New fluoroalkyl end-capped 2-acrylamido-2-methylpropanesulfonic acid oligomers [R_F- (AMPS) _nR_F] were prepared by the reaction of the corresponding monomer (AMPS) with fluoroalkanoyl peroxide as a key intermediate. These fluorinated AMPS oligomers thus obtained were found to form gels not only in water but also in organic solvents such as methanol, dimethyl sulfoxide, and N, N-dimethylformamide under non-crosslinked conditions, although the corresponding non-fluorinated AMPS oligomer could cause no gelation in these solvents. These fluorinated AMPS oligomer gels had a strong metal ion binding power. More interestingly, it was demonstrated that these fluorinated AMPS oligomer gels are potent and selective inhibitors of HIV-1 replication in cell culture. Additionally, fluoroalkyl end-capped AMPS cooligomer gels containing poly (oxyethylene) units are applicable to new fluorinated gelling polymer electrolytes, and these fluorinated gels containing lithium ions exhibited a considerable high ionic conductivity of the level of 10^-3 S/cm at room temperature. Fluoroalkyl end-capped AMPS oligomer hydro-gels were also applicable to a new reaction medium for aldol reaction, and these fluorinated gels were reused without loss of the catalytic activity. Fluoroalkyl end-capped oligomers containing hydroxyl segments were also found to cause a gelation, where the aggregations of fluoroalkyl segments and the hydrogen-bonding interaction are involved in establishing a physical gel network not only in water but also in organic solvents under non-crosslinked conditions. Fluoralkyl end-capped tri- or tetra-ol cooligomer gels containing poly (oxyethylene) (or carboxyl) segments in lithium ions exhibited higher ionic conductivities at 10^-3 S/cm levels. Especially, fluoroalkyl end-capped tetraol cooligomer gels containing carboxyl segments exhibited a proton conductivity at 10^-4 S/cm level. These fluorinated oligomer gels are applicable to not only lithium ions but also proton conductive polymer electrolytes, especially new fluorinated ionic conductive materials. Fluoroalkyl end-capped N- (1, 1-dimethyl-3-oxobutyl) acrylamide homo-oligomers were not able to cause a gelation in various solvents; however, these fluorinated oligomers can form the self-assembled molecular aggregates in organic media, and these aggregates provide suitable host moieties with 300-600 nm size to interact strongly with hibitane, which is well-known to be a potent low-molecular weight biocide, as a guest molecule. On the other hand, fluoroalkyl end-capped N- (1, 1-dimethy1-3-oxobutyl) acrylamide cooligomers containing triol segments could cause a gelation in water, DMSO and DMF, and these fluorinated co-oligomer gels were applied to the controlled release of anticancer drugs such as methotrexate.

View full abstract