Ionized fatty acids

For this water concentration, the micellar region for the bile salt mixture is large for all oleyl compounds except oleic acid. Oleic acid is distinguished from the other compounds in that it does not form a lyotropic liquid crystalline phase spontaneously in water and, similarly, is present as oil droplets in bile salt solution when its micellar solubility is exceeded. Figure 1 shows also that the micellar area of an equimolar mixture of monoolein and sodium oleate is considerably greater than that of an equimolar mixture of monoolein and oleic acid, indicating that fatty acid ionization also enhances micellar solubility when monoolein is present. The equimolar mixture of sodium oleate and oleic acid has a micellar area similar in size to that of monoolein, as does the equimolar combination of all three compounds. 

The data clearly indicate that the surface pH of the bile salt micelle is higher than the surface pH of a lauryl taurate micelle for a given bulk pH—i.e., the difference between bulk and surface pH is less with the bile salt micelle. The bile salt micelle should have a lower charge density and therefore a lower concentration of protons at the surface of the micelle. Therefore, the observed bulk pH at which micellar fatty acid ionizes is closer to the bulk pKa of molecularly dispersed fatty acid (4.9) in bile salt solution than in lauryl taurate solution. 

Because of the charged nature of many Langmuir films, fairly marked effects of changing the pH of the substrate phase are often observed. An obvious case is that of the fatty-acid monolayers these will be ionized on alkaline substrates, and as a result of the repulsion between the charged polar groups, the film reverts to a gaseous or liquid expanded state at a much lower temperature than does the acid form [121]. Also, the surface potential drops since, as illustrated in Fig. XV-13, the presence of nearby counterions introduces a dipole opposite in orientation to that previously present. A similar situation is found with long-chain amines on acid substrates [122]. 

APCl in positive mode ionization and triple quadrupole detection was used for determination of free and bound carotenoids in paprika, obtaining the [M + H]+ and losses of fatty acids as neutral molecules from the [M + H]+ with MeOH, MTBE, and H2O as eluent from the C30 column. The positions of the fatty acids on unsymmetrical xanthophylls could not be established by the MS data. 

Fe-TPAA Fe(III)-tris[N-(2-pyridylmethyl)-2-aminoethyl] amine Fe-TPEN Fe(II)-tetrakis-N,N,N, N -(2-pyridyl methyl-2-aminoethyl)amine FFA Free fatty acids FGF Fibroblast growth factor FID Flame ionization detector FITC Fluorescein isothiocyanate FKBP FK506-binding protein FLAP 5-lipoxygenase-activating protein... 

The same approach derived for weak bases can also be applied to the uptake of simple weak acids, and to the transbilayer transport of acidic lipids, such as fatty acids and some phospholipids. We consider uptake of a simple weak acid into an LUV with basic interior. Let [AH], ([A ]o) and [AH] ([A ] ) refer to the concentrations of the neutral (ionized) form(s) of the weak acid on the outside and inside of the vesicle, respectively. Then, the total external and internal concentrations of the weak acid can be written as... 

Up to now we have focused on measurement of permeability and membrane retention at pH 7.4. Since the GIT covers a range of pH values, with pH 5-8 characterizing the small intestine, it is necessary to address the pH dependence of the transport of drug molecules. Even nonionizable molecules may be affected by pH dependence, since several biological membrane components themselves are ionizable (pKa values listed in Fig. 7.4). For example, with PS, PA, and DA (free fatty acid) undergoing changes in charge state in the pH 5-8 interval. In this section, we examine the consequences of pH dependence. 

Egreet-Charlier, M., A. Sanson, M. Ptak, and O. Bouloussa. 1978. Ionization of fatty acids at lipid-water interface. FEBSLett. 89 313-316. 

Fig. 10.5 Schematic diagrams a micelle consisting of ionized fatty acid molecules, a phospholipid bilayer and the vesicle bilayer of a liposome...

To identify the kind of oil, Keune et al. [2005] used the classical approach based on the palmitic acid/stearic acid (P/S) ratio usually obtained from GC/MS data. Ratios less than 2 correspond to linseed oil, whereas ratios higher than 5 correspond to poppy seed oil. Intermediate values can be attributed to walnut, poppy seed oil or mixtures [Schilliing and Khaijan 1996]. Keune et al. first show that ionization efficiency is the same for the two fatty acids in negative ion mode permitting the use of ToF-SIMS for the calculation of the P/S ratio. A test on the oil-paint model system shows a ratio of 2.0 for linseed oil and 3.6 for poppy seed oil, which can allow the two oils to be differentiated. Nevertheless, it is important to note that the ratio is not constant all over the cross-section. 

Fatty acids were extracted following the above procedure. Fatty acids are analyzed by GC-MS. The GC used was a Perkin-Elmer 8600 fitted with flame ionization detector. An SE-54 quartz capillary column (30m) was used. The... 

An official gas chromatographic method [29] is available from the determination of volatile fatty acids in sewage sludge. This method is based on gas liquid chromatographic estimation with a flame ionization detector, and is applicable up to 2000mg total volatile fatty acids per litre, while the concentrations of individual fatty acids can also be determined. Where this method is not practicable an empirical method based on the spectrophotometric determination of ferric hydroxamates can be used, giving a value for total fatty acids expressed as acetic acid. For control purposes a rapid test is described in which the volatile fatty acids are determined by electrometric titrimetry on the neutralized sludge obtained from the determination of alkalinity. 

Several original papers must be mentioned that deal with mass spectrometric techniques which the numerous reviews do not comprise. Kaufmann and coworkers268,288 studied the mass spectrometric analysis of carotenoids and some of their fatty acid esters using matrix-assisted laser desorption/ionization (MALDI) mass spectrometry and its post-source-decay (PSD) variant. Some advantages concerning the thermal instability and limited solubility were discussed, but the fragmentation paths of the carotenoid cations were found to be essentially the same as those observed with conventional techniques. 

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