Hideo Sawada

Reactions of arenesulfonyl chlorides with olefins catalyzed by a ruthenium(II) complex

Etude des reactions des chlorures darenesulfonyle avec des styrene, chloro-4 styrene et phenyl-2 propene. Obtention de sulfones vinyliques

Recognition of hydrophilic amino and N,N-dimethylamino compounds by the self-assembled aggregates of fluoroalkylated end-capped N-(1,1-dimethyl-3-oxobutyl)acrylamide oligomer

Self-assembled aggregates of new fluoroalkylated end-capped N-(1,1-dimethyl-3-oxobutyl)acrylamide oligomer can recognize selectively hydrophilic amino and N,N-dimethylamino compounds such as methylene blue, methyl orange, acriflavine hydrochloride and 3-aminophenylboronic acid, and transfer these compounds from aqueous solutions to organic media; in contrast, these aggregates were not able to recognize hydrophilic compounds such as 4-hydroxyazobenzene-4′-sulfonic acid sodium salt, acridine hydrochloride, 4-methoxyphenylboronic acid, 4-methyl-3-nitrophenylboronic acid, and phenylboronic acid.

Fluorinated functional materials possessing biological activities : gel formation of novel fluoroalkylated end-capped 2-acrylamido-2-methylpropanesulfonic acid polymers under non-crosslinked conditions

New fluoroalkylated end-capped 2-acrylamido-2-methylpropanesulfonic acid homopolymers were prepared by reaction of fluoroalkanoyl peroxides with 2-acrylamido-2-methylpropanesulfonic acid (AMPS). Similarly, fluoroalkylated end-capped copolymers were prepared by reaction of fluoroalkanoyl peroxides with AMPS and the comonomers such as trimethylvinylsilane and methyl methacrylate. These thus-obtained fluoroalkylated end-capped AMPS polymers were found to form gels not only in water but also in organic polar solvents such as methanol, ethanol,N,N-dimethylformamide and dimethyl sulfoxide under non-crosslinked conditions. On the other hand, AMPS polymer containing fluoroalkylene units {[-RF-(AMPS)q]p-} could cause no gelation under similar conditions. This suggests that fluoroalkylated end-capped AMPS polymers can cause gelation where strong aggregation of the end-capped fluoroalkyl segments is involved sterically in establishing the physical gel network in these media. Interestingly, these fluoroalkylated end-capped AMPS polymer hydrogels had a strong metal ion binding power. Moreover, it was demonstrated that these fluoroalkylated gelling polymers are potent and selective inhibitors of HIV-1 replication in cell culture. In addition, one of these gelling polymers was found to possess antibacterial activity againstStaphylococcus aureus. Therefore, these fluorinated gelling polymers are suggested to have high potential for new functional materials through their gelling ability and biological activity.

Gelation of fluoroalkylated 2-acrylamido-2-methylpropanesulfonic acid oligomers as potential for prevention of HIV-1 transmission

Abstract End-capped fluoroalkyl segments in 2-acrylamido-2-methylpropanesulfonic acid oligomers could serve as a new interaction for gelation in both water and organic polar solvents under non-cross-linked conditions, and these gelling oligomers were found to be selective inhibitors of human immunodeficiency virus type 1 (HIV-1) replication, suggesting that the compounds have the potential to prevent HIV-1 transmission through their chemical and biological properties.

Antibacterial activity of fluoroalkylated allyl-and diallyl-ammonium chloride oligomers

Abstract A series of fluoroalkylated allyl-and diallyl-ammonium chloride oligomers were prepared using fluoroalkanoyl peroxides as key intermediates, and their antibacterial activities against Staphylococcus aureus and Escherichia coli were studied. Antibacterial activity was found to be sensitive to the structure of these oligomers. Fluoroalkylated allyl-type co-oligomers containing carboxy, sulfo and trimethylsilyl segments were inactive; however, the allyl-or diallyl-type homo-and co-oligomers were in general active. Of these, the perfluoro-l-methyl-2-oxapentylated allylammonium chloride-diallylammonium chloride co-oligomer was found to be the most active against both S. aureus and E. coli . Furthermore, the fluoroalkylated oligomers possessing antibacterial activity were able to reduce the surface tension of water to around 10 mN m 1 . Therefore, these fluoroalkylated oligomers are new attractive functional materials possessing not only unique properties imparted by fluorine but also antibacterial activity.

Synthesis and properties of fluoroalkylated end-capped betaine polymers

Abstract Perfluoropropylated and some perfluoro-oxaalkylated end-capped 2-(3-acrylamidopropyldimethylammonio)- ethanoate (APDMAE) polymers were prepared by the reactions of fluoroalkanoyl peroxides with the corresponding monomer. These fluoroalkylated end-capped betaine polymers were soluble in water, methanol and ethanol. However, in these fluorinated APDMAE polymers, longer perfluoro-oxaalkylated end-capped APDMAE polymers were found to form highly viscoelastic fluids in water at concentrations above 10xa0g dm −3 under non-crosslinked conditions. The series of fluoroalkylated end-capped APDMAE polymers, especially longer perfluoro-oxaalkylated polymers, were able to reduce the surface tension of water effectively with a clear break point resembling a CMC at ca. 0.2xa0g dm −3 . In addition, some of these fluoroalkylated end-capped APDMAE polymers exhibited antibacterial activity against Staphylococcus aureus and Penicillium aeruginosa . Therefore, these fluoroalkylated end-capped polymers are suggested to have high potential for new functional materials through not only their unique physical properties, such as surfactant and gelling characteristics, but also antibacterial activity.

Direct aromatic fluoroalkylations of poly(p-phenylene) with fluoroalkanoyl peroxides: an approach to highly soluble fluorinated conducting polymers

Abstract Direct aromatic fluoroalkylations of poly( p -phenylene) (PPP) using fluoroalkanoyl peroxides were found to give excellent to moderate fluoroalkylated ratios even in heterogeneous systems. The fluoroalkylated products (PPP-R F ) were shown to possess dramatically higher solubilities than parent PPP, and the improvement in the solubility enabled measurements of the molecular weights of PPP-R F to be made by gel permeation chromatography analyses. Perfluoropropylated PPP formed a monomolecular film at the air-water interface. This deposited film was found to conduct electricity, and its electric conductivity was comparable with the conductivities of similar films formed from other compounds of potential interest in this field.

Synthesis and properties of novel perfluorocyclohexylated compounds with bis(perfluorocyclohexane carbonyl) peroxide

Bis(perfluorocyclohexane carbonyl) peroxide was prepared by the reaction of the corresponding acyl fluoride and hydrogen peroxide. This peroxide was applied to the preparation of perfluorocyclohexylated end-capped oligomers via a radical process under very mild conditions. In cyclic perfluorocyclohexylated end-capped oligomers containing hydroxy segments, these oligomers could cause a gelation in water and in polar organic solvents such as MeOH, EtOH, dimethylformamide (DMF), and dimethylsulfoxide (DMSO), and the gelling ability of these oligomers was superior to that of the corresponding linear perfluorooxaalkylated oligomers. Furthermore, perfluroocyclo-hexylation of polystyrene or benzene was proceeded via a single electron transfer reaction by using this peroxide.

RD6-2198, a novel betain-type fluoroalkylated oligomer, inhibits the replications of human immunodeficiency virus type 1 and other enveloped viruses

We have examined a novel betain-type fluoroalkylated oligomer, RD6-2198, for its inhibitory effects on the replication of human immunodeficiency virus type 1 (HIV-1) and other enveloped viruses, including herpes simplex virus types 1 and 2 (HSV-1 and HSV-2, respectively) and respiratory syncytial virus (RSV) in cell cultures. We have found that the compound is a potent and selective inhibitor of these viruses. RD6-2198 inhibited the replication of HIV-1IIIB at a concentration of 0.85 microg/ml with a selectivity index greater than 59 in MT-4 cells. Furthermore, its 50% effective concentration (EC50) values for HSV-1, HSV-2 and RSV, were 0.51, 0.94 and 3.0 microg/ml, respectively. We found that the RD6-2198 suppressed the gp120-CD4 interaction (as monitored by an enzyme-linked immunosorbent assay (ELISA) method). RD6-2198 also inhibited the binding of anti-gp120 monoclonal antibody to gp120 expressed on MOLT-4/IIIB cells (MOLT-4 cells chronically infected with HIV-1IIIB). However, the compound did not inhibit the interaction of anti-CD4 antibody with CD4. These results suggest that RD6-2198 interacts with the viral envelope glycoprotein and thereby inhibits the viral adsorption process. In addition, RD6-2198 was also found to suppress the proliferation of MOLT-4/IIIB cells. When applied topically, RD6-2198 at a concentration of 10 mg/ml completely protected mice from an intravaginal HSV-2 infection.

The binding of free calcium ions in aqueous solution using fluoroalkyl end-capped acryloylmorpholine oligomers

Abstract Fluoroalkyl end-capped acryloylmorpholine oligomers which are obtained by the reactions of fluoroalkanoyl peroxides with acryloylmorpholine were shown to have an extraordinarily high calcium binding ability compared with the corresponding non-fluorinated oligomer or the common organic chelating materials such as poly(acrylic acid).