Improvement in flow-sheet of extraction chromatography for trivalent minor actinides recovery

Journal of Radioanalytical and Nuclear Chemistry - Extraction chromatography flow-sheet employing octyl(phenyl)-N,N-diisobutylcarbonoylmethylphosphine oxide and bis(2-ethylhexyl) hydrogen phosphate...     

The required sample size in measuring oblique incidence absorption coefficient Experimental study

It is an important issue to clarify the minimum required size of a specimen for the accurate measurement of oblique incidence absorption coefficient. Investigation is made on the basis of experimental studies in a laboratory, using Aoshima's time stretched pulse technique. Measurements are carried out for glass fiber with thickness of 50 and 100 mm as highly absorbing materials and for ceramic with a thickness of 52 mm as relatively low absorbing material. The tested surface areas range from 0.0625 to 42 m² for glass fiber and from 0.1563 to 39.168 m² for ceramics. The absorption coefficients are determined at incidence angles from 0 to 45° in increments of 15°. With consideration of an active surface bounded by ellipse orbit, the minimum required surface area is 16 m² with a ratio of length to width of about 1.25. This value is twice the area size of the active surface, which is calculated from the geometry of source and microphone, and the width of the temporal window.     

Development of Non-Halogen Flame Retardant Optical Fiber and Optical Fiber Cord

A non-halogen highly flame-retardant 0.9mm optical fiber and 2.0mm simplex optical cord, which are harmonized with the ecosystem, have been developed. The characteristics of them are presented in this paper.     

Anomalous PL brightening caused by partial Auger recombination of a (D, X) complex during an impact ionization avalanche in n-GaAs

Partial Auger recombination of the (D⁰, X) bound-exciton in n-GaAs at 4.2 K during an impact ionization avalanche under an applied pulse voltage has been investigated. The bright photoluminescence (PL)-pattern observed by applying the pulse voltage, characterizes well the formation of a current density filament. The observation of the bright PL spectra inside the current density filament gives a quite new result concerning the partial Auger recombination process of the (D⁰, X) complex, leaving the neutral donor in the excited states.     

Ethylene polymerization by chromium complexes with phosphorous‐bridged bisphenoxy ligand

Chromium catalysts combined with phosphorous‐bridged bisphenoxy ligands were found to be highly active for ethylene polymerization. The most efficient catalyst precursor among them, generated by combining bis[3‐tert‐butyl‐5‐methyl‐2‐hydroxyphenyl](phenyl)phosphine hydrochloride ( 1a ) and CrCl₃(THF)₃, was characterized. X‐ray analysis of (3‐tert‐butyl‐5‐methyl‐2‐phenoxy)(3‐tert‐butyl‐5‐methyl‐ 2‐hydroxyphenyl)(phenyl)phosphine bis(tetrahydrofuran)chromium dichloride ( 6 ), obtained by the reaction of 1a and CrCl₃(THF)₃ in the presence of NaH, revealed a unique structure in which one phenol moiety of the bisphenol did not coordinate to the chromium center. Complex 6 showed higher activities than those observed in the in situ catalyst system. Polyethylene of various molecular weights was obtained with differing activators. The highest activity (113.5 kg mmol (cat)^?1 h^?1) was observed when TIBA/TB was used as a cocatalyst. A medium molecular weight polymer with narrow molecular weight distribution (M_w = 128,700, M_w/M_n = 1.8) was obtained using a 6 ‐TIBA/B(C₆F₅)₃ system. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3668–3676, 2007     

First thermally responsive supramolecular polymer based on glycosylated amino acid

In materials science, a dynamic property sensitive to an environmental change (heat, light, electric current, pH, and other chemical or physical changes) is indispensable for intelligent materials. Such organic materials, however, are very limited even in conventional polymers. This paper clearly demonstrates that, regardless of the low molecular weight, a glycosylated amino acid derivative newly screened by a combinatorial method forms a macroscopic supramolecular hydrogel that reversibly swells or shrinks in response to the external temperature. Using the unique thermal response of the present hydrogel, we carried out the controlled release of DNA and the perfect removal of bisphenol A from the polluted water. Recently, advanced supramolecular polymers, in which monomers are noncovalently connected, are expected to be highly advantageous over traditional polymers because of their tunable and recyclable characteristics. The present result newly confers a dynamic feature on the supramolecular polymers, which is desirable for the sophisticated application in many fields.     

Resolution of lymphocyte subpopulations derived from rat spleen by polyamine-graft-PHEMA copolymer

The retention behavior of lymphocyte subpopulations, B cell, T cell and null cell, derived from rat spleen to polyamine-graft-poly(2-hydroxyethyl methacrylate) copolymer (HA) surface was investigated, focusing on the conformational transition of the polyamine side chain as well as the protonation of amino groups in the polyamine grafts. Furthermore, the availability of HA was discussed as a column adsorbent for separation of lymphocyte subpopulations derived from spleen. The conformational transition of polyamine grafts significantly influenced the mode of retention of lymphocyte subpopulations. When polyamine grafts existed in an aggregated conformation (protonatin degree α < 0.5), the retention of lymphocyte subpopulations was decreased in the order B cell> null cell> T cell. On the other hand, when polyamine existed in an extended conformation into the aqueous interior from the matrix interface (α > 0.5), T cell retention became greater than null cell retention, resulting in a decreased B cell> T cell> null cell order. These results indicate that the differential retention of spleen lymphocyte subpopulations is attributed to their differential responses to the change in matrix interface accompanied by the protonation of amino groups. Furthermore, spleen lymphocytes were compared with lymph node lymphocytes in terms of resolution efficacy by an HA copolymer column.     

Secondary hypervalent I(III)...O interactions: synthesis and structure of hypervalent complexes of diphenyl-lambda3-iodanes with 18-crown-6

Reported here for the first time are the synthesis and characterization of supramolecular complexes between diaryl-lambda(3)-iodanes and 18-crown-6 (18C6). Slow evaporation of solvents afforded 1:1 and 2:1 complexes between Ph(2)IBF(4) and 18C6 as stable crystals, depending on the conditions. X-ray crystal structures of these complexes indicated that each iodine atom contacts with the three adjacent oxygen atoms of 18C6 through two hypervalent secondary bonding and a weak interaction. (1)H NMR analyses and CSI-MS spectra showed that, in dichloromethane solution, Ph(2)IBF(4) exclusively forms the 1:1 complex with 18C6 (binding constant K(a), 1.02 x 10(3) M(-)(1)). The binding constants decrease with the increased solvent donor ability (Gutmann's DN). Changing the heteroatom ligand from BF(4) to the less nucleophilic PF(6) and AsF(6) increased the binding constant by about six times. Substitution of an electron-withdrawing group onto the para position of Ph(2)IBF(4) tends to increase in the complex stability. A linear Hammett relationship (rho = 0.59) between log K(a) and sigma(p)(+) values of substituents indicates that the diaryl-lambda(3)-iodanes with electropositive iodine(III) interact more efficiently with 18C6. Decreased binding magnitude was measured with 15C5, dibenzo-18C6, dibenzo-21C7, and dibenzo-30C10.     

Dependence of selective enclathration on types of cholic acid crystals

Competitive recrystallizations of cholic acid (CA) from 1:1 binary mixtures of seven mono-substituted benzenes are demonstrated. The order of preference for guests to be incorporated into the cholic acid crystals are as follows: benzene, toluene > n-amylbenzene, n-hexylbenzene > ethylbenzene, n-propylbenzene, n-butylbenzene. These seven compounds afford bilayer type inclusion crystals that are classified into four types based on the host frameworks and host-guest stoichiometries. The order of selective enclathration corresponds to the four types as follows: 1:1 alpha G > 2:1 alpha G > 1:1 beta T or 2:1 alpha T. The preference for the alpha G type was also confirmed by investigating the host frameworks of the crystals obtained from binary mixtures. The dependence of the selectivity on the different types of CA crystals can be understood in terms of the fit of the guest molecule in the host cavity.     

Benzoyl(acetylacetonato)nickel(II) complexes containing tertiary phosphine ligands. Their synthesis,dynamic behavior in solution,and decarbonylation

Carbon monoxide is readily inserted into the phenyl—nickel bond of PhNi(acac)(PR₃)_n to give benzoylnickel complexes, PhCONi(acac)PR₃ (R = Ph, Et, cyclo-C₆H₁₁), which were characterized by elemental analysis, IR and NMR spectroscopy, as well as chemical reactions. The reactions of the benzoylnickel complexes with methyl iodide and alcohols give acetophenone and corresponding benzoates, respectively, accompanied by some decomposition reactions. The solid benzoylnickel complexes when heated at elevated temperatures are decarbonylated and biphenyl, benzophenone and carbon monoxide are liberated. The dynamic behavior of the acac ligand in acetone solution was studied and the activation parameters for the acac exchange reactions were obtained. The decarbonylation reaction of the benzoyl complex PhCONi(acac)PPh₃ in acetone was studied by NMR, and found to be first order in the benzoylnickel complex.