Influence of dodecyltrimethylammonium halides on interaction of phenyltin compounds with model membranes.

The effects were studied of dodecyltrimethylammonium chloride (DTAC), dodecyltrimethylammonium bromide (DTAB) and dodecyltrimethylammonium iodide (DTAI) on thermotropic phase behaviour of phosphatidylcholine bilayers, as well as on 1H NMR and 31P NMR spectra, in the presence of diphenyltin dichloride (DPhT) and triphenyltin chloride (TPhT). The obtained results indicate that in the presence of the surfactant studied the interaction of phenyltin compounds with model membranes was changed and the changes depended on the kind of the counterion. The surfactants studied (especially DTAC) decrease the ability of phenyltin compounds to induce structural changes in the bilayer. It is suggested that DTAB, and especially DTAC, prevent DPhT induced interdigitated phase formation as well as formation of an inverted hexagonal phase (H(II)) in the case of TPhT/DPPC liposomes.

Counterion effects on interaction of amphiphilic quaternary ammonium salts with model membranes.

The micellization as well as the interaction with model membranes of dodecyltrimethylammonium halides (DTAX) and N-dodecyl-N,N-dimethyl-N-benzylammonium halides (DBeAX) were studied at 298K and 313K by means of titration calorimetry. The calorimetric curves reflect both the counterion and benzyl group effects on the interaction of the surfactants studied with the lipid bilayer. Bromide as counterion enhanced the interactions more than chloride of both DTAX and DBeAX compounds with model membranes. Further, we studied the influence of DTAX and DBeAX on calcium ion desorption from the liposome membrane using a radioactive tracer method. DBeAX proved more efficient in desorption of calcium than DTAX. Iodides of these compounds enhanced this process more than bromides and chlorides.

Micellization process--temperature influence on the counterion effect.

The micellization process of dodecyltrimethylammonium chloride (DTAC) and bromide (DTAB) was studied at 313 K. Nuclear magnetic resonance and calorimetric methods were used. The calorimetric titration curves permitted determination of the critical micelle concentration (CMC) and enthalpy of the micellization process (deltaHm) of the compounds studied. The results obtained were compared to those obtained at 298 K. It was found that calorimetric curves obtained at 313 K for both compounds were similar to each other in contrast to 298 K. Especially a great difference in the shape of curves was observed for DTAC. NMR (1H NMR and 13C NMR) spectra were taken below and above the CMC values and chemical shifts (delta) analysed as a function of concentration of the compounds. Comparison of chemical shift-concentration plots with those obtained from measurements performed at lower temperature showed that chemical shifts are of very similar character in both cases for analyzed groups. However, there are some quantitative differences that indicate at smaller difference in hydration of DTAB and DTAC micelles at elevated temperature. This may be the reason of decrease of differences between micellization processes of DTAC and DTAB compounds. The smaller hydration may be, in turn, the result of diminishing differences in physicochemical properties of bromide and chloride ions with temperature.

Influence of dodecyltrimethylammonium halides on thermotropic phase behaviour of phosphatidylcholine/cholesterol bilayers.

Effects of dodecyltrimethylammonium chloride (DTAC), dodecyltrimethylammonium bromide (DTAB) and dodecyltrimethylammonium iodide (DTAI) on thermotropic phase behaviour of phosphatidylcholine bilayers containing cholesterol as well as on 1H NMR spectra were studied. Two series of experiments were performed. In the first one the surfactants were added to the water phase while in the other directly to the lipid phase (a mixed film from cholesterol, surfactant and phosphatidylcholine was formed). The effects of particular surfactants on the main phase transition temperature, Tm, were more pronounced when added to the lipid phase (2nd method) than to the water phase (1st method); the opposite happened when cholesterol was absent (Rózycka-Roszak and Pruchnik 2000, Z. Naturforsch. 55c, 240-244). Furthermore, in the case of the first method the transitions were asymmetrical while in the second method nearly symmetrical. It is suggested that surfactant poor and surfactant rich domains are formed when surfactants are added to the water phase.

Hydration of alkylammonium salt micelles--influence of bromide and chloride counterions.

The micellization process of dodecyltrimethylammonium chloride (DTAC) and bromide (DTAB) was studied. Nuclear magnetic resonance method was used. The 1H NMR and 13C NMR spectra were taken at higher and lower concentrations than the critical micelle concentrations (CMC) of the compounds studied. Chemical shifts were analysed. The studies performed were prompted by earlier calorimetric measurements which showed that there were significant qualitative and quantitative differences in the micellization process of the compounds studied. Namely, DTAB micelle dissociation was found to be an endothermic process while that of DTAC was exothermic. The differences found must be the result of differentiated influence of bromide and chloride counterions on the micellization process, including the phenomenon of micelle hydration. The objective of the work was to check whether cationic surfactant counterions can influence the micelle hydration process. Indeed, DTAB and DTAC, as monomers, exhibit similar hydrophobic hydration, but DTAB micelles are more hydrated than DTAC ones. It seems that the differences found in micellization of both salts studied may be attributed to different physicochemical properties of bromide and chloride ions, such as their mobilities and radii of their hydrated forms. Moreover, the effect of anions on the water structure must be taken into account. It is important whether the anions can be classified as water ordering kosmotropes, that hold the first hydration shell tightly, or water disordering chaotropes, that hold water molecules in that shell loosely.

Effect of counterions on the influence of dodecyltrimethylammonium halides on thermotropic phase behaviour of phosphatidylcholine bilayers.

Effects of dodecyltrimethylammonium chloride (DTAC), dodecyltrimethylammonium bromide (DTAB) and dodecyltrimethylammonium iodide (DTAI) on thermotropic phase behaviour of phosphatidylcholine bilayers as well as on 1H NMR spectra were studied. In order to enhance the effect of counterions on water structure two series of experiments were performed. In the first one the surfactants were added to the water phase and in the other one directly to lipid phase (a mixed film was formed). The effects of particular surfactants on the main phase-transition temperature were more pronounced when they were added to the water phase (1st method) instead of the lipid phase (2nd method). Furthermore, in the case of the first method the transitions were found asymmetrical while in the second method nearly symmetrical. It is suggested that surfactant-poor and surfactant-rich domains are formed when surfactants are added to the water phase.

1H NMR Studies of Aqueous Micellar Solutions of N-Dodecyl- N,N-dimethyl-N-benzylammonium Chloride.

(1)H NMR studies of the micellization process in N-dodecyl-N,N-dimethyl-N-benzylammonium chloride (DBeAC) were carried out. The spectra were measured at concentrations below and above the critical micelle concentration (CMC). The chemical shifts and Nuclear Overhauser Effect (NOE) measurements were analyzed as a function of the concentration. This allowed us to provide experimental evidence that the benzyl group of DBeAC changes its position during micellization and, as a consequence, is located inside the micelle. Copyright 1999 Academic Press.

Influence of counterions on the interaction of pyridinium salts with model membranes.

The interaction of pyridinium salts (PS) with red blood cells and planar lipid membranes was studied. The aim of the work was to find whether certain cationic surfactant counterion influence its possible biological activity. The counterions studied were Cl-, Br-, I-, ClO4-, BF4- and NO3-. The model membranes used were erythrocyte and planar lipid membranes (BLM). At high concentration the salts caused 100% erythrocyte hemolysis (C100) or broke BLMs (CC). Both parameters describe mechanical properties of model membranes. It was found that the efficiency of the surfactant to destabilize model membranes depended to some degree on its counterion. In both, erythrocyte and BLM experiments, the highest efficiency was observed for Br-, the lowest for NO3-. The influence of all other anions on surfactant efficiency changed between these two extremities; that of chloride and perchlorate ions was similar. Some differences were found in the case of BF4- ion. Its influence on hemolytic possibilities of PS was significant while BLM destruction required relatively high concentration of this anion. Apparently, the influence of various anions on the destructive action of PS on the model membrane used may be attributed to different mobilities and radii of hydrated ions and hence, to different possibilities of particular anions to modify the surface potential of model membranes. This can lead to a differentiated interaction of PS with modified bilayers. Moreover, the effect of anions on the water structure must be taken into account. It is important whether the anions can be classified as water ordering kosmotropes that hold the first hydration shell tightly or water disordering chaotropes that hold water molecules in that shell loosely.

The role of counterions in the interaction of bifunctional surface active compounds with model membranes.

Interaction of two series of bifunctional surfactants (bromides and chlorides) with red blood cells and planar lipid membranes was studied. The aim of the work was to determine the role of counterions in the mechanism of interaction of bifunctional cationic surfactants with model membranes. In each case bromides influenced model membranes to a greater degree than the corresponding chlorides. The possible explanation of the obtained results is presented. It seems that the greater ability of bromides to destabilize model membranes in comparison with chlorides can be attributed to the greater mobility and the smaller radius of the hydrated bromide ion. This may underlie the greater ease that this anion can modify the surface potential of the lipid bilayer, thus enhancing the interaction of the cationic surfactant with such a modified bilayer.

Interaction between model membranes and a new class of surfactants with antioxidant function.

The effect of two series of amphiphilic quaternary ammonium salts on some properties of phospholipid membranes was studied. The compounds of one series, N-benzyl-N,N-dimethyl-N-alkyl ammonium bromides, exert a destructive effect on membranes and are treated as reference compounds. The compounds of the other series, N-(3,5-di-t-butyl-4-hydroxy)benzyl-N,N-dimethyl-N-alkyl ammonium bromides, are derivatives of the former ones, exhibit antioxidant properties, and do only relatively slight damage to the membranes. The aim of the work was to explain the difference in molecular interaction with membranes between the two kinds of hydrophobic compounds. Thermodynamic methods, a new mixing technique, and monolayer and quantum calculation methods were used. It has been shown that the antioxidant molecules are less hydrophobic than those of the reference compounds and disturb the membrane organization to a lesser extent. On the basis of monolayer data, we suggest that the studied antioxidant behaves like a substitutional impurity, whereas the reference behaves like an interstitial one.