Effect of the structure of cationic polysulfone on the flocculation of kaolinite

The behavior of polycations as flocculants for kaolinite was examined by means of turbidity measurement, with the use of the following four kinds of cationic polysulfones, with molecular weights ranging from 14,000 to 330,000; diallyldimethylammonium chloride SO₂ copolymer [P(DADMAmCl? SO₂)], diallyldiethylammonium chloride–SO₂ copolymer [P(DADEAmCl? SO₂)], diallylmethylamine hydrochloride–SO₂ copolymer [P(DAMA? HCl? SO₂)], diallylamine hydrochloride–SO₂ copolymer [P(DAAHCl? SO₂)]. The effect of the degree of polymerization on the flocculation was remarkable at low molecular weight range. The flocculation value, which is defined as the quantity of the polycation required to obtain 50% transparency at 660 mμ of the supernatant fluid of 2% kaolinite suspension, was inversely proportional to the degree of polymerization to the 0.734 power in the case of P(DADMAmCl? SO₂). This can be understood as the extension of Schulze-Hardy's law. The four different kinds of polysulfones having a similar molecular weight show almost the same capacity for flocculation in acidic or neutral solution. In alkaline solution, however, P(DAMAHCl? SO₂) and P(DAA? HCl? SO₂) are less effective and have higher flocculation values than P(DADMAmCl? SO₂) and P(DADEAmCl? SO₂), which are classified as polyquaternary ammonium chlorides. Moreover the difference increases with increasing pH. This may be attributable to the difference of the dissociability of the polycation. The degree of dissociation of P(DAMA? HCl? SO₂) or P(DAA? HCl? SO₂) decreases with increasing pH and more additive is required to neutralize negative charges on kaolinite. On the other hand, P(DADMAmCl? SO₂) and P(DADEAmCl? SO₂) are almost completely dissociated and are good flocculants over a wide range of pH.     

Development of new dosimetry using extended DNA fibers

We applied fluorescent microscopy to monitor the damage of DNA upon exposure to gamma radiation. Our developed dosimetry demonstrated that the number of breaks in DNA is proportional to the dose of the irradiation but is not dependent on dose rate of the irradiation and the GC content of DNA.     

Hydration of halide anions in ion-exchange resin and their dissociation from cationic groups

The local structures of Cl- and Br- in an anion-exchange resin have been investigated by X-ray absorption fine structure (XAFS). The resins, which have been equilibrated under various partial water vapor pressures to allow the anions to have various hydration numbers, are provided for XAFS measurements. The XAFS spectra indicate that two scattering groups around the counteranion are present, that is, water molecules and an ion-exchange group. Regression analyses allow the separation of the contributions from these two scattering groups; thus, the average hydration number (N) is determined. The hydration number linearly increases with increasing the number of water molecules (n) adsorbed by an ion-exchange pair (an ion-exchange group and a counteranion) until the ion-exchange pair adsorbs ca. 3 water molecules, indicating that all of the adsorbed water molecules coordinate the counteranion. However, an increase in N with increasing n becomes small as n exceeds 3; N finally reaches 3.9 (+/-0.4) for Cl- and ca. 3.4 (+/-0.5) for Br-. Detailed studies of the water adsorption isotherms imply that the maximum hydration number of these anions is three when they are bound by the ion-exchange groups, and as more water molecules are supplied, they are dissociated from the ion-exchange groups; ca. 40% of total counteranions are dissociated from the ion-exchange groups.     

Some new sulfo-spinels containing iron-group transition metals

The study of the cation site preferences related to Rh³⁺ or Sn⁴⁺ ions in the spinel lattice leads to a series of new spinels. Various sulfo-spinels containing some of the transition elements such as Mn, Fe, Co and Ni, have been synthesized and the cation distributions and u-parameters were determined. Some magnetic and electrical properties were measured for Fe₂RhS₄ and Cd_1?xFe_1+xSnS₄ (0 ≤ x ≤ 0.9).     

Rate of emulsion polymerization of styrene

In emulsion polymerization, the Smith and Ewart theory gives about two or three times the number of polymer particles obtained by experiment. In this paper, a reaction model is proposed which, from the standpoint of reactor design, can give an adequate explanation of the whole course of an emulsion polymerization of monomer highly insoluble in water. Among other things, the generating process of polymer particles is examined in detail. It is demonstrated experimentally that a new parameter proposed here, which represents the degree of difficulty of monomer initiation in micelles, is indispensable in explaining that process. Also confirmed is that monomer initiation takes place more easily in polymer particles than in micelles. According to the new model, the progress of polymerization, i.e., monomer conversion, the number of the polymer particles, and properties of polymer thus produced can be estimated with satisfactory accuracy. Furthermore, approximate equations are derived for easier estimation.     

Determination of standard gibbs energies of formation of Fe2Mo3O12, Fe2Mo3O8, Fe2MoO4, and FeMoO4 of the Fe-Mo-O ternary system and μ phase of the Fe-Mo binary system by electromotive force measurement using a Y2O3-stabilized ZrO2 solid electrolyte

The standard Gibbs energies of formation of Fe₂Mo₃O₁₂, Fe₂Mo₃O₈, FeMoO₄, and Fe₂MoO₄ of the Fe-Mo-O ternary system and the μ phase of the Fe-Mo binary system have been determined by measuring electromotive forces of galvanic cells having an Y₂O₃-stabilized ZrO₂ solid electrolyte. The results are as follows: $$\begin{gathered} \Delta _f G^\circ (FeMoO_4 )/kJ \cdot mol^{ - 1} = - 1053.5 + 0.2983(T/K) \pm 0.4 \hfill \\ Temperature range: 1112 to 1339 K \hfill \\ \Delta _f G^\circ (Fe_2 Mo_3 O_8 )/kJ \cdot mol^{ - 1} = - 2347 + 0.6814(T/K) \pm 1 \hfill \\ Temperature range: 1112 to 1339 K \hfill \\ \Delta _f G^\circ (Fe_2 Mo_3 O_{12} )/kJ \cdot mol^{ - 1} = - 2993 + 0.9105(T/K) \pm 2 \hfill \\ Temperature range: 1040 to 1145 K \hfill \\ \Delta _f G^\circ (Fe_{0.58} Mo_{0.42} )/kJ \cdot mol^{ - 1} = - 18.7 + 0.0117(T/K) \pm 0.1 \hfill \\ Temperature range: 1162 to 1223 K \hfill \\ \Delta _f G^\circ (Fe_2 MoO_4 )/kJ \cdot mol^{ - 1} = - 1174 + 0.342(T/K) \pm 1 \hfill \\ Temperature range: 1243 to 1466 K \hfill \\ \end{gathered} $$ where the standard pressure is 1 bar (100 kPa).     

Profile structure of magnetic flux lines in type-II superconductor from a rectangular electron hologram

Profile magnetic configuration of a quantized flux line and flux-line lattice penetrating a type-II superconductor thin foil, niobium, was observed by electron holography and Lorentz microscopy using a 300 kV field-emission electron microscope. Each single flux line was distributed periodically as lattice structure in the mixed state just below its critical temperature of 8.5 K, while at low temperature of 5 K the flux lines were weakly bound as bundles. In order to observe the flux-line distribution over a wide area, discrete Fourier transform reconstruction in the holography was extended for a rectangular area without loss of information and data precision.     

Immunolocalization of steroidogenic enzymes in the corpus luteum and placenta of the Japanese black bear, Ursus thibetanus japonicus, during pregnancy

The Japanese black bear, Ursus thibetanus japonicus, is a seasonal breeder and shows delayed implantation for several months during pregnancy. The objective of this study was to clarify the steroidogenic capability of the corpus luteum and placenta during pregnancy, including both delayed implantation and fetal development, by immunolocalization of steroidogenic enzymes in these organs of the Japanese black bear. Ovaries and placentae from 15 wild Japanese black bears, which had been killed legally by hunters and were thought to be pregnant, were used in an immunocytochemical study to localize the cholesterol side chain cleavage cytochrome P450 (P450scc), 3beta-hydroxysteroid dehydrogenase (3betaHSD), 17alpha-hydroxylase cytochrome P450 (P450c17) and aromatase cytochrome P450 (P450arom) by the avidin-biotin-peroxidase complex method using polyclonal antisera raised in mammals against P450scc, 3betaHSD, P450c17 and P450arom. P450scc and 3betaHSD were localized in all luteal cells throughout pregnancy. P450c17 was present in a few luteal cells, especially in the outer area of the corpus luteum throughout pregnancy, but the number of positively immunostained cells decreased during the post-implantation period. Cells positively immunostained for P450c17 were significantly smaller than negatively immunostained cells (P < 0.01). P450arom was present sporadically in a few luteal cells throughout pregnancy, but the number of positively immunostained cells decreased during the post-implantation period. The size of cells positively immunostained for P450arom was not significantly different from that of negatively immunostained cells. The whole placenta was negatively immunostained for P450scc, 3betaHSD and P450c17, but P450arom was present in the syncytiotrophoblasts and endothelial cells of maternal blood vessels. These results indicate that, in the Japanese black bear, corpora lutea are a source of progesterone which may play an important role in the maintenance of delayed implantation and fetal development during pregnancy. Corpora lutea have a minimum capability to synthesize androgen in small luteal cells and oestrogen in normal-sized luteal cells during pregnancy, and placentae have the ability to synthesize oestrogen during late pregnancy.     

Evaluation of 4-nonylphenols and 4-tert-octylphenol contamination of fish in rivers by laboratory accumulation and excretion experiments

Laboratory accumulation and excretion experiments of 4-nonylphenols (NP) and 4-tert-octylphenol (OP) were performed for killifish (Oryzias latipes). The bioconcentration factors (BCF, wet weight) in the whole fish were mean +/- SD of 167 +/- 23 (n = 4) for NP and 261 +/- 62 (n = 4) for OP. The biological half-lives in the whole fish were 9.9 h for NP and 7.7 h for OP. Parallel to the laboratory experiments, field survey on the chemicals contamination for water and ayu fish (Plecoglossus altivelis) from rivers flowing into Lake Biwa was performed. The contamination was not so high in agreement with the laboratory experimental data and the field BCF values (wet weight) in the ayu fish were 21 +/- 15 (n = 8) for NP and 297 +/- 194 (n = 3) for OP.