Characterization of a low-wettable surface based on perfluoroalkyl acrylate copolymers

The low-wettable surfaces based on perfluoroalkyl acrylate (FA)/n-alkyl acrylate copolymers with various amounts of FA units were presented to analyze their surface properties. The FA copolymers were prepared by soap-free emulsion polymerization in the presence of sodium 2-acrylamide-2-methyl propanesulfonate (AMPSNa) used as a reactive surfactant. Low-wettability properties resulted from the self-assembly of fluorine-containing side chains, surface density and extent of orientation of perfluoroalkyl (R_F) groups. The wetting behavior of the low-wettable surfaces was discussed from a standpoint of dynamic contact angles measurement, which implied an enrichment of perfluoroalkyl groups on the topmost surface. Increased R_F surface densities and orientation, measured by attenuated total reflectance spectra of infrared (ATR-IR), X-ray photoelectron spectroscopy (XPS) and scanning force microscopy (SFM), respectively, were consistent with higher angles.     

A metal-free three components procedure for the synthesis of perfluoroalkyl substituted amidines

An interesting multicomponent reaction for the synthesis of perfluoroalkyl substituted amidines has been developed. By using perfluoroalkyl iodides, tert-butyl isocyanides and amines as the substrates, the reactions proceed via somophilic isocyanide insertion. In this catalytic system, no transition-metal catalyst, additional ligands and additives were required. The reaction proceed smoothly and a variety of desired amidines were obtained in moderate to excellent yields.     

Indium-mediated radical addition of perfluoroalkyl iodide in water

Reaction of perfluoroalkyl groups with carbon-carbon unsaturated compounds using indium in water proceeded smoothly to provide the addition products in high yields.     

One-step synthesis of epoxy(perfluoroalkyl)alkenes

Epoxy(perfluoroalkyl)alkenes were synthesized in one step by reaction of perfluoroalkyl iodides with 2-(allyloxymethyl)oxirane and 2-(oct-7-en-1-yl)oxirane in the presence of sodium dithionite and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) under mild conditions.     

Redox system for perfluoroalkylation of arenes and α-methylstyrene derivatives using titanium oxide as photocatalyst

Photoirradiation of titanium oxide (TiO₂) excites the electrons from the valence band to the conduction band, leaving holes in the valence band. Using these holes and electrons, it is possible to perform one-electron oxidations and reductions. We developed a method for the photocatalytic perfluoroalkylation of aromatic rings such as benzene and its derivatives, naphthalene and benzofuran with perfluoroalkyl iodide by the combination of reduction and oxidation reactions with TiO₂. Perfluoroalkyl iodide was reduced to a perfluoroalkyl radical by the excited electrons in the conduction band of TiO₂, and the resulting radical reacted with an aromatic ring to form an arenium radical that was successively oxidized to a cation by the holes in the valence band of TiO₂. Similarly, the photocatalytic reaction of α-methylstyrene with perfluoroalkyl iodide afforded perfluoroalkylated α-methylstyrene, in which the perfluoroalkyl group is on a methyl carbon.     

Synthesis, structure and properties of intercalation compounds containing perfluoroalkyl groups

Synthesis, structure and properties of various layered materials containing perfluoroalkyl groups in their interlayer space were summarized. They were obtained by ion exchange method for layered materials with ion exchange capacity and by silylation technique for those possessing acidic hydroxyl groups. The orientation of perfluoroalkyl groups greatly changed depending on their contents in the layered materials. The nature of the interlayer space of them changed from hydrophilic to hydrophobic and they were well dispersed in appropriate organic solvents. Some of them formed so called nanosheet solution and film samples were prepared from it. Organic molecules were introduced into the intercalation compounds by co-adsorption or exfoliation-restacking methods. The empty space surrounded by perfluoroalky chains where organic molecules are included showed unique properties. The weak interaction between perfluoroalkyl chains and included organic molecules lead the easy diffusion of them in the interlayer space, which caused the aggregation of them or affected the distribution of isomers obtained by photochemical reaction. The low vibrational C-F bonding in perfluoroalky groups reduced radiational quenching, accordingly enhanced the fluorescence from included organic dyes.     

An on-line solid phase extraction-liquid chromatography tandem mass spectrometry method for the determination of perfluoroalkyl substances in the Antarctic ice core samples

An on-line solid phase extraction-high performance liquid chromatography-tandemmass spectrometry method for the analysis of perfluoroalkyl substances (PFASs) in water samples was developed. The optimal analytical conditions were obtained through the optimization of the extraction efficiency of online solid phase extraction column, sample loading rate and loading volume, and the concentration of ammonium acetate in mobile phase. Under the optimal condition, the analytical method displayed good linearity (r² > 0.99) for 12 PFASs (C5-C14 perfluoroalkyl carboxylic acids and C6/C8 perfluoroalkyl sulfonic acids) over a concentration range of 0.5-100 ng/L. The limits of quantitation for samples were between 0.025 ng/L and 0.5 ng/L and the relative standard deviations (RSD) of five consecutive analyses were less than 10% for 1 ng/L standard solution. Satisfactory results were obtained using this analytical method for the analysis of perfluoroalkyl substances in Antarctic ice core samples. The recoveries of all perfluoroalkyl substances were in a range of 73%-117% when the sampleswere spiked with standards at the concentrations of 2.5 ng/L and 25 ng/L.     

Evaluation of the hydrophobicity of perfluoroalkyl chains in amphiphilic compounds that are incorporated into cell membrane

Incubation of animal cells in the presence of amphiphilic glycosides having a lactoside residue (hydrophilic moiety) and various kinds of perfluoroalkyl chain (hydrophobic moiety) resulted to glycosylation of the saccharide chain by cellular enzymes and afforded glycolipid-like compounds. The amounts of amphiphilic glycoside and glycolipid-like compounds found in the cell and culture medium fractions, respectively, varied depending on the fluorine content of the perfluoroalkyl chain. To investigate further, the hydrophobicity of the perfluoroalkyl chain was estimated from the critical micelle concentration values and was found to be 1.5 times larger in hydrophobicity than the hydrocarbon chain [CF₂ = 1.5CH₂]. Liposomes resembling cells in size were also prepared and the amphiphilic glycosides were introduced. Results showed a positive correlation between hydrophobicity and localization of amphiphilic glycoside into liposomes. The amount of amphiphilic glycosides localized in liposomes increased with increasing hydrophobicity that is attributed mainly to the fluorine content of the aglycon. In spite of the low affinity of fluorous chain for hydrocarbon chain, the amphiphilic fluorous compounds showed high affinity for cell membrane that is composed of amphiphilic phospholipids.     

Studies on the reactions of silyl enol ether with perfluoroorganic compounds I. The reaction of silyl enol ether with perfluoroalkyl iodide

The reaction of silyl enol ethers ( 1a-1e ) with perfluoroalkyl iodides ( 2f–2k ) initiated with sodium dithionite was studied. α-Perfluoroalkyl ketones (3) were synthesized in excellent yield by this method. α, β-Unsaturated fluorinated ketones (4) were obtained easily by dehydrofluorination of the α-perfluoroalkyl ketones. A radical mechanism was proposed.     

Enthalpic and polar effects in the reactions of perfluoroalkyl radicals: New selective synthetic developments with alkenes and heteroaromatic bases

Perfluoroalkyl radicals, generated by iodine abstraction from perfluoroalkyl iodides by phenyl radical, react with low selectivity with protonated heteroaromatic bases, due to their electrophilic character and the prevalent enthalpic effect on the reaction. In the presence of alkenes, perfluoroalkyl radicals add very rapidly to the double bond and the polar character of the radical adduct is reversed, allowing the selective substitution of protonated heteroaromatic bases. The mechanism of the reaction and the key role of enthalpic and polar effects are discussed.     

Stability of perfluoroalkyl halide emulsions

The stability of oil-in-water emulsions of several perfluoroalkyl chlorides and bromides stabilized by sodium dodecylsulphate (SDS) has been examined. It has been shown that introducing the above substituents in the molecules of fluorocarbons only slightly affects the stability of their emulsions; on the contrary, their lipophilicity and, presumably, excretion rate from the human body are substantially increased.     

Effect of the perfluoroalkyl groups on the preparation of carbon-based transparent and conductive thin films from silylated graphite oxides

Carbon-based transparent thin films were prepared from the pyrolysis of silylated graphite oxide containing perfluoroalkyl groups. The saturated amount of n-hexadecylamine molecules which accommodated between the layers of silylated graphite oxide containing larger pefluoroalkyl groups was smaller than that observed for silylated graphite oxide without perfluoroalkyl groups. The resulting intercalation compounds were dispersed in a chloroform/cyclohexane solution and precursor thin films were obtained by a cast method. The sheet resistance of the obtained carbon-based films was about 5 times smaller than that of the films prepared from silylated graphite oxide prepared with the analogous hydrocarbon substituents. The spectroscopic measurements indicated that the number of defects within the carbon layers was larger, however, that of carbon atoms participating π-conjugating system was larger. This probably ascribed to the active fluorine species formed as the result of thermal decomposition of perfluoroalkyl groups. The latter was responsible for the lower sheet resistance of carbon-based thin films.     

Synthesis and characterization of a new class of polyfluorinated alkanes: tetrakis(perfluoroalkyl)alkane

The synthesis and physico-chemical characterization of 1,1,2,2-tetrakis(perfluoroalkyl-methylene)ethane {[F(CF₂)_nCH₂]₂CH}₂ (n=6, TK6; n=8, TK8) are reported. The synthesis consists of four steps: (1) addition of allyl alcohol to a perfluoroalkyl iodide, F(CF₂)_nI (n=6,8) to give the corresponding iodo-adduct; (2) dehalogenation of the adduct by treatment with zinc in aqueous acetic acid, yielding 3-perfluoro-n-alkyl-1-propene; (3) addition of 3-perfluoro-n-alkyl-l-propene to perfluoroalkyl iodide, F(CF₂)_nI (n=6,8) to give 1,3-perfluoro-n-alkyl-2-iodo-propane; (4) coupling of 1,3-perfluoro-n-alkyl-2-iodo-propane by zinc in acetic anhydride giving the final products. TK6 and TK8 are characterized by very low surface tension values and exhibit very good properties as potential ski-waxes.     

A new method for the preparation of α-(perfluoroalkyl) carbonyl and γ-(perfluoroalkyl)-α,β-unsaturated carbonyl compounds

R_fI(Ph)OSO₂CF₃ or R_fI(Ph)OSO₃H smoothly reacted with various trimethylsilyl enol ethers under mild conditions to give α-(perfluoroalkyl) carbonyl and γ=(perfluoroalkyl)-α,β-unsaturated carbonyl compounds in high yields.     

Synthesis of 2-(perfluoroalkyl)ethyl potassium sulfates based on perfluorinated Grignard reagents

The first example of nucleophilic substitution with perfluoroalkyl Grignard reagents on the sp³ carbon centre is described. Thus, a series of organometals R_F-MgBr, prepared from perfluorinated alkyl iodides R_F-I with R_F = C₄F₉, C₆F₁₃, C₈F₁₇, C₁₀F₂₁ and C₁₂F₂₅, reacted with 1,3,2-dioxathiolane-2,2-dioxide to afford the corresponding 2-(perfluoroalkyl)ethyl magnesium sulfates, which were isolated after metathesis to the corresponding potassium salts. In the model reaction, perfluorohexylmagnesium iodide was reacted with methyl triflate yielding polyfluorinated alkane. The attempts to extend the reaction to 1,3,2-dioxathiane-2,2-dioxide were unsuccessful due to its inferior reactivity and only reduced polyfluoroalkane and the product of coupling were detected in the reaction mixture. Polyfluorinated sulfates are easily hydrolyzed with hydrochloric or triflic acid to the corresponding alcohols, which is an alternative to standard transformation of perfluoroalkyl iodides to 2-(perfluoroalkyl)ethanols. Quantum-chemical calculations of the PES of the reaction with both sulfur-containing heterocycles found that the failure of the reaction with 1,3,2-dioxathiane-2,2-dioxide is caused by higher activation energy of the process.     

Synthesis of 2,3-bis(perfluoroalkyl)quinoxalines and 2,3-bis(perfluoroalkyl)-1,4-benzoxazines from oxides of internal perfluoroolefins

The reactions of oxides of internal trans-, cis-perfluoroolefins with o-phenylenediamine and 2-aminophenol in dioxane gave 2,3-bis(perfluoroalkyl)quinoxalines and 2,3-bis(perfluoroalkyl)-2H-1,4-benzoxazin-2-ols respectively in yields of 23-67%. When N,N-dimethylacetamide was used as a solvent an anionic isomerization of the oxides into ketones, which further yielded 2-(perfluoroalkyl)benzimidazoles in the case of o-phenylenediamine and 2-hydroxy-N-perfluoroalkanoylanilines in the case of 2-aminophenol, became the main path of these reactions. Unusual cyclization resulting in 2-pentafluoroethyl-2-pentafluoropropanoylbenzoxazolidine occurs on interaction between dodecafluoro-3,4-epoxyhexane and 2-aminophenol in N,N-dimethylacetamide.     

高效液相色谱-三级四级杆质谱测定食品接触材料中6种全氟羧酸类化合物

采用高效液相色谱-串联质谱仪建立了食品接触材料中6种全氟羧酸类化合物(PFCAs)残留量的检测方法。通过对超声、振荡和离子配对3种方法的比较,选择超声法作为提取食品接触材料中PFCAs的提取方法,提取时间为30 min,提取溶剂体积为10 mL。提取物经C18色谱柱分离后由串联质谱检测。最低检测限为0.5μg/kg,添加回收率在84.6%～114.6%之间。     

Asymmetric reduction of perfluoroalkyl ketones with chiral lithium alkoxides

Reduction of perfluoroalkyl ketones with chiral lithium alkoxides gave chiral α-perfluoroalkyl alcohols in high enantiomeric excesses. Interestingly, reaction of 2,2,2-trifluoroacetophenone (1) with lithium (S)-1-phenylethoxide (2) gave (S)-2,2,2-trifluoro-1-phenylethanol (3), while the same reaction of perfluorooctan-1-one (7) with 2 gave (R)-1H-1-phenylperfluorooctanol (8). Based on the speculation of mechanism, the order of steric effects on this reaction is estimated as C₇F₁₅ > substituted phenyl > CF₃.     

Brønsted acidic imidazolium salts containing perfluoroalkyl tails catalyzed one-pot synthesis of 1,8-dioxo-decahydroacridines in water

One-pot three-component synthesis of 1,8-dioxo-9,10-diaryl-decahydroacridines in water was efficiently realized in the presence of the Brønsted acidic imidazolium salts containing perfluoroalkyl tails in good yields. The method provided several advantages such as low catalyst loading; recycle of the catalyst and simple work procedure.     

Sequential perfluoroalkylation and asymmetric reduction of nitriles triggered with perfluoroalkyl titanates: catalytic asymmetric synthesis of perfluoroalkyl amines

Highly enantio-enriched perfluoroalkyl amines are shown to be synthesized by perfluoroalkylation and asymmetric reduction of nitriles. Perfluoroalkylation of nitriles can be attained by the Lewis acidic perfluoroalkyl titanate reagents to give acyclic ketimines. Catalytic asymmetric hydrogenation of the acyclic ketimines affords the perfluoroalkyl amine products in up to 93% ee.