Masatoshi Oue

Liquid-liquid extraction of silver ion with benzothiacrown ether derivatives

Abstract The extraction behavior of mono-, poly-, anal bis-(benzothiacrown ether)s is studied for alkali, alkaline-earth, heavy, and transition metal ions in the presence of picrate. These ethers show high selectivity for silver ion. Silver extractions from binary and quaternary mixtures of silver with heavy or transition metal ions were successful, except for mixtures with mercury(II) ion. Silver was extracted from a copper ore with ca. 80% recovery.

Synthesis and surfactant properties of novel acrylic acid co-oligomers containing fluoroalkylated end-groups: a new approach to polymeric inhibitors of human immunodeficiency virus type-1

Abstract Reactions of fluoroalkanoyl peroxides with acrylic acid, and with alkyl methacrylates or trimethylvinylsilane, give a series of new fluoroalkylated acrylic acid/alkyl methacrylate and /trimethylvinylsilane co-oligomers in excellent to moderate yield under very mild conditions. Fluoroalkylated acrylic acid/alkyl methacrylate co-oligomers are soluble in common organic solvents such as methanol, DMSO and tetrahydrofuran, and slightly soluble in non-polar aromatic solvents such as benzene, toluene and xylene. However, these co-oligomers do not have good solubility in both water and aromatic solvents. In contrast, fluoroakylated acrylic acid/trimethylvinylsilane co-oligomers are readily soluble in not only in water but also in common organic solvent such as methanol, ethanol, tetrahydrofuran, carbon tetrachloride, chloroform, DMF, DMSO, benzene, toluene and xylene. This feature is due to the trimethylsilyl side-chains possessing good oleophilic properties. Fluoroalkylated co-oligomers, in particular fluoroalkylated acrylic acid/trimethylvinylsilane co-oligomers, reduce the surface tension of both water and m -xylene effectively to around 15–20 mN m −1 , the same as for low-molecular weight fluorinated surfactants, though the co-oligomers have high molecular weights. These fluoroalkylated silicon-containing co-oligomers exhibit a clear break point resembling a CMC, which suggest that they form intra- or inter-molecular aggregations in aqueous solutions owing to their unique structure (fluoroalkylated end-capped structure). The fluoroalkylated acrylic acid co-oligomers inhibit HIV-1 induced cytopathogenesis. Relative to dextran sulfate, superior anti-HIV-1 activity could be obtained with fluoroalkylated acrylic acid/trimethylvinylsilane co-oligomers; however, fluoroalkylated acrylic acid cooligomers containing hydroxy groups were inactive. An obvious correlation exists between anti-HIV-1 activity and the hydrophilic or lipophilic property of these co-oligomers, i.e. they provide a most adequate HLB value for anti-HIV-1 activity. More hydrophilic or more oleophilic fluoroalkylated co-oligomers were less active (or inactive), suggesting that more hydrophilic or more oleophilic fluoroalkylated co-oligomers have a weaker effect on the interaction between gp/120 (or gp41) in HIV-1 and CD4 receptors. In fluoroalkylated silicon co-oligomers, as the degree of the reduction in surface tension of water becomes higher the anti-HIV-1 activity becomes higher, suggesting that the more adsorbable co-oligomers at the water/air interface have a higher anti-HIV-1 activity. A new correlation between anti-HIV-1 activity and properties of fluoroalkylated acrylic acid co-oligomers is indicated, affording a useful new strategy for exploring potent new polymeric inhibitors of HIV-1.

Extraction-spectrofluorimetric determination of silver ion using benzothiacrown ether and eosin

As benzothiacrown ether exhibited high selectivities for silver ion over several heavy metals on cation extraction, silver ion spectrofluorimetry was carried out by using an ion-pair extraction system with benzothiacrown ether as the ligand and eosin Y as the fluorescent anion. It was possible to determine 2–10 p.p.b. of silver ion, and the method was subject to only low interferences by alkali, alkaline earth and heavy metal ions, except mercury(II) ion. This method was successfully applied to the determination of trace amounts of silver ion in river water.

Synthesis and surfactant properties of novel fluoroalkylated allyl- and diallylammonium chloride oligomers

Abstract New fluoroalkylated allyl- and diallylammonium chloride oligomers with carbon—carbon bond formation have been prepared by the oligomerization of allylammonium chloride and the cyclo-oligomerization of diallylammonium chloride by the use of fluoroalkanoyl peroxides, respectively. These obtained fluoroalkylated cationic oligomers were able to reduce the surface tension of water to around 10 mN m−1, and are applicable to new cationic oligosurfactants containing fluoroalkyl groups.

Synthesis and surfactant properties of novel acrylic acid oligomers containing perfluoro-oxa-alkylene units: an approach to anti-human immunodeficiency virus type-1 agents

Abstract A new polymeric perfluoro-oxa-alkane diacyl peroxide has been prepared by the reaction of the corresponding perfluoro-oxa-alkane diacid fluoride and hydrogen peroxide under alkaline conditions. The decomposition behavior of this peroxide was quite similar to those of the fluoroalkanoyl peroxides [(RFCOO2)2; RF = perfiuoroalkyl and perfluoro-oxa-alkyl groups]. This peroxide decomposed homolytically with decarboxylation to afford the -RF- unit and, in addition, was useful for the introduction of the perfluoro-oxa-alkylene (-RF-) unit into acrylic acid homo- and co-oligomers via a radical process. These new acrylic acid oligomers containing the perfluoro-oxa-alkylene unit were shown to be soluble in water, methanol, ethanol, and tetrahydrofuran and were not only able to reduce the surface tension of water effectively but also to confer a good oil repellency. Furthermore, acrylic acid co-oligomers containing this perfluoro-oxa-alkylene unit were found to be potent and selective inhibitors of human immunodeficiency virus type 1 (HIV-1) in vitro.

Specific behavior of crowned crystal violet in cation complexation and photochromism

Abstract Absorption-spectral changes of a Crystal Violet derivative carrying a tris(monoaza-15-crown-5) structure in the presence of alkali metal ions were investigated under dark and UV-irradiated conditions. The absorption, 1 H NMR, and mass spectra indicate a dramatic conformational change of triscrowned Crystal Violet on its cesium–ion complexation under dark condition. In-situ photoirradiation measurement shows that the complexation decelerates the photochemical reaction of the triscrowned Crystal Violet.

Synthesis and properties of novel fluoroalkylated allyl alcohol oligomers

Abstract Allyl alcohol and allyl alcohol containing the polyoxyethylene unit were found to react with fluoroalkanoyl peroxides to afford the corresponding fluoroalkylated allyl alcohol oligomers via a radical process under very mild conditions. In particular, fluoroalkylated allyl alcohol oligomers containing the polyoxyethylene unit were shown to be effective in reducing the surface tension of water, and to be applicable for new non-ionic fluorinated amphiphiles.

Lipophilic thiacrown ether derivatives as neutral silver-ion selective carriers

Lipophilic mono- and di-thiacrown ethers have been synthesized and their ion selectivities evaluated as neutral carriers of polymeric membrane Ag+-selective electrodes. High Ag+-selectivities and excellent electrode properties were realized with the thiacrown ethers.

Synthesis and surfactant properties of novel fluoroalkylated amphiphilic oligomers

New fluoroalkylated oligomers containing morpholino groups are prepared by the reactions of fluoroalkanoyl peroxides with acryloyl morpholine; these oligomers show a good solubility in not only water but also common organic solvents, including non-polar solvents, and are applicable to non-ionic fluorinated amphiphilic oligosurfactants owing to reducing the surface tension of both water and in particular m-xylene quite effectively.

Photoinduced Potential Change by Crowned Triphenylmethane Dye Derivatives in Poly(vinyl chloride)-Based Liquid Membranes

ABSTRACT Photoirradiation effect on potential response to sodium ion concentrations and photoinduced potential change were investigated with plasticized poly(vinyl chloride) membranes based on triphenylmethane dye derivatives carrying a bis(monoaza-15-crown-5) moiety and a tris(monoaza-15-crown-5) moiety. A drastic photoinduced switching in potential response to sodium ion concentrations was realized by membranes containing crowned triphenylmethane dye derivatives. The photoinduced potential change was affected by complexing species such as a multinuclear complex.