the experiments was set to be the same as that of next large scale pilot test in Nagoya. The concentrations of NO_x and SO_x were 225 ppm and 800 ppm, respectively. The temperature of the system was 65°C. The effect of multiple irradiation was observed for NO_x removal. The target SO_x and NO_x removals (94% and 80%, respectively) with low NH₃ leakage (less than 10 ppm) were achieved at 9 kGy irradiation with 0.9 NH₃ stoichiometry during 7 hours continuous operation. The facility for the pilot plant (12,000 Nm³/hr) has just built at the site of Shin-Nagoya power plant of Chubu Electric Power Company and will be started in full operation in November 1992.