Anthroyloxy fatty acid

FIG. 11 Order parameter variation along acyl chains in red cell ghosts ( ), small unilamellar vesicles of egg phosphatidylcholine (V), and paraffin oil (+), as determined by the fluorescence anisotropy decay of the w-anthroyloxy fatty acid probes. (Reprinted by permission from Ref. 12.)... 

Kleinfeld, A.M., Chu, P. and Storch, J. (1997) Flip-flop is slow and rate-limiting for the movement of long chain anthroyloxy fatty acids across lipid vesicles. 

M. Vincent and J. Gallay, Time-resolved fluorescence anisotropy study of effect of a cis double bond on structure of lecithin and cholesterol-lecithin bilayers using n-(9-anthroyloxy) fatty acids as probes, Biochemistry 23, 6514-6522 (1984). 

K. R. Thulbom, L. M. Tilley, W. H. Sawyer, and E. Treloar, The use ofn-(9-anthroyloxy) fatty acids to determine fluidity and polarity gradients in phospholipid bilayers, Biochim. Biophys. Acta 558, 166-178 (1979). 

M. Vincent, B. de Foresta, J. Gallay, and A. Alfsen, Nanosecond fluorescence anisotropy decays of n-(9-anthroyloxy) fatty acids in dipalmitoylphosphatidylcholine vesicles with regard to isotropic solvents, Biochemistry 21, 708-716 (1982). 

A. M. Kleinfeld and M. F. Lukacovic, Energy-transfer study of cytochrome b5 using the anthroyloxy fatty acid membrane probes, Biochemistry 24, 1883-1890 (1985). 

D. B. Chalpin and A. M. Kleinfeld, Interaction of fluorescence quenchers with the -(9-anthroyloxy) fatty acid membrane probes, Biochim. Biophys. Acta 731, 465 174 (1983). 

In the past decade a number of physical techniques have been used to evaluate the unique barrier properties of mammalian skin [1]. This chapter deals with the use of another physical technique, fluorescence spectroscopy, to study the barrier properties of the human stratum corneum (SC), specifically with respect to the transport of ions and water. The SC is the outermost layer of the human epidermis and consists of keratinized epithelial cells (comeo-cytes), physically isolated from one another by extracellular lipids arranged in multiple lamellae [2]. Due to a high diffusive resistance, this extracellular SC lipid matrix is believed to form the major barrier to the transport of ions and water through the human skin [3-5]. The objective of the fluorescence studies described here is to understand how such extraordinary barrier properties are achieved. First the phenomenon of fluorescence is described, followed by an evaluation of the use of anthroyloxy fatty acid fluorescent probes to study the physical properties of solvents and phospholipid membranes. Finally, the technique is applied to the SC to study its diffusional barrier to iodide ions and water. 

B. The Use of Anthroyloxy Fatty Acid Probes in Solvents and Membranes... 

Membranes exhibit a common stmcture, with lipid molecules arranged in the form of one or more bilayers, or lamellae. Since lipids are generally nonfluo-rescent, lipid-bound fluorophores are an excellent tool to study this environment. These membrane probes are poorly soluble in water, and hence they partition readily into the hydrophobic regions of the membranes. The derivatives of anthroyloxy fatty acids (AF), with the fluorophore 9-anthroic acid esterfied to the 2, 6,9, 12, or 16 position along a fatty acid acyl chain (stearic acid or palmitic acid), are frequently used. The stmcture of an AF probe is shown schematically in Fig. 1... 

Matayosi, E. D. and Kleinfeld, A. M. Emission wavelength-dejjendent decay of the 9-anthroyloxy-fatty acids membrane probes. Biophys. J. 55 215-235, 1981. Garrison, L. M. Doh, L. A. R. M. Pechtold, R. O. Potts, and W. Abraham. Fluorescence spectroscopic evaluation of stratum comeum lipids and related model systems. In K. R. Brain, V. J. James, and K. A. Walters (eds.), Predictions of Percutaneous Penetration, I.B.C. Technical Services Ltd., London, 1993, pp. 1-7. 

Hutterer R, Schneider FW, Lanig H, Hof M (1997) Solvent relaxation behaviour of n-anthroyloxy fatty acids in PC-vesicles and paraffin oil a time-resolved emission spectra study. Biochim Biophys Acta Biomemhr 1323(2) 195—207. doi 10.1016/s0005-2736(96)... 

Figure 5 Structural formulas for some commonly used fluorophores in fluorescence anisotropy experiments l,6-diphenyl-l,3,5-hexalriene (DPH), ira/w-parinaric acid (f-PA), and the n-(9-anthroyloxy) fatty acid series (9-AS).

Faria, J. L. Berberan-Santos, M. Prieto, M. J. E. A comment on the localization of cyanine dye binding to brush-border membranes by the fluorescence quenching of n-(9-anthroyloxy) fatty acid probes. Biochim. Biophys. Acta, Biomembr. 1990, 1026, 133-134. 

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