Reactions Of Fluoroalkanoyl Peroxides Research Articles

Wettability Control between Oleophobic/Superhydrophilic and Superoleophilic/Superhydrophobic Characteristics on the Modified Surface Treated with Fluoroalkyl End-Capped Oligomers/Micro-Sized Polystyrene Particle Composites

Fluoroalkyl end-capped vinyltrimethoxysilane-N,N-dimethylacrylamide cooligomer [RF-(CH2-CHSi(OMe)3)x-(CH2-CHC(=O)NMe2)y-RF; RF = CF(CF3)OC3F7: RF-(VM)x-(DMAA)y-RF] was synthesized by reaction of fluoroalkanoyl peroxide [RF-C(=O)O-O(O=)C-RF] with vinyltrimethoxysilane (VM) and N,N-dimethylacrylamide (DMAA). The modified glass surface treated with the cooligomeric nanoparticles [RF-(VM-SiO3/2)x-(DMAA)y-RF] prepared under the sol-gel reaction of the cooligomer under alkaline conditions was found to exhibit an oleophobic/superhydrophilic property, although the corresponding fluorinated homooligomeric nanoparticles [RF-(VM-SiO3/2)n-RF] afforded an oleophobic/hydrophobic property on the modified surface under similar conditions. RF-(VM-SiO3/2)n-RF/RF-(VM-SiO3/2)x-(DMAA)y-RF/PSt (micro-sized polystyrene particles) composites, which were prepared by the sol-gel reactions of the corresponding homooligomer and cooligomer in the presence of PSt particle under alkaline conditions, provided an oleophobic/superhydrophilic property on the modified surface. However, it was demonstrated that the surface wettability on the modified surface treated with the RF-(VM-SiO3/2)n-RF/RF-(VM-SiO3/2)x-(DMAA)y-RF/PSt composites changes dramatically from oleophobic/superhydrophilic to superoleophilic/superhydrophilic and superoleophilic/superhydrophobic characteristics, increasing with greater feed ratios (mg/mg) of the RF-(VM)n-RF homooligomer in homooligomer/cooligomer from 0 to 100 in the preparation of the composites. Such controlled surfac

Synthesis and applications of novel fluoroalkyl end‐capped cooligomers containing diphenylacetylene segments: a new approach to the surface arrangement of diphenylacetylene segments on the traditional organic polymer

AbstractFluoroalkyl end‐capped cooligomers containing diphenylacetylene segments [RF‐(DPMA)x‐(Co‐M)y‐RF] were prepared by reaction of fluoroalkanoyl peroxide with 4‐(phenylethynyl)phenyl methacrylate (DPMA) and radical polymerizable comonomers such as N,N‐dimethylacrylamide (DMAA) and acryloylmorpholine (ACMO) under very mild conditions. Fluorinated cooligomers containing diphenylacetylene segments thus obtained exhibited a good solubility in a variety of organic solvents. These fluorinated cooligomers were also applied to the surface modification of traditional organic polymers such as poly(methyl methacrylate) (PMMA) to exhibit not only a good surface active property imparted by fluorine but also a fluorescent characteristic related to diphenylacetylene segments on their surface. In addition, these fluorinated cooligomers could form the nanometer size‐controlled fluorinated molecular aggregates in chloroform. Interestingly, some benzenes and biphenyl (BP) derivatives could interact with these fluorinated oligomeric aggregates as guest molecules, and in particular 2‐chloro‐5‐nitrobenzotrifluoride (CNB) was most effective for enhancing the fluorescent intensity of these guest molecules. Copyright © 2009 John Wiley & Sons, Ltd.

Preparation of size-controlled cross-linked fluoroalkyl end-capped oligomer/gold nanocomposites

Cross-linked fluoroalkyl end-capped cooligomeric nanoparticles, which were prepared by reaction of fluoroalkanoyl peroxide with poly(oxyethylene) unit-containing dimethacrylate monomer and acrylic acid, were applied to the preparation of novel cross-linked fluorinated cooligomer/gold nanocomposites. These fluorinated gold nanocomposites were prepared by reactions of gold ions with poly(methylhydrosiloxane) in the presence of the corresponding fluorinated nanoparticles in 1,2-dichloroethane at room temperature. The size of these fluorinated gold nanocomposites thus obtained is nanometer size-controlled, and the absorbance around 530 nm related to the formation of gold nanoparticles was found to increase by the addition of trioctylamine under these preparative conditions. The size of these composites increased effectively from 67 nm to 160 nm levels with increasing the amounts of trioctylamine. In particular, the plasmon absorption bands related to the gold nanocomposites were also dramatically red-shifted from around 530 nm to 900 nm levels under similar conditions.

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.

Preparation and applications of novel fluoroalkyl end-capped 2-acrylamido-2-methylpropanesulfonic acid oligomer/clay nanocomposites

New fluoroalkyl end-capped 2-acrylamido-2-methylpropanesulfonic acid oligomers/clay composites were prepared by reaction of fluoroalkanoyl peroxide with the corresponding monomer in the presence of clay in aqueous solutions. These obtained fluorinated composites were nanometer size-controlled and were found to exhibit a good dispersibility in water and polar organic solvents such as methanol. The contents of clay in these nanocomposites were estimated to be 3∼19% by the thermogravimetric analysis measurements. X-ray diffraction spectra showed the successful intercalation of fluorinated oligomers into the interlayer spaces of clay. These fluorinated clay nanocomposites were applied to the surface modification of poly(vinyl alcohol). In addition, these fluorinated nanocomposites were found to interact with methylene blue effectively to afford the fluorinated oligomers/clay/methylene blue nanocomposites.

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).

Reactions of fluoroalkanoyl peroxides with single‐walled carbon nanotubes: application to sidewall modification of single‐walled carbon nanotubes with the introduction of fluoroalkyl groups

AbstractFluoroalkanoyl peroxides reacted with single‐walled carbon nanotubes (SW‐CNTs) to afford fluoroalkylated SW‐CNT derivatives under very mild conditions. Fluoroalkylated SW‐CNT derivatives [RF‐(SW‐CNT)s] thus obtained exhibited no solubility in aqueous and traditional organic media; however, RF‐(SW‐CNT)s were solubilized into water more effectively than the parent SW‐CNT by the use of fluoroalkyl end‐capped homooligomers. However, fluroalkyl end‐capped SW‐CNT cooligomers were obtained by the reactions of fluroalkanoyl peroxides with SW‐CNTs in the presence of radical polymerizable monomers, and these fluoralkylated SW‐CNT cooligomers were found to exhibit a good solubility in aqueous and organic media. Copyright © 2006 John Wiley & Sons, Ltd.

SYNTHESIS OF FLUOROALKYL END-CAPPED OLIGOMERS CONTAINING PENDANT PHOSPHINIC AND PHOSPHONIC ACID SEGMENTS—APPLICATION TO NOVEL FLUORINATED BIOACTIVE POLYMERS POSSESSING ANTIBACTERIAL AND ANTI-HIV-1 ACTIVITIES

A variety of fluoroalkyl end-capped homo- and co-oligomers containing pendant phosphinic acid segments were prepared by the reactions of fluoroalkanoyl peroxides with 3-acryloxypropylbutylphosphinic acid (APBPA) [or 3-acryloxypropyloctylphosphinic acid (APOPA)] and comonomers such as N,N-dimethylacrylamide (DMAA) and acrylic acid (ACA). These fluorinated APBPA and APOPA homo-oligomers thus obtained were insoluble in water but were soluble in common organic solvents, and were able to reduce the surface tension of m-xylene quite effectively. Fluorinated APBPA- and APOPA cooligomers were in general soluble in water and common organic solvents, and exhibited a good surfactant property against water. In addition, PMMA [poly(methyl methacrylate)] surface modified with these fluorinated oligomers containing pendant phosphinic acid segments was found to exhibit a strong oleophobicity imparted by fluorine at the surface. Similarly, fluoroalkyl end-capped homooligomers containing pendant phosphonic acid segments were prepared by the reactions of fluoroalkanoyl peroxides with 3-acryloxypropylphosphonic acid (APPA) under mild conditions. These obtained fluorinated oligomers containing pendant phosphonic acid segments were shown to have no solubility in water and organic solvents; however, these fluorinated oligomers could cause a gelation in water. Of particular interest, fluorinated oligomers containing pendant phosphinic acid segments were found to exhibit strong antibacterial activity against Staphylococcus aureus and Pseudomonas aeruginosa. Moreover, these fluorinated oligomers were also demonstrated to exhibit a potent and selective anti-HIV-1 (human immunodeficiency virus type 1) activity in vitro.

SYNTHESIS AND APPLICATIONS OF NOVEL FLUOROALKYL END-CAPPED OLIGOMERS CONTAINING 3,5-DIMETHYL-4-HYDROXYBENZYL AND 3-(2H-BENZOTRIAZOL-2-yl)-4-HYDROXYPHENYL SEGMENTS

New fluoroalkyl end-capped co-oligomers containing 3,5-dimethyl-4-hydroxybenzyl segments [RF‒(DMHB)x‒(DMAA)y–RF] were prepared by the reactions of fluoroalkanoyl peroxides with N-(3,5-dimethyl-4-hydroxybenzyl)methacrylamide [DMHB] and N,N-dimethylacrylamide (DMAA). Similarly, fluoroalkyl end-capped homo- and co-oligomers containing 3-(2H-benzotriazol-2-yl)-4-hydroxyphenyl segments [RF–(BTRI)x–(Co–M)y–RF] were prepared by the reactions of fluoroalkanoyl peroxides with 2-[3–(2H‒benzotriazol–2–yl)–4–hydroxyphenyl]ethyl methacrylate [BTRI] and co-monomers [Co–M] such as acrylic acid (ACA), DMAA, and acryloylmorpholine (ACMO). The fluoroalkyl end-capped DMHB and BTRI co-oligomers thus obtained were soluble not only in water but also in common organic solvents. In addition, these fluorinated co-oligomers were able to reduce the surface tension of 0.1 N NaOH solutions quite effectively to around 20 mN/mlevels, although the corresponding non-fluorinated co-oligomers were not effective in reducing the surface tension of 0.1 N NaOH solutions. A modified polystyrene film surface treated with these fluoroalkyl end-capped DMHB and BTRI co-oligomers was found to exhibit a good oleophobicity imparted by fluorine with an excellent hydrophilicity. XPS analyses showed that end-capped fluoroalkyl groups in RF-(BTRI)n-RF homo-oligomer were arranged regularly above the modified polystyrene surface. Of particular interest, it was demonstrated that the self-assembled molecular aggregates formed by RF-(DMHB)x-(DMAA)y-RF co-oligomers could interact strongly with 7,7,8,8-tetracyanoquinodimethane (TCNQ) as a guest molecule to form a host–guest intermolecular complex, though such a host–guest interaction was not observed in the corresponding non-fluorinated DMHB co-oligomer.

Synthesis and properties of fluoroalkyl end‐capped sulfobetaine polymers

AbstractA variety of fluoroalkyl end‐capped 3‐[N‐(3‐acrylamido)propyl‐N,N‐dimethylammonio]propanesulfonate polymers [RF–(APDAPS)n–RF] were prepared by the reactions of fluoroalkanoyl peroxides with the corresponding monomer under very mild conditions. Similarly, fluoroalkyl end‐capped 2‐vinylpyridinio propane sulfonate polymer was obtained by the use of fluoroalkanoyl peroxide. These fluoroalkyl end‐capped sulfobetaine polymers exhibited a good solubility in water; however, these polymers have a poor solubility in other solvents. In particular, RF–(APDAPS)n–RF polymers caused gelation in methanol, although RF–(VPPA)n–RF polymer showed no gelation in methanol. RF–(APDAPS)n–RF polymers were found to form the self‐assembled molecular aggregates with the aggregations of the end‐capped fluoroalkyl segments and the ionic interactions between sulfobetaine segments in aqueous solutions. On the other hand, it was suggested that RF–2‐vinylpyridinio propane sulfonate (VPPS)n–RF polymer is not likely to form the self‐assemblies in aqueous solutions because of the steric hindrance of pyridiniopropyl betaine units in polymer. We also studied the surfactant properties of RF–(APDAPS)n–RF and RF–(VPPS)n–RF polymers compared with those of other fluoroalkyl end‐capped betaine‐type polymers such as 2‐acrylamido‐2‐methylpropanesulfonic acid polymers and 2‐(3‐acrylamidopropyldimethylammonio) ethanoate polymers. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1144–1153, 2004

Synthesis and properties of novel fluoroalkyl end‐capped oligomers containing silsesquioxane segments

AbstractFluoroalkyl end‐capped homo‐ and co‐ oligomers containing silsesquioxane segments were prepared by the reactions of fluoroalkanoyl peroxides with the corresponding methacrylate monomer‐bearing silsesquioxane unit (Si‐MMA) and comonomers such as N,N‐dimethylacrylamide (DMAA) and acrylic acid (ACA). These new fluorinated Si‐MMA oligomers were easily soluble in various organic solvents and were able to reduce the surface tension of m‐xylene effectively. The modified poly(methyl methacrylate) [PMMA] and glass surface treated with fluorinated Si‐MMA homo‐oligomers exhibited a strong oleophobicity, although these fluorinated oligomers possess high oleophilic silsesquioxane segments. In contrast, the modified PMMA surface treated with fluorinated Si‐MMA–DMAA cooligomers exhibited a good hydrophilicity with a strong oleophobicity. In a series of fluorinated Si‐MMA oligomers, fluorinated Si‐MMA homo‐oligomers had a relatively high thermal stability. Therefore, these fluoroalkyl end‐capped Si‐MMA oligomers are suggested to have high potential for new functional materials through their unique properties such as a high solubility and surface active properties. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3486–3493, 2002

Synthesis of Amphiphilic Fluoroalkoxyl End-Capped Cooligomers Containing Oxime-Blocked Isocyanato Segments: Architecture and Applications of New Self-Assembled Fluorinated Molecular Aggregates

New fluoroalkoxyl end-capped cooligomers containing oxime-blocked isocyanato segments were prepared by the reactions of fluoroalkanoyl peroxides with isocyanatoethyl methacrylate 2-butanone oxime adduct (IEM-BO) and N,N-dimethylacrylamide (DMAA). Fluoroalkoxyl end-capped IEM-BO−DMAA cooligomers thus obtained were easily soluble in water and common organic solvents except for hexane. These amphiphilic fluoroalkoxyl end-capped cooligomers were able to reduce the surface tension of water quite effectively around to 18 mN/m levels with a clear break point resembling a cmc (critical micelle concentration). Static and dynamic light scattering measurements showed that fluoroalkoxyl end-capped IEM-BO−DMAA cooligomers are likely to form the self-assembled molecular aggregates in aqueous solutions. In particular, the longest fluoroalkoxyl end-capped IEM-BO−DMAA cooligomer can form the self-assemblies, which are considered to consist of around 100 fluorinated oligomeric molecules with 17−18 nm size even in the lower concentrations of the cooligomer, compared to the other fluoroalkoxylated cooligomers. The molecular assemblies formed by the longest fluoroalkoxyl end-capped IEM-BO−DMAA cooligomer could interact strongly with ethidium bromide (Etd-Br) as a guest molecule to form the host−guest intermolecular complex. Additionally, fluoroalkoxyl end-capped IEM-BO−DMAA cooligomers were found to become useful precooligomers for the introduction of various aromatic segments into the cooligomer chains. In fact, amphiphilic fluoroalkoxyl end-capped cooligomer-bound functional aromatic moieties such as 5-fluorouracil(5-FU) and 9-aminoacridine were prepared in good yields by the reactions of the corresponding fluorinated precooligomers with the parent aromatic compounds. In particular interest, it was demonstrated that fluoroalkoxyl end-capped cooligomer-bound 5-FU could have a remarkably strong interaction with oligoDNA.

Synthesis and surface properties of novel fluoroalkyl end-capped amphiphilic fullerene cooligomers

New fluoroalkyl end-capped fullerene cooligomers were prepared by the reactions of fluoroalkanoyl peroxides with fullerene and comonomers such as acryloylmorpholine, N, N-dimethylacrylamide and acrylic acid. These fluorinated fullerene cooligomers were easily soluble in water and common organic solvents, and were able to reduce the surface tensions of both water and benzene, quite effectively. Additionally, these fullerene cooligomers were found to form a stable monomolecular film at the air–water interface, and the modified polystyrene surface treated with these cooligomers was shown to have a strong hydrophilicity with good oil repellency.

Synthesis and antibacterial activity of novel fluoroalkyl end-capped cooligomers containing dimethyl(octyl)ammonium segments

New fluoroalkyl end-capped cooligomers containing dimethyl(octyl)ammonium segments were prepared by the reactions of fluoroalkanoyl peroxides with 2-(acryloxyethyl)dimethyl(octyl)ammonium chloride (AEMOAC) and comonomers such as N, N-dimethylacrylamide, acrylic acid, and acryloylmorpholine (ACMO). These fluorinated AEMOAC cooligomers thus obtained were in general soluble not only in water but also in organic solvents such as methanol, ethanol, THF, chloroform, DMSO, and DMF. Especially, fluoroalkylated AEMOAC–ACMO cooligomers were readily soluble in these solvents, and were able to reduce the surface tension of water quite effectively with a clear breakpoint resembling a critical micelle concentration, the same as for low-molecular weight fluorinated surfactants. Furthermore, the modified poly(methyl methacrylate) (PMMA) surface treated with these fluorinated AEMOAC–ACMO cooligomers was shown to have a strong hydrophilicity with a good oil repellency. In particular interest, the modified PMMA surface with these cooligomers was clarified to exhibit a high antibacterial activity. Therefore, these new partially fluoroalkylated AEMOAC cooligomers are applicable to new functional materials possessing not only the surface antibacterial activity but also the surface active property imparted by fluorine.

Synthesis and properties of fluoroalkylated end-capped betaine polymers

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 10 g 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. 0.2 g 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.

Synthesis and Properties of Gelling Fluoroalkylated End-Capped Oligomers Containing Hydroxy Segments

Reactions of fluoroalkanoyl peroxides with 3-methacryloxy-2-hydroxypropyltrimethylammonium chloride (MHPTA) or 2-hydroxy-2-[1-oxoprop-2-enyl)amino]acetic acid (HOPPA) were found to give new fluoroalkylated end-capped oligomers containing 2-hydroxypropyltrimethylammonium or carboxy-hydroxymethylamido segments, respectively, under very mild conditions. These fluoroalkylated end-capped oligomers form a highly viscoelastic fluid (“gel-like”) or cause gelation either in water or in polar organic solvents such as MeOH, EtOH, N,N-dimethylformamide (DMF), and dimethyl sulfoxide (DMSO), whose behavior is governed by the synergistical interactions of strong aggregations of fluoroalkyl segments within oligomers and intermolecular hydrogen bonding between hydroxy or carboxy segments under the non-crosslinked conditions. The fluorinated MHPTA oligomer possessing “gel-like” characteristic was able to reduce the surface tension of water effectively to around 15 mN m−1 with a clear break point, resembling critical micell concentration (CMC). These fluoroalkylated MHPTA oligomer hydrogels had strong metal ion binding or releasing power, and exhibited antibacterial activity to some extent against Staphylococcus aureus. They should thus have high potential for new fluorinated functional materials owing to possessing not only common fluorinated properties such as surface activity and biological activity, but also gelling ability by the aggregation of fluoroalkyl segments.

Syntheses and Properties of Fluoroalkylated Oligomers Containing Oligo (oxyethylene) Units

New fluoroalkylated end-capped co-oligomers containing oligo (oxyethylene) units were prepared by reactions of fluoroalkanoyl peroxides with oligo (oxyethylene) units -containing vinylsilane (or methacrylates) and co-monomers such as acrylic acid, dimethylacrylamide and isopropylacry-lamide. By these fluorinated co-oligomers containing oligo (oxyethylene) units, the surface tension of water could be reduced effectively with a clear break point resembling CMC and appeared to be formed intra- or inter molecular aggregates resembling micelles in water. The co-oligomers containing oli-go (oxyethylene) units were found useful for extracting various metal cations and oligomer electrolyte film containing LiCF3SO3 showed high ionic conductivity of 4×10-5S/cm at room temperature. Of particular interest is the finding that the fluoroalkylated end-capped acrylic acid co-oligomers containing oligo (oxyethylene) units were found to strongly and selectively inhibit HIV-1 replication in vitro.

Synthesis of novel fluoroalkylated 4-vinylpyridinium chloride oligomers as functional materials possessing surfactant and biological properties

Perfluoropropylated and perfluoro-oxaalkylated 4-vinylpyridinium chloride oligomers were prepared by the reactions of fluoroalkanoyl peroxides with 4-vinylpyridinium chloride under very mild conditions. A series of fluoroalkylated 4-vinylpyridinium chloride co-oligomers containing carboxyl or trimethylsilyl segments were also obtained by the reactions of fluoroalkanoyl peroxides with 4-vinylpyridinium chloride and acrylic acid or trimethylvinylsilane under similar conditions. These fluoroalkylated homo- and co-oligomers containing carboxyl or trimethylsilyl segments were soluble in water and methanol. Furthermore, these oligomers were able to reduce the surface tension of water to 10–18 mN m −1 levels with a clear break point resembling a CMC (critical micelle concentration), and are applicable to new fluorinated cationic oligosurfactants. Fluoroalkylated co-oligomers were found to possess antibacterial activity against Staphylococcus aureus. In addition, fluoroalkylated co-oligomers containing carboxyl groups were potent and selective inhibitors of HIV-1 (human immunodeficiency virus type 1) in MT-4 cells. Interestingly, one of these fluoroalkylated co-oligomers containing carboxyl groups was clarified to show both antibacterial and anti-HIV-1 activities. Therefore, these oligomers are suggested to have high potential for new functional materials through their surfactant and biological properties.

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

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).

Synthesis of Hydrophilic Fluorosilane Coupling Oligomers Possessing Anti-Human Immunodeficiency Virus Type-1 Activity

New fluoroalkyl end-capped oligomeric silane coupling agents were prepared by reactions of fluoroalkanoyl peroxides with trimethylvinylsilane, trimethoxyvinylsilane and acrylic acid. Fluoroalkylated co-oligomers thus obtained were found to be soluble not only in water but common organic solvents as well. The co-oligomers had a good hydrophilicity with a strong oleophobicity above the surface. They were also noted to possess a potent and selective anti-HIV-1 activity even under crosslinked conditions.