Fluoroalkanoyl Peroxides Research Articles

Synthesis and properties of fluoro-alkylated end-capped acrylamide oligomers

New fluoro-alkylated end-capped acryloylmorpholine (ACMO), N, N-dimethylacrylamide (DMAA) and N-isopropylacrylamide (NIPAM) homo-oligomers were prepared by the reactions of the corresponding monomers with fluoro-alkanoyl peroxides under very mild conditions. Furthermore, fluoro-alkylated end-capped acryloylmorpholine co-oligomers were prepared by the co-oligomerizations with comonomers such as DMAA and NIPAM under similar conditions. It was found that these fluorinated oligomers, thus, obtained are soluble not only in water but also in common organic solvents such as methanol, ethanol, tetrahydrofuran, ethyl acetate, benzene, toluene, xylene, chloroform, tetrachloromethane, dichloromethane and acetone, although fluoro-alkylated NIPAM homo-oligomers are insoluble in water. Interestingly, these fluorinated acrylamide oligomers were able to reduce the surface tension of water and m-xylene quite effectively with a clear breakpoint resembling a critical micelle (or reverse micelle) concentration around 15 and 10 mN/m levels, respectively, which are almost the same levels as that achieved by the usual low molecular weight fluorinated surfactants. This suggests that these fluoro-alkylated end-capped acrylamide oligomers could form the intra- or inter-molecular aggregates with the aggregations of end-capped fluoro-alkyl segments in aqueous and m-xylene solutions. More interestingly, fluoro-alkylated end-capped acryloylmorpholine homo- and co-oligomers were found to have an extremely high calcium ion binding power, compared to traditional organic chelating agents and the corresponding non-fluorinated oligomers. These fluorinated oligomers were also able to transfer alkali metal and heavy metal ions from aqueous solutions into organic media. Therefore, these acrylamide oligomers are suggested to have high potential for new fluorinated materials through their surfactant and metal ion binding properties.

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 Fluoroalkylated End-capped Oligomers Containing Hydroxy and Dihydroxy Segments

New fluoroalkylated end-capped oligomers containing hydroxy and dihydroxy segments were prepared by reactions of N- (2-hydroxypropyl) methacrylamide (HPMA) and N, N- (2, 2-dihydroxyethyl) acrylamide (DHEAA) with fluoroalkanoyl peroxides as key intermediates, respectively. Perfluorooxaalkylated end-capped HPMA oligomers thus obtained were soluble in organic polar solvents such as methanol, ethanol and tetrahydrofuran. Perfluoro-1-methyl-2-oxapentylated HPMA oligomer became slightly soluble in water as well as these organic polar solvents and GPC analysis of the HPMA oligomer indicated molecular aggregates to possibly form in water. Fluoroalkylated end-capped DHEAA oligomers were readily soluble not only in water but polar solvents such as methanol and ethanol. The fluorinated DHEAA oligomers were capable of reducing the surface tension of water effectively with a clear breakpoint resembling the critical micelle concentration and had an extremely high calcium ion binding power compared to traditional polymeric chelating agents [poly (acrylic acid)] and the corresponding nonfluorinated oligomer.

フッ素の凝集効果が発現された新しい分子集合体の構築と応用

It was demonstrated that a series of fluoroalkylated end-capped oligomers containing various functional segments such as carboxy, amide, betaine, and hydroxy groups can be prepared by the use of fluoroalkanoyl peroxides as key intermediates. These thus-obtained fluoroalkylated end-capped oligomers were soluble in water and organic solvents, and were capable of reducing the surface tension of water effectively with a clear break point resembling a CMC, which is almost the same level as that achieved by the usual low molecular weight fluorinated surfactants. This is a unique and interesting feature of our fluoroalkylated end-capped oligo-surfactants. Furthermore, fluoroalkylated end-capped oligomers were suggested to form the molecular assemblies imparted by strong aggregation of the fluoroalkylated end-groups in aqueous solutions, and fluoroalkylated end-capped acrylic acid and sulfonic acid oligomers were also shown to be potent and selective inhibitors of human immunodeficiency virus type 1 (HIV-1) in vitro. More interestingly, fluoroalkylated end-capped oligomers containing betaine or hydroxy segments could cause gelation, where the synergistic interactions of both the strong aggregation of the end-capped fluoroalkyl segments and the ionic or hydrogen-bonding interaction are involved in establishing a gel network in water and polar organic solvents.

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.

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 End-Capped Oligomers Containing Triol Segments under Non-Crosslinked Conditions, and Binding or Releasing of Metal Ions by These Oligomers

Abstract New fluoroalkylated end-capped oligomers containing triol segments were prepared by the reactions of N-tris(hydroxymethyl)methylacrylamide and fluoroalkanoyl peroxides. Under the non-crosslinked conditions, these fluoroalkylated oligomers were 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. Therefore, it was demonstrated that the aggregation of the end-capped fluoroalkyl segments in water and/or in organic media become a new driving factor for gelation as well as such well-known interactions as the hydrogen bond and ionic interaction. These thus-obtained fluorinated oligomer hydrogels had a high Cr3+ or Co2+ binding power, and the metal ions were easily released from the metal ions-bound oligomers into water.

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

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 of novel fluoroalkyl end-capped N-vinyl-2-pyrrolidone-acrylic acid co-oligomers by use of fluoroalkanoyl peroxides, and their properties

The reaction of a fluoroalkanoyl peroxide with N-vinyl-2-pyrrolidone was initiated by single electron transfer from the substrate to peroxide to afford the 11 adduct (fluoroalkylated N-vinyl-2-pyrrolidone); however, in the presence of acrylic acid, this peroxide afforded a fluoroalkylated N-vinyl-2-pyrrolidone-acrylic acid co-oligomer via a radical process under very mild conditions. The fluorinated co-oligomers thus obtained were soluble not only in water but also in polar organic solvents such as methanol, ethanol, N,N′-dimethylformamide and dimethylsulfoxide, and were able to reduce effectively the surface tension of water. Furthermore, these co-oligomers showed a high calcium binding power compared to common organic chelating agents, and exhibited antibacterial activity to some extent (from 10 8 to 10 6 colony forming units levels) against Staphylococcus aureus.

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).

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

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 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.

Synthesis and surfactant properties of fluoroalkylated sulfonic acid oligomers as a new class of human immunodeficiency virus inhibitors

New fluoroalkylated 2-(methacryloxy ) ethane sulfonic acid homo-oligomers were prepared in excellent to moderate yields by the reactions of fluoroalkanoyl peroxides with 2-(methacryloxy) ethane sulfonic acid (MES) under very mild conditions. These fluoroalkylated oligomers were easily soluble not only in water but also in polar solvents such as methanol, ethanol, N,N-dimethylformamide and dimethyl sulfoxide. These oligomers were able to reduce the surface tension of water to around 18 mN m −1, and had a clear breakpoint resembling a CMC (critical micelle concentration). These fluoroalkylated homo-oligomers were also shown to be potent and selective inhibitors of human immunodeficiency virus type 1 (HIV-1 ) in vitro, and were about 10-times more inhibitory to HIV-1 than dextran sulfate. Furthermore, a series of fluoroalkylated 2-( methacryloxy )ethanesulfonic acid co-oligomers containing dimethylsilicone, trimethylsilyl and alkyl segments were prepared by the reactions of fluoroalkanoyl peroxides with MES and the corresponding monomers. These co-oligomers had a similar solubility and anti-HIV-1 activity to those of the corresponding homo-oligomer.

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

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.

Synthesis of fluoroalkylated N-vinyl-2-pyrrolidone–acrylic acid cooligomers from fluoroalkanoyl peroxides; a receptor for binding free calcium ions

New fluoroalkylated N-vinyl-2-pyrrolidone–acrylic acid cooligomers are prepared by treating fluoroalkanoyl peroxides with N-vinyl-2-pyrrolidone (NVP) and acrylic acid (ACA); these fluoroalkylated cooligomers reduce the surface tension of water and have a high calcium ion binding power compared to traditional organic chelating agents.

Fluoroalkylated Oligo-Surfactants

Synthesis and properties of a series of fluoroalkylated oligomers by using fluoroalkanoyl peroxides have been reviewed. The synthetic methods of fluoroalkylated acrylic acid, nonionic, and cationic oligomers were illustrated. These fluoroalkylated oligomers, in particular, fluoroalkylated acrylic acid, nonionic, and cationic oligomers were in general shown to become soluble not only in water but also in common organic solvents such as methanol, ethanol, dimethyl sulfoxide, benzene and toluene. These fluoroalkylated oligomers have quite unique structure that fluoroalkyl groups are substituted only on the both terminals of oligomer chain, and can be regarded as double-chain type surfactant. They exhibit excellent surface active properties attributable to fluoroalkyl groups, such as quite low surface and interfacial tension, and anti-foaming property, and so on.Fluoroalkylated acrylic acid homo-and co-oligomers were demonstrated to exhibit a potent anti-HIV-1 activity in vitro. Furthermore, fluoroalkylated cationic oligomers were found to have an antibacterial activity. Therefore, these fluoroalkylated acrylic acid and cationic oligomers have been widely applicable to various fields as the novel functional materials which possess both a unique property imparted by fluorine and an anti-HIV-1 or antibacterial activity.

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.

Synthesis and Surface Properties of Novel Fluoroalkylated Flip-Flop-Type Silane Coupling Agents

New fluoroalkylated oligomeric silane coupling agents containing morpholino groups were prepared by the reactions of fluoroalkanoyl peroxides with trimethoxyvinylsilane and acryloylmorpholine. The modified glass surface treated with these silane coupling agents was shown to have a strong hydrophilicity with good oil repellency, and these fluoroalkylated oligomers are applicable to new flip-flop-type silane coupling agents.