Cross-linked fluoroalkyl end-capped co-oligomeric nanoparticle-encapsulated fullerenea new approach to the surface modification of traditional organic polymers with fullerene-containing nanoparticles.

Cross-linked fluoroalkyl end-capped co-oligomeric nanoparticle-encapsulated fullerenes, prepared by deprotecting a fluoroalkyl end-capped isocyanatoethyl methacrylate 2-butanone oxime adduct-1-hydroxy-5-adamantylacrylate co-oligomer in the presence of fullerene, were of well-defined size in the nanometer range (28-82 nm) and exhibited good dispersibility in a variety of solvents such as methanol, ethanol, isopropyl alcohol, tetrahydrofuran, N,N-dimethylformamide, dimethyl sulfoxide, and 1,2-dichloroethane. Transmission electron microscopy images also showed that these nanocomposites were particles with a mean diameter of 45 nm and that the fullerenes were tightly encapsulated into fluorinated nanoparticle cores. In methanol, these fluorinated nanoparticles emitted fluorescence related to the presence of fullerene and were applied in the surface modification of traditional organic polymers such as poly(methyl methacrylate) (PMMA) to effect good oleophobicity imparted by fluorine on the modified film surfaces. Interestingly, a higher fluorescent intensity of fullerene was observed on the modified PMMA surfaces, although the reverse side of these film surfaces yielded an extremely weak fluorescent intensity. More interestingly, a fluorescence microscopy image of the cross-section of the modified PMMA film showed that encapsulated fullerene was arranged regularly above the modified PMMA film surface.

Architecture of linear arrays of fluorinated co-oligomeric nanocomposite-encapsulated gold nanoparticles: a new approach to the development of gold nanoparticles possessing an extremely red-shifted absorption characteristic.

Fluoroalkyl end-capped co-oligomeric nanoparticles, which were prepared by the reaction of fluoroalkanoyl peroxide with 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and 1-hydroxy-5-adamantylacrylate (Ad-HAc), were applied to the preparation of novel fluorinated co-oligomeric nanocomposite-encapsulated gold nanoparticles. These fluorinated gold nanocomposites were easily prepared by the reductions of gold ions with poly(methylhydrosiloxane) (PMHS) in the presence of the corresponding fluorinated nanoparticles and tri -n-octylamine (TOA) in 1,2-dichloroethane (DE) at room temperature. These fluorinated gold nanoparticles were isolated as wine-red powders and were found to exhibit good dispersibility in a variety of traditional organic solvents such as DE, methanol, and t-butyl alcohol to afford transparent wine-red solutions. The morphology and stability of these fluorinated co-oligomeic nanocomposite-encapsulated gold nanoparticles were characterized using transmission electron microscopy (TEM), dynamic light scattering measurements (DLS), and UV-vis spectroscopy. DLS measurements and UV-vis spectroscopy showed that these particles are nanometer-size-controlled very fine nanoparticles (185-218 nm) that exhibit a plasmon absorption band at around 530 nm. TEM images also showed that gold nanoparticles are tightly encapsulated into fluorinated co-oligomeric nanoparticle cores. Interestingly, these fluorinated co-oligomeric nanocomposites-encapsulated gold nanoparticles were found to afford linear arrays of these fluorinated nanoparticles with increases in the feed amounts of TOA. More interestingly, these fluorinated gold nanoparticles were able to afford the extremely red-shifted plasmon absorption band at around 960 nm.

Thermoresponsive characteristics of fluoroalkyl end-capped co-oligomers in aqueous solutions and on the poly(methyl methacrylate) film surface.

Fluoroalkyl end-capped N-(1,1-dimethyl-3-oxobutyl)acrylamide--acryloylmorpholine co-oligomers were prepared by the co-oligomerizations of fluoroalkanoyl peroxides with the corresponding monomers. These fluorinated co-oligomers exhibited a lower critical solution temperature (LCST) characteristic in aqueous solutions. Of particular interest, a steep time dependence of contact angle values for dodecane was observed from 40 to 60 degrees C to decrease their values, effectively, on the modified PMMA [poly(methyl methacrylate)] film surface treated with fluorinated co-oligomer possessing the LCST: 36 degrees C (in water), although such a steep time dependence was not observed from 20 to 30 degrees C.

Preparation of novel fluoroalkyl-end-capped 2-acrylamido-2-methylpropanesulfonic acid cooligomeric nanoparticles containing adamantane units possessing a lower critical solution temperature characteristic in organic media.

Fluoroalkyl-end-capped 2-acrylamido-2-methylpropanesulfonic acid cooligomers containing adamantyl segments were prepared by reaction of fluoroalkanoyl peroxide with 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and 3-hydroxy-1-adamantyl acrylate (Ad-HAc). These obtained fluorinated AMPS-Ad-HAc cooligomers were found to form nanometer-size-controlled fine particles not only in water but also in a large variety of traditionally organic solvents. In addition, these fluorinated cooligomeric nanoparticles showed a good dispersibility in these solvents. Interestingly, the size of these fluorinated nanoparticles is extremely sensitive to solvent changes, and an increase of the particle size was observed in the solvents, in which the dielectric constant is higher or lower. More interestingly, these fluorinated AMPS-Ad-HAc cooligomeric nanoparticles exhibited a lower critical solution temperature around 52 degrees C in an organic medium (tert-butyl alcohol).

Synthesis and applications of novel fluorinated dendrimer-type copolymers by the use of fluoroalkanoyl peroxide as a key intermediate.

Fluoroalkanoyl peroxide reacted with 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane (TTRV-Si) to afford fluoroalkyl end-capped oligomers containing some unreacted vinyl segments under very mild conditions. Fluoroalkyl end-capped cyclosiloxane oligomers containing some vinyl segments thus obtained reacted with N,N-dimethylacrylamide and fluoroalkanoyl peroxide to afford new fluorinated dendrimer-type block copolymers in good isolated yield. Similar reactions were also occurred by the use of 1,3,5-trivinyl-1,3,5-trimethylcyclotrisiloxane instead of TTRV-Si, and the corresponding fluorinated dendrimer-type block copolymer was obtained in good isolated yield. These fluorinated dendrimer-type block copolymers had an excellent solubility not only in water but also in traditional organic solvents including aliphatic fluorinated solvents. Interestingly, these fluorinated block copolymers were found to form the self-assembled dendrimer-type polymeric aggregates in aqueous solutions. More interestingly, these fluorinated block copolymers had an extremely higher dispersion ability of not only single-walled carbon nanotube and fullerenes but also magnetic nanoparticles into water, compared to that of the corresponding two fluoroalkyl end-capped oligomers.