Thickening process of polyethylene single crystals at an early stage of annealing

The thickening process of polyethylene single crystals was simulated with computer by the Monte Carlo method. According to the experimental results in the previous report, the time dependence of the long period changed greatly with annealing temperature; at lower temperatures the long period increased gradually, while at high temperatures the long period rapidly increased at a very early stage of annealing and then increased gradually after passing through a plateau. Through computer simulation, it was shown that such a great change in the time dependence of the long period with annealing temperature can be explained by combining two mechanisms: (A) sliding diffusion of molecular segments along the chain axis and (B) local melt-recrystallization (namely, local melting followed by recystallization).     

Elimination of ingredients effect to improve the detection of anti HIV-1 p24 antibody in human serum using SPR apparatus.

Highly sensitive detection of proteins in serum becomes difficult in some cases during surface plasmon resonance (SPR) measurements, because some ingredients in the serum hugely enhance non-specific reactions on the sensing chip of SPR. It is well recognized that the antibody against core protein p24 of HIV in serum is one of the most important proteins in the accurate diagnosis of infection with HIV. In this study, we could attain the accurate detection of anti p24 antibody in human serum by eliminating the serious effects of the ingredients in serum on the measurement of SPR by employing these procedures: 1) blocking the gold surface of the sensing chip with human serum and 2) heating the serum sample at 56 degrees C for 30 min. Without these treatments, the signal of SPR was considerably suppressed on the measurements of the anti p24 antibody which contained human serum, making the accurate detection difficult. However, with introducing the above two treatments, the sensing of anti p24 antibody in human serum was improved, while a small non-specific reaction was still observed. By removing the non-specific reaction caused by the ingredients in the serum, we could accurately measure the antibody for p24 in human serum sample over the range from 1 to 20 micrograms/ml.     

Concentration of chlorophenols in water to dialkyated catinonic surfactant-silica gel admicelles

Chlorophenols including monochlorophenol, dichlorophenol, trichlorophenol, tetrachlorophenol, and pentachlorophenol in water were extracted into dialkylated cationic surfactant-silica gel admicelles. The dialkylated cationic surfactants such as didecyldimethylammonium bromide (DC10) and didodedyldimethylammonium bromide (DC12) sorbed on silica gel surfaces to form admicelles at pH 9. Approximately 200mg of DC10 was quantitatively sorbed on 1g of silica gel. The sorption further increased by further addition of DC10. This is in contrast to the fact that the maximum sorption of mono-alkylated cetyltrimethyammonium chloride (CTAC) was only ca. 100mg. Based on the fluorescent spectra of a molecular probe, N-phenyl-1-naphthylamine, DC10- and DC12-silica gel admicelles were more hydrophobic than CTAC-silica gel admicelles. The extents of the extraction of chlorophenols into DC10-silica gel admicelles were greater than those into CTAC-silica gel admicelles. However, the extractions to DC12-silica gel admicelles were insufficient due to leakage of DC12 vesicles. Consequently, DC10-silica gel admicelles were the most adequate for concentrating chlorophenols in water. An admicelle column was prepared by passing aqueous buffer solution of DC10 through a Bond Elut Jr. silica gel solid-phase extraction cartridge. It was successfully applied to the 500-fold concentration of chlorophenols including hydrophilic mono-substituted chlorophenol in water samples prior to their HPLC analysis.     

Influence of addition of ethylene on the γ-ray-induced alternating copolymerization of ethylenimine and carbon monoxide

The influence of the addition of ethylene on the γ-ray-induced alternating copolymerization of ethylenimine and carbon monoxide was investigated. A mixture of ethylenimine, carbon monoxide, and ethylene was irradiated to produce a polymer containing these monomeric units. The infrared spectrum of the copolymer showed the characteristic absorption peaks of the secondary amide and ketone bond and was different from that of the reaction product of polyketone with ethylenimine and that of the γ-ray irradiation product of ethylene and poly-ß-alanine. The x-ray diffraction diagram of the copolymer was different from those of poly-ß-alanine and polyketone and exhibited an amorphous structure. Paper chromatographic analysis showed that the hydrolysis product of the copolymer contained ß-alanine and δ-aminovaleric acid. These results indicate that terpolymerization of ethylenimine, carbon monoxide, and ethylene took place under γ-ray irradiation and gave an amorphous polymer containing the units \documentclass{article}\pagestyle{empty}\begin{document}$ \rlap{} ({\rm CH}_{\rm 2} {\rm CH}_{\rm 2} {\rm NHCO}\rlap{}),\rlap{} ({\rm CH}_{\rm 2} {\rm CH}_{\rm 2} {\rm CO}\rlap{}),{\rm and}\rlap{} ({\rm CH}_{\rm 2} {\rm CH}_{\rm 2} {\rm CH}_{\rm 2} {\rm CH}_{\rm 2} {\rm NHCO}\rlap{}) $\end{document}     

Synthesis of perfluorochemicals for use as blood substitutes,Part I. Electrochemical fluorination of N-methyldecahydroquinoline and N-methyldecahydroisoquinoline

Electrochemical fluorination of N-methyldecahydroquinoline afforded mainly a mixture of $\text{cis}$ and $\text{trans}$ N-(F-methyl)-F-decahydroquinoline, their rearranged isomers and F-propyl-F-cyclohexane arising from the cleavage at carbon-nitrogen bonds, in a ratio of approximately 2:4:6:3. N-Methyldecahydroisoquinoline was also fluorinated electrochemically to give a mixture of $\text{cis}$ and $\text{trans}$ N-(F-methyl)-F-decahydroisoquinoline, their rearranged isomers and 1-(F-ethyl)-2-(F-methyl)-F-cyclohexane in a ratio of approximately 4:4:6:1. No correlation was found between the $\text{cis}$ and $\text{trans}$ ratio of starting materials and that of the corresponding perfluorinated amines. Fluorination of N-methyl-1,2,3,4-tetrahydroquinoline gave much lower yields.     

Observation of photoexcitation of Fe-oxide grown on TiO<Subscript>2</Subscript>(100) by visible light irradiation

Electronic excitation of materials is of fundamental and technological importance and interest in terms of photoinduced phase transition, photovoltaics, and photocatalysis. In the present study, photoexcitation of Fe₂ O ₃ epitaxially grown on rutile TiO₂(100) was investigated with conversion electron Mössbauer spectroscopy (CEMS) under dominantly visible-light irradiation. ⁵⁷Fe was deposited on the substrate at a substrate temperature of 973 K, and the resulting film was characterized by RHEED and XPS. After deposition of Fe on TiO₂(100), it was found that Fe was oxidized to Fe ³⁺, and the structure was analyzed to be the rhombohedral phase of Fe₂ O ₃. While the CEMS spectrum without light irradiation showed a quadrupole splitting of 0.80 mm/s with an isomer shift of +0.25 mm/s, an additional component with a quadrupole splitting of 0.85 and an isomer shift of +0.67 mm/s was observed under light irradiation. The latter component corresponds to a reduced state of Fe at the octahedral site surrounded by oxygen atoms. The lifetime of this photoexcited state is discussed.     

2D Nanoarchitectonics: Soft Interfacial Media as Playgrounds for Microobjects,Molecular Machines,and Living Cells

Soft and flexible two-dimensional (2D) systems, such as liquid interfaces, would have much more potentials in dynamic regulation on nano–macro connected functions. In this Minireview article, we focus especially on dynamic motional functions at liquid dynamic interfaces as 2D material systems. Several recent examples are selected to be explained for overviewing features and importance of dynamic soft interfaces in a wide range of action systems. The exemplified research systems are mainly classified into three categories: (i) control of microobjects with motional regulations; (ii) control of molecular machines with functions of target discrimination and optical outputs; (iii) control of living cells including molecular machine functions at cell membranes and cell/biomolecular behaviors at liquid interface. Sciences on soft 2D media with motional freedom and their nanoarchitectonics constructions will have increased importance in future technology in addition to popular rigid solid 2D materials.     

May Trifluoromethylation and Polymerization of Styrene Occur from a Perfluorinated Persistent Radical (PPFR)?

The radical polymerization of styrene (St) initiated by a trifluoromethyl radical generated from a perfluorinated highly branched persistent radical (PPFR) is presented with an isolated yield above 70 %. The release of ^.CF₃ radical occurred from a temperature above 85 °C. Deeper ¹H and ¹⁹F NMR spectroscopies of the resulting fluorinated polystyrenes (CF₃-PSts) evidenced the presence of both CF₃ end-group of the PSt chain and the trifluoromethylation of the phenyl ring (in meta-position mainly). [PPFR]₀/[St]₀ initial molar ratios of 3:1, 3:10 and 3:100 led to various molar masses ranging from 1750 to 5400 g mol⁻¹ in 70–86 % yields. MALDI-TOF spectrometry of such CF₃-PSts highlighted polymeric distributions which evidenced differences between m/z fragments of 104 and 172 corresponding to styrene and trifluoromethyl styrene units, respectively. Such CF₃-PSt polymers were also compared to conventional PSts produced from the radical polymerization of St initiated by a peroxydicarbonate initiator. A mechanism of the polymerization is presented showing the formation of a trifluoromethyl styrene first, followed by its radical (co)polymerization with styrene. The thermal properties (thermal stability and glass transition temperature, T_g) of these polymers were also compared and revealed a much better thermal stability of the CF₃-PSt (10 % weight loss at 356–376 °C) and a T_g of around 70 °C.