Partitioning of perfluorooctanoate into phosphatidylcholine bilayers is chain length-independent.

The chain length dependence of the interaction of PFOA, a persistent environmental contaminant, with dimyristoyl- (DMPC), dipalmitoyl- (DPPC) and distearoylphosphatidylcholine (DSPC) was investigated using steady-state fluorescence anisotropy spectroscopy, differential scanning calorimetry (DSC) and dynamic light scattering (DLS). PFOA caused a linear depression of the main phase transition temperature T(m) while increasing the width of the phase transition of all three phosphatidylcholines. Although PFOA's effect on T(m) and the transition width decreased in the order DMPC>DPPC>DSPC, its relative effect on the phase behavior was largely independent of the phosphatidylcholine. PFOA caused swelling of DMPC but not DPPC and DSPC liposomes at 37 degrees C in the DLS experiments, which suggests that PFOA partitions more readily into bilayers in the fluid phase. These findings suggest that PFOA's effect on the phase behavior of phosphatidylcholines depends on the cooperativity and state (i.e., gel versus liquid phase) of the membrane. DLS experiments are also consistent with partial liposome solubilization at PFOA/lipid molar ratios>1, which suggests the formation of mixed PFOA-lipid micelles.

[1]  K. Tappura,et al.  Influence of perfluorinated compounds on the properties of model lipid membranes. , 2007, The journal of physical chemistry. B.

[2]  E. Kissa,et al.  Fluorinated Surfactants and Repellents , 2001 .

[3]  K. Miyakawa,et al.  Interaction of surfactants with vesicle membrane of dipalmitoylphosphatidylcholine. Effect on gel-to-liquid-crystalline phase transition of lipid bilayer. , 1986, Chemistry and physics of lipids.

[4]  H. Kawasaki,et al.  Properties of two-component Langmuir monolayer of single chain perfluorinated carboxylic acids with dipalmitoylphosphatidylcholine (DPPC). , 2005, Colloids and surfaces. B, Biointerfaces.

[5]  C. Lau,et al.  Perfluorooctanoic acid induced developmental toxicity in the mouse is dependent on expression of peroxisome proliferator activated receptor-alpha. , 2007, Toxicological sciences : an official journal of the Society of Toxicology.

[6]  Scott A Mabury,et al.  Bioconcentration and tissue distribution of perfluorinated acids in rainbow trout (Oncorhynchus mykiss) , 2003, Environmental toxicology and chemistry.

[7]  P. Mukerjee,et al.  Nonideality of mixing of micelles of fluorocarbon and hydrocarbon surfactants and evidence of partial miscibility from differential conductance data , 1976 .

[8]  Hans-Joachim Lehmler,et al.  Synthesis of environmentally relevant fluorinated surfactants--a review. , 2005, Chemosphere.

[9]  H. Sakai,et al.  Effects of poly(ethylene glycol) (PEG) concentration on the permeability of PEG-grafted liposomes. , 2005, Chemical & pharmaceutical bulletin.

[10]  J. Custódio,et al.  The active metabolite hydroxytamoxifen of the anticancer drug tamoxifen induces structural changes in membranes. , 1993, Biochimica et biophysica acta.

[11]  P. Bummer,et al.  Mixing of perfluorooctanesulfonic acid (PFOS) potassium salt with dipalmitoyl phosphatidylcholine (DPPC). , 2006, Colloids and surfaces. B, Biointerfaces.

[12]  M. Caffrey,et al.  Phases and phase transitions of the phosphatidylcholines. , 1998, Biochimica et biophysica acta.

[13]  C. J. Vidal,et al.  Effects of the pyrethroid insecticide permethrin on membrane fluidity. , 1996, Chemistry and physics of lipids.

[14]  D. Cafiso,et al.  Perfluorooctyl bromide has limited membrane solubility and is located at the bilayer center. Locating small molecules in lipid bilayers through paramagnetic enhancements of NMR relaxation. , 2002, Journal of medicinal chemistry.

[15]  T. Inoue,et al.  Effect of sodium octanoate and sodium perfluorooctanoate on gel-to-liquid-crystalline phase transition of dipalmitoylphosphatidylcholine vesicle membrane. , 1988, Chemistry and physics of lipids.

[16]  D. Ewing,et al.  Phospholipid phase transitions. Effects of n-alcohols, n-monocarboxylic acids, phenylalkyl alcohols and quaternary ammonium compounds. , 1976, Biochimica et biophysica acta.

[17]  Scott A Mabury,et al.  Dietary accumulation of perfluorinated acids in juvenile rainbow trout (Oncorhynchus mykiss) , 2003, Environmental toxicology and chemistry.

[18]  T. Inoue,et al.  Interaction of surfactants with vesicle membrane of dipalmitoylphosphatidylcholine: fluorescence depolarization study. , 1988, Chemistry and physics of lipids.

[19]  K. Edwards,et al.  Vesicle Solubilization by Alkyl Sulfate Surfactants: A Cryo-TEM Study of the Vesicle to Micelle Transition , 1996 .

[20]  A. Winfield,et al.  In vitro evaluation of a series of sodium carboxylates as dermal penetration enhancers , 1994 .

[21]  M. Rosen,et al.  Gene expression profiling in the lung and liver of PFOA-exposed mouse fetuses. , 2007, Toxicology.

[22]  P. Bummer,et al.  Interaction of a partially fluorinated heptadecanoic acid with diacyl phosphatidylcholines of varying chain length , 2003 .

[23]  P. Bummer,et al.  Effect of potassium perfluorooctanesulfonate, perfluorooctanoate and octanesulfonate on the phase transition of dipalmitoylphosphatidylcholine (DPPC) bilayers. , 2007, Biochimica et biophysica acta.

[24]  P. Bummer,et al.  Mixing of perfluorinated carboxylic acids with dipalmitoylphosphatidylcholine. , 2004, Biochimica et biophysica acta.

[25]  C. J. Vidal,et al.  The pyrethroid insecticide deltamethrin modifies the thermotropic properties and lipid packing order of model membranes , 1996 .

[26]  H. Westerhoff,et al.  Movement of fatty acids, fatty acid analogues, and bile acids across phospholipid bilayers. , 1993, Biochemistry.

[27]  J. Custódio,et al.  The anticancer drug tamoxifen induces changes in the physical properties of model and native membranes. , 1993, Biochimica et biophysica acta.

[28]  H. Heerklotz Interactions of surfactants with lipid membranes , 2008, Quarterly Reviews of Biophysics.

[29]  Mahendra K. Jain,et al.  Effect of small molecules on the dipalmitoyl lecithin liposomal bilayer: III. Phase transition in lipid bilayer , 1977, The Journal of Membrane Biology.

[30]  K. Behar,et al.  Determination of liposomal encapsulation efficiency using proton NMR spectroscopy. , 2004, Chemistry and physics of lipids.

[31]  C. Lau,et al.  Perfluoroalkyl acids: a review of monitoring and toxicological findings. , 2007, Toxicological sciences : an official journal of the Society of Toxicology.

[32]  R. Veldhuizen,et al.  The role of lipids in pulmonary surfactant. , 1998, Biochimica et biophysica acta.

[33]  E. Gratton,et al.  Effect of hydrostatic pressure on water penetration and rotational dynamics in phospholipid-cholesterol bilayers. , 1997, Biophysical journal.

[34]  P. Bummer,et al.  Interaction of a partially fluorinated long-chain nicotinate with dipalmitoylphosphatidylcholine Published, JLR Papers in Press, September 8, 2005. DOI 10.1194/jlr.M500231-JLR200 , 2005, Journal of Lipid Research.

[35]  J. Seelig,et al.  Correlation of membrane/water partition coefficients of detergents with the critical micelle concentration. , 2000, Biophysical journal.

[36]  K. Lohner Effects of small organic molecules on phospholipid phase transitions. , 1991, Chemistry and physics of lipids.

[37]  Paul D. Jones,et al.  Alterations in cell membrane properties caused by perfluorinated compounds. , 2003, Comparative biochemistry and physiology. Toxicology & pharmacology : CBP.

[38]  A. Boyanov,et al.  Gel-state metastability and nature of the azeotropic points in mixtures of saturated phosphatidylcholines and fatty acids , 1987 .

[39]  J. Goerke,et al.  Pulmonary surfactant: functions and molecular composition. , 1998, Biochimica et biophysica acta.

[40]  C. Lau,et al.  Effects of perfluorooctanoic acid exposure during pregnancy in the mouse. , 2006, Toxicological sciences : an official journal of the Society of Toxicology.

[41]  S. Nokes,et al.  Liposome fluidization and melting point depression by pressurized CO2 determined by fluorescence anisotropy. , 2005, Langmuir : the ACS journal of surfaces and colloids.

[42]  D. Lichtenberg Characterization of the solubilization of lipid bilayers by surfactants. , 1985, Biochimica et biophysica acta.