Multitracer screening for in vivo element-element interrelations

Radioactive multitracer technique was applied to study the screening of in vivo interrelations between radioactive tracers (⁴⁶Sc, ⁵⁴Mn, ⁵⁸Co, ⁶⁵Zn, ⁷⁵Se, ⁸³Rb, ⁸⁵Sr and ⁸⁸Zr) and stable Zn species. Comparative uptake rates were examined in the blood, nine organs (thymus, lung, cardiac muscle, spleen, pancreas, kidney, liver, testes and bone) and eight brain regions (cerebral cortex, striatum, hippocampus, thalamus and hypothalamus, midbrain, cerebellum, pons and medulla, olfactory bulb) using 3-week-old mice fed by four kinds of Zn-deficient, -adequate and -excessive diets with Zn content from 0.7 to 3520 ppm. As a result, no significant difference between the dietary Zn-deficient state (Zn content: 3.6 ppm) and Zn-adequate state (Zn content: 36 ppm) was observed in the uptake rates of ⁶⁵Zn and other ⁴⁶Sc, ⁵⁴Mn, ⁵⁸Co and ⁷⁵Se, except for ⁸³Rb. In addition, significant differences among the organ and brain regional uptakes of ⁴⁶Sc, ⁵⁴Mn, ⁵⁸Co, ⁷⁵Se and ⁸³Rb were found in the dietary Zn-excessive state (Zn content: 3520 ppm). These results indicate that the organ and brain regional uptakes of tracers in Zn-deficient and excessive mice are strongly correlated with the blood uptakes and retentions of the tracers. Furthermore, the multitracer screening gives us new findings concerning the diet-related element-element interrelations in living bodies.     

Spectroscopic studies of poly(vinyl chloride) and its deuterated derivatives

Poly(vinyl chloride) (PVC) and all its deuterated derivatives were prepared by variation of the polymerization method and polymerization temperature to study the structure of PVC and the mechanism of addition polymerization by infrared spectroscopy and high resolution NMR spectroscopy. The CH and CH₂ stretching modes of PVC were assigned completely from the infrared spectra of PVC-αd₁, PVC-β,βd₂ and PVC-d₃. The frequencies of the CCI stretching modes of the polymers depended not only on the substituents in the trans position to the Cl atom across both adjacent C? C bonds, but also on the atom attached to the C atom of the C? Cl bond. The frequency shifts were used to assign the CCl stretching modes of PVC-βd₁ and PVC-α,βd₂ and to study the opening of the double bond of VC in the addition polymerization. The differences of the chemical shifts of the α and β protons of PVC due to the tacticity were determined experimentally by PVC-β,βd₂ and PVC-αd₁ without using the spin-decoupling technique. With PVC-α,βd₂, the conception of the tetrad was required to interpret the four observed peaks whose intensities changed with the polymerization temperature and the trans–cis composition of the monomer used.     

A highly effective asymmetric synthesis of α-hydroxy acids by alkylation of chiral n-(benzyloxyacetyl)-trans-2,5-bis(methoxymethoxymethyl)pyrrolidine

Alkylation of lithiated $\text{N}$-(benzyloxyacetyl)-$\text{trans}$-2,5-bis(mehtoxyymethoxymethyl)- pyrrolidine proceeded with high stereoselectivity (≥96% de) and subsequent transformations of the alkylated products gave synthetically useful α-benzyloxy acids or α-hydroxy acids of high enantiomeric purity.     

Polymerization of vinyl chloride

Polymerization of vinyl chloride (VC) was studied. natural evolution of HCl from VC occurred in the polymerization. VC, VC-αd₁, VC-β,βd₂ and VC-d₃ were used to study the reactivities of the hydrogen atoms in the polymerization and the β-hydrogen atoms contributed to the chain transfer. Chemical and physical methods were used to observe irregular structures, such as branching, double bonds, and head-to-head or tail-to-tail addition, and also to confirm the relation between conversion and the irregular structures.     

Solvent extraction of Au(III) for preparation of a carrier-free multitracer and an Au tracer from an Au target

Separation of Au(III) and various carrier-free radionuclides by solvent extraction was investigated using an Au target irradiated by an energetic heavy-ion beam. Percentage extraction of Au(III) and coextraction of the radionuclides were determined with varying parameters such as kinds of solvent, molarity of HCl or pH, and Au concentration. Under the conditions where Au(III) was effectively extracted, namely extraction with ethyl acetate or isobutyl methyl ketone from 3 mol·dm^–3 HCl, carrier-free radionuclides of many elements were found to be more or less coextracted. Coextraction of radionuclides of some elements was found to increase with an increase in the concentration of Au(III). This finding is ascribed to the formation of strong association of the complex of these elements with chloroauric acid. In order to avoid serious loss of these elements by the extraction, lowering of the Au(III) concentration or the use of a masking agent such as sodium citrate is necessary. Gold(III) was shown to be effectively back extracted with a 0.1 mol·dm^–3 aqueous solution of 2-amino-2-hydroxymethyl-1,3-propanediol. Thus, a radiochemical procedure has been established for preparing a carrier-free multitracer and an Au tracer with carrier form from an Au target irradiated with a heavy-ion beam. Both tracers are now used individually for chemical and biological experiments.     

Direct measurement of hydrophobic particle–bubble interactions in aqueous solutions by atomic force microscopy: Effect of particle hydrophobicity

Direct measurements of the interaction forces between a spherical silica particle and a small air bubble have been conducted in aqueous electrolyte solutions by using an atomic force microscope (AFM). The silica particle was hydrophobized with a silanating reagent, and the interaction forces were measured by using several particles with different surface hydrophobicities. In the measured force curves, a repulsive force was observed at large separation distances as the particle moved towards the bubble. The origin of the repulsive force was attributed to an electrostatic double-layer force because both the particle and bubble were negatively charged. After the repulsive force, an extremely long-range attractive force acted between the surfaces. These results indicate that the intervening thin water film between the particle and bubble rapidly collapsed, resulting in the particle penetrating the bubble.

The instability of the thin water film between the surfaces suggests the existence of an additional attractive force. By comparing the repulsive forces of the obtained force curves with the DLVO theory, the rupture thickness was estimated. The hydrophobicity of the particle did not significantly change the rupture thickness, whereas the pH of the solution is considered to be a critical factor.     

Toughness and the existence ofk-factors. II

In a paper with the same title [3], we proved Chvátal's conjecture thatk-tough graphs havek-factors if they satisfy trivial necessary conditions. In this paper, we prove the following stronger result: Suppose|V(G)| k + 1,k |V(G)| even, and|S| k w(G – S) – 7/8k ifw(G – S) 2, wherew(G – S) is the number of connected components ofG – S. ThenG has ak-factor.     

Ab-initio calculations of Raman, IR-active vibrational modes in isotopically modified B12 icosahedral clusters

Computational calculations of Becke's three-parameter hybrid method using the LYP correlation functional (B3LYP) have been performed on (B₁₂H₁₂)²⁻ dodecaborane anions with different boron isotopic compositions. This was done in order to investigate isotopic dependence of vibrational spectral properties of B₁₂ icosahedra, and for comparison of the optical vibrational properties of the icosahedral molecule with the characteristics of inter- or intra-icosahedral optical phonon vibrational modes in boron-rich crystals.