Fluoroalkyl End-capped Acrylic Acid Research Articles

Preparation of Fluoroalkyl End-Capped Oligomers/Hexagonal Boron Nitride Nanocomposites Possessing No Weight Loss Behavior in Nanocomposites Even after Calcination at 800°C

Fluoroalkyl end-capped acrylic acid oligomer [RF-(ACA)n-RF]/hexagonal boron nitride (h-BN) nanocomposites [RF-(ACA)n-RF/h-BN] were prepared by reaction of the corresponding oligomer with h-BN nanoparticles (mean diameter: 50 nm) under non-catalytic or alkaline conditions, respectively. Fluoroalkyl end-capped N,N-dimethylacrylamide oligomer/h-BN nanocomposites [RF-(DMAA)n-RF/h-BN] were also obtained under similar conditions. It was demonstrated that RF-(ACA)n-RF/h-BN nanocomposites, which were prepared under alkaline conditions, afforded a clear weight loss in proportion to the contents of the oligomer in the composites after calcination at 800°C; however, the non-catalytic conditions enabled the RF-(ACA)n-RF/h-BN nanocomposite to give no weight loss behavior corresponding to the contents of the oligomer even after calcination. In fact, it was demonstrated that the RF-(ACA)n-RF/h-BN nanocomposites possessing a clear weight loss property could afford the fluorescent peak around 370 nm related to h-BN in the composites; however, the same fluorescent intensity of this nanocomposite after calcination at 800°C as that of the original h-BN was observed, indicating that this nanocomposite could give a clear weigh loss behavior corresponding to the content of the oligomer during the calcination process. In contrast, the RF-(ACA)n-RF/h-BN nanocomposites possessing no weigh loss behavior were found to exhibit the similar fluorescent intensity before and even after calcination at 800°C, suggesting that the corresponding nanocomposites could provide no weight loss ability corresponding to the contents of the oligomer in the composites even after calcination. Similarly, RF-(DMAA)n-RF/h-BN nanocomposites, which were prepared under non-catalytic or alkaline conditions, were found to provide no weight loss corresponding to the contents of the oligomer even after calcination, respectively. These fluorinated h-BN nanocomposites were applied to the surface modification of PMMA [poly(methyl methacrylate)] to exhibit an oleophobic property on the modified PMMA surface. RF-(ACA)n-RF/h-BN nanocomposites possessing a clear weight loss behavior, whose composites were calcinated at 800°C, afforded not oleophobic but oleophilic property on the modified PMMA surface, quite similar to that of the pristine PMMA film surface; however, more interestingly, we found that RF-(ACA)n-RF/ and RF-(DMAA)n-RF/h-BN nanocomposites possessing no weight loss characteristic, whose composites were calcined at 800°C, could supply a good oleophobic property related to the fluoroalkyl segments in the composites on the modified PMMA surfaces, respectively.

Facile one-pot preparation of gold nanoparticles in the presence of fluoroalkyl end-capped oligomers, fluoroalkyl end-capped oligomers/silica nanocomposites, and fluoroalkyl end-capped oligomers/polyaniline nanocomposites

A variety of fluoroalkyl end-capped oligomers, such as fluoroalkyl end-capped acrylic acid oligomer [RF-(ACA) n -RF], acryloylmorpholine oligomer [RF-(ACMO) n -RF], 2-acrylamido-2-methylpropanesulfonic acid oligomer [RF-(AMPS) n -RF], 2-(methacryloyloxy)ethanesulfonic acid oligomer [RF-(MES) n -RF], and N,N-dimethylacrylamide oligomer [RF-(DMAA) n -RF], were applied to the autoreduction of gold ions to give the corresponding oligomers/gold nanocomposites, of whose sharp plasmon absorption bands are observed around 535 nm. In these fluorinated oligomers, RF-(ACA) n -RF oligomer and RF-(ACMO) n -RF were effective for the one-pot preparation of the gold nanoparticles under very mild conditions; although the other fluorinated oligomers and the corresponding non-fluorinated–(ACMO) n -oligomer were unable to afford the gold nanoparticles. RF-(ACA) n -RF/SiO2 nanocomposites and RF-(ACMO) n -RF/SiO2 nanocomposites, which were prepared by the sol–gel reactions of tetraethoxysilane in the presence of silica nanoparticles and the corresponding oligomers under alkaline conditions, were also applied to the encapsulation of gold nanoparticles into these fluorinated nanocomposite cores through the autoreduction of gold ions at room temperature. Interestingly, these fluorinated oligomers/silica nanocomposite-encapsulated gold nanocomposites before and after calcination at 800 °C were found to exhibit the same plasmon absorption band around 525 nm. RF-(MES) n -RF oligomer and RF-(AMPS) n -RF oligomer are not suitable for the autoreduction of gold ions; however, RF-(MES)n-RF[or RF-(AMPS) n -RF]/polyaniline [PAn] nanocomposites, which were prepared by the polymerization of aniline initiated by ammonium persulfate in the presence of the corresponding oligomer, enabled the formation of gold nanoparticles through the oxidation of PAn in the composites at room temperature. The reversible conformational change of PAn in the nanocomposites from the polyemeraldine salt to the oxidized pernigraniline base was observed during such oxidation process.

Fluoroalkyl end-capped oligomers possessing nonflammable characteristic in calcium carbonate nanocomposites

Calcium chloride reacted with sodium carbonate in the presence of a variety of fluoroalkyl end-capped oligomers such as fluoroalkyl end-capped acrylic acid oligomer (RF-[ACA]n-RF), 2-methacryloyloxyethanesulfonic acid oligomer (RF-[MES]n-RF), N,N-dimethylacrylamide oligomer (RF-[DMAA]n-RF) and acryloylmorpholine oligomer (RF-[ACMO]n-RF) to afford the corresponding fluorinated oligomers/calcium carbonate composites. Each fluorinated oligomer/calcium carbonate composite thus obtained is nanometer size-controlled very fine particles (25–114 nm) possessing a good dispersibility and stability in a variety of solvents including water. Thermal stability of these fluorinated calcium carbonate nanocomposites was studied by thermogravimetic analyses measurements. Fluorinated oligomes, in which the theoretical oligomer content in the composites is 19%, were able to give no weight loss corresponding to the content of oligomer in each case even after calcination at 800 °C. On the other hand, a slight weight loss corresponding to the contents of oligomers in the composites after calcination at 800 °C was observed in RF-(MES)n-RF/, RF-(DMAA)n-RF/ and RF-(ACMO)n-RF/calcium carbonate nanocomposites, in which the theoretical contents of the oligomers were 36–53%, although RF-(ACA)n-RF/calcium carbonate nanocomposites gave a clear weight loss corresponding to the contents of oligomer under similar conditions. Fluorinated oligomers/calcium carbonate nanocomposites possessing no weight loss at 800 °C were applied to the surface modification of poly(methyl methacrylate) (PMMA) to exhibit a good oleophobicity imparted by fluorines on the surfaces. Interestingly, these fluorinated calcium carbonate nanocomposites after calcination at 800 °C were found to exhibit the similar oleophobic characteristic on the modified PMMA surfaces as well as that of the nanocomposites before calcination. Copyright © 2013 John Wiley & Sons, Ltd.

Preparation of novel fluoroalkyl end-capped oligomers/polyaniline and/N,N′-diphenyl-1,4-phenylenediamine nanocomposites

Fluoroalkyl end-capped acrylic acid oligomer [RF-(ACA)n-RF]/, 2-(methacryloyloxy)ethanesulfonic acid oligomer [RF-(MES)n-RF]/, 2-acrylamido-2-methylpropanesulfonic acid oligomer [RF-(AMPS)n-RF]/polyaniline [PAn] nanocomposites were prepared by the polymerization of aniline initiated by ammonium persulfate in the presence of the corresponding oligomers, respectively. These fluorinated oligomers were also applied to the preparation of the corresponding fluorinated oligomers/phenyl-capped aniline dimer (An-dimer: N,N′-diphenyl-1,4-phenylenediamine) nanocomposites by the interaction of the fluorinated oligomers with An-dimer. These fluorinated composites thus obtained were found to afford nanometer size-controlled fine particles possessing a good dispersibility and stability in water and traditional organic media such as methanol. UV–vis spectra of RF-(MES)n-RF/PAn nanocomposites and RF-(AMPS)n-RF/PAn nanocomposites showed the similar absorption peaks around 350, 430, and 780 nm to those of the usual Bronsted acid-doped PAn; however, interestingly, RF-(ACA)n-RF/PAn nanocomposites were found to exhibit only an absorption peak around 430 nm based on the polaron transition.

Preparation of novel cross-linked fluoroalkyl end-capped cooligomeric nanoparticles–encapsulated cytochrome c in water and ionic liquids

Cross-linked fluoroalkyl end-capped acrylic acid cooligomer containing poly(oxyethylene) units can form the nanometer size-controlled fine particles in aqueous solutions, and these cross-linked nanoparticles interact with cytochrome c (Cyto-c) to afford the corresponding cooligomeric nanoparticles–encapsulated Cyto-c effectively. Interestingly, we can easily isolate the fluorinated nanoparticles–encapsulated Cyto-c powder by the simple centrifugal separation of the corresponding aqueous solutions. The cross-linked fluorinated cooligomer also enables an effective transfer of Cyto-c from aqueous solution to ionic liquids such as 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide to afford the immobilized Cyto-c with the corresponding fluorinated cooligomer in quantitatively immobilized ratio (∼100%). The immobilized Cyto-c exhibited a good dispersibility in the parent ionic liquid to afford the nanometer size-controlled fluorinated particles–encapsulated Cyto-c. Similarly, the cross-linked fluorinated cooligomer in ionic liquids such as 3-methylpyrazolium tetrafluoroborate (3MP-BF4) interacted with Cyto-c to afford the corresponding nanoparticles–encapsulated Cyto-c in quantitatively encapsulated ratio (∼100%). These cross-linked fluorinated nanoparticles–encapsulated Cyto-c in water and ionic liquids were applied to the oxidation of guaiacol with hydrogen peroxide, and an extremely higher catalytic activity for this oxidation was observed in the ionic liquid (3MP-BF4).

Surface Modification of Aluminum Plate with Fluoroalkyl End-capped Acrylic Acid Oligomer/silica Nanocomposites— Oleophobic to Hydrophilic Switching Behavior Adapted to the Environmental Change on the Modified Plate Surface

Surface Modification of Aluminum Plate with Fluoroalkyl End-capped Acrylic Acid Oligomer/silica Nanocomposites— Oleophobic to Hydrophilic Switching Behavior Adapted to the Environmental Change on the Modified Plate Surface

Preparation and applications of a variety of fluoroalkyl end-capped oligomer/hydroxyapatite composites

A variety of fluoroalkyl end-capped oligomers were applied to the preparation of fluorinated oligomer/hydroxyapatite (HAp) composites (particle size: 38–356 nm), which exhibit a good dispersibility in water and traditional organic solvents. These fluoroalkyl end-capped oligomer/HAp composites were easily prepared by the reactions of disodium hydrogen phosphate and calcium chloride in the presence of self-assembled molecular aggregates formed by fluoroalkyl end-capped oligomers in aqueous solutions. In these fluorinated HAp composites thus obtained, fluoroalkyl end-capped acrylic acid oligomers and 2-methacryloyloxyethanesulfonic acid oligomer/HAp nanocomposites afforded transparent colorless solutions toward water; however, fluoroalkyl end-capped N , N -dimethylacrylamide oligomer and acryloylmorpholine oligomer were found to afford transparent colorless solutions with trace amounts of white-colored HAp precipitants under similar conditions. HAp could be encapsulated more effectively into fluorinated 2-methacryloyloxyethanesulfonic acid oligomeric aggregate cores to afford colloidal stable fluorinated oligomer/HAp composites, compared to that of fluorinated acrylic acid oligomers. These fluorinated oligomer/HAp composites were applied to the surface modification of glass and PVA to exhibit a good oleophobicity imparted by fluorine. HAp formation was newly observed on the modified polyethylene terephthalate film surface treated with fluorinated 2-methacryloyloxyethanesulfonic acid oligomers and acrylic acid oligomer/HAp composites by soaking these films into the simulated body fluid.

Dispersion of single-walled carbon nanotubes in water by the use of novel fluorinated dendrimer-type copolymers

New fluorinated dendrimer-type block copolymers were applied to the dispersion of single-walled carbon nanotubes (SW-CNTs) and single-walled carbon nanotubes containing carboxy groups [(SW-CNT)-COOH] in water. Fluorinated block copolymer could disperse SW-CNTs more effectively in water, compared to that of the corresponding ABA triblock-type fluoroalkyl end-capped dimethylacrylamide oligomer [RF-(DMAA)n-RF]. Dynamic light-scattering (DLS) measurements and transmission electron microscopy (TEM) images show that SW-CNTs could be smoothly encapsulated into fluorinated copolymeric aggregates cores. Interestingly, it was demonstrated that SW-CNTs could be in part released from the fluorinated copolymeric aggregates/SW-CNTs composites or encapsulated into these composites with increasing the dispersion times. On the other hand, fluorinated block copolymer and RF-(DMAA)n-RF oligomer were not able to disperse well (SW-CNT)-COOH in water; however, ABA triblock-type fluoroalkyl end-capped acrylic acid oligomer was able to disperse quite effectively (SW-CNT)-COOH in water.

Preparation of fluoroalkyl end-capped cooligomers/silica nanoparticles: A new approach to fluorinated nanoparticle inhibitors of Human Immunodeficiency Virus Type 1 and Simian Immunodeficiency Virus (SIV mac)

Fluoroalkyl end-capped acrylic acid and sulfonic acid cooligomers reacted with tetraethoxysilane (TEOS) and silica/nanoparticles under alkaline conditions to afford the corresponding cooligomers/silica nanoparticles (mean diameters: 32–173 nm) with a good dispersibility and stability in aqueous and organic media. Interestingly, fluorinated nanoparticles containing carboxy groups were found to exhibit a potent and selective anti-HIV-1 activity in vitro. In contrast, fluorinated cooligomers containing sulfo groups were shown to have a potent and selective anti-SIV mac activity in vitro.

Preparation and Applications of Novel Fluoroalkyl End-Capped Acrylic Acid Oligomers/Silica Nanocomposites-Encapsulated Fullerenes

Fluoroalkyl end-capped acrylic acid oligomers/fullerenes nanocomposites reacted smoothly with tetraethoxysilane (TEOS) and silica nanoparticles under alkaline conditions to give fluoroalkyl end-capped oligomers/silica composites-encapsulated fullerenes. Interestingly, these isolated fluorinated composites were found to afford nanometer size-controlled colloidal particles with a good dispersibility in a variety of organic solvents including water. More interestingly, these fluorinated silica nanocomposites-encapsulated fullerenes were applied to a new type of surface modification agent, and these nanocomposites were able to disperse well above the poly(methyl methacrylate) films to exhibit not only surface active property imparted by fluorine but also a unique characteristic related to fullerenes in the nanocomposites on the surface, effectively.

Preparation and applications of novel fluoroalkyl end-capped oligomers/calcium carbonate nanocomposites

Calcium chloride reacted with sodium carbonate in the presence of a variety of self-assembled molecular aggregates formed by fluoroalkyl end-capped acrylic acid, 2-methacryloyloxyethane sulfonic acid, dimethylacrylamide, and acryloylmorpholine oligomers in aqueous solutions to afford the corresponding fluorinated oligomers/calcium carbonate composites in excellent to moderate isolated yields. These fluorinated calcium carbonate composites thus obtained were shown to have a good dispersibility not only in water but also in traditional organic media including fluorinated solvents. Dynamic light scattering measurements (DLS), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) showed that these fluorinated composites are nanometer-size-controlled particles and well dispersed in these media. Cross-linked fluoroalkyl end-capped acrylic acid co-oligomer containing poly(oxyethylene) units was also applied to the preparation of new cross-linked fluorinated calcium carbonate nanocomposites under similar conditions. The obtained cross-linked fluorinated calcium carbonate nanocomposites were found to have an extremely higher dispersibility in aqueous and organic media including fluorinated solvents, compared to that of the corresponding fluoroalkyl end-capped oligomer nanocomposites. In particular, it was verified that these fluorinated calcium carbonate nanocomposites are applicable to the dispersion above poly(methyl methacrylate) (PMMA) film surface. Interestingly, field-emission SEM (FE-SEM) images of the cross-section of the modified PMMA films showed that calcium carbonate particles dispersed into these PMMA films could be arranged regularly above the modified film surface. More interestingly, cross-linked fluorinated oligomeric aggregates were able to provide suitable host moieties for the crystallization of calcium carbonate.

Solubilization and applications of single-walled carbon nanotubes into aqueous and organic media by the use of nanometer size-controlled fluoroalkyl end-capped oligomeric aggregates

We have studied on the solubilization of single-walled carbon nanotubes (SW-CNTs) into aqueous and organic media by the use of a variety of nanometer size-controlled fluorinated self-assemblies, which were formed by the aggregations of end-capped fluoroalkyl segments in fluoroalkyl end-capped acrylic acid oligomers [R F–(ACA) n –R F], N, N-dimethylacrylamide oligomers [R F–(DMAA) n –R F], acryloylmorpholine oligomers [R F–(ACMO) n –R F], and N-(1,1-dimethyl-3-oxobutyl)acrylamide oligomers [R F–(DOBAA) n –R F]. Fluorinated self assemblies formed in organic media (colorless solutions) could solubilize SW-CNTs into organic media to afford the transparent pale yellow solutions. The dynamic light scattering measurements showed that the size of fluorinated self-assemblies increased after the solubilization of SW-CNTs into organic media. It was suggested that the solubilization of SW-CNTs into organic media is due to the encapsulation of SW-CNTs into fluorinated assemblies. Fluorinated assemblies were also able to solubilize SW-CNTs into water to give the transparent gray solutions. Among a variety of fluorinated assemblies, fluorinated assemblies formed by R F–(ACMO) n –R F [R F = CF(CF 3)OC 6F 13] oligomer was more effective for the solubilization of SW-CNTs into both aqueous and organic media. Contact angle measurements of dodecane and the fluorescence spectra for poly(methyl methacrylate) cast film modified by fluorinated self-assemblies—SW-CNTs complexes showed that SW-CNTs are dispersed above the PMMA surface.

Preparation of magnetic nanoparticles by the use of self-assembled fluorinated oligomeric aggregates—A new approach to the dispersion of magnetic particles on poly(methyl methacrylate) film surface

Fluoroalkyl end-capped acrylic acid oligomer-encapsulated magnetic nanoparticles were prepared by the coprecipitation of aqueous ferric and ferrous ions in the presence of the corresponding oligomers under alkaline conditions. The dynamic light scattering measurements showed that these fluorinated oligomer magnetic nanoparticles were encapsulated in the self-assemblies of fluoroalkyl end-capped oligomers. Fluoroalkyl end-capped oligomer-encapsulated magnetic nanoparticles thus obtained were applied to the dispersion of magnetic particles on the poly(methyl methacrylate) film surface to exhibit not only the surface active property imparted by fluorine but also magnetic behavior toward a permanent magnet.

DISSOLUTION OF CARBON NANOTUBES IN WATER AND ORGANIC MEDIA WITH A VARIETY OF FLUOROALKYL END-CAPPED OLIGOMERS

Dissolution of single-wall carbon nanotube (SW-CNT) in water and organic media was studied by the use of fluoroalkyl end-capped acrylic acid oligomers [RF‒(ACA)n‒RF], N,N-dimethylacrylamide oligomers [RF‒(DMAA)n‒RF], acryloyl-morpholine oligomers [RF‒(ACMO)n‒RF], and N-(1,1-dimethyl-3-oxobutyl) acrylamide oligomers [RF‒(DOBAA)n‒RF]. Among these fluorinated oligomers, it was demonstrated that RF‒(ACMO)n‒RF; RF˭CF(CF3)OC6F13] oligomer is more effective for the dissolution of SW-CNT in both aqueous and organic media. Additionally, it was demonstrated that RF‒(DOBAA)n‒RF oligomer is a convenient tool for the arrangement of SW-CNT on PMMA surface.