Determination of Benzyl-hexadecyldimethylammonium 1,4-Bis(2-ethylhexyl)sulfosuccinate Vesicle Permeability by Using Square Wave Voltammetry and an Enzymatic Reaction.

This report describes the studies performed to determine the permeability coefficient value (P) of 1-naphthyl phosphate (1-NP) through the benzyl-hexadecyldimethylammonium 1,4-bis(2-ethylhexyl)sulfosuccinate (AOT-BHD) vesicle bilayer. 1-NP was added in the external phase and must cross the bilayer of the vesicle to react with the encapsulated enzyme (alkaline phosphatase) to yield 1-naphtholate (NPh-), the product of the enzymatic hydrolysis. This product is electrochemically detected, at basic pH value, by a square wave voltammetry technique, which can be a good alternative over the spectroscopic one, to measure the vesicle solutions because scattering (due to its turbidity) does not make any influence in the electrochemical signal. The experimental data allow us to propose a mathematical model, and a value of P = (1.00 ± 0.15) × 10-9 cm s-1 was obtained. Also, a value of P = (2.0 ± 0.5) × 10-9 cm s-1 was found by using an independent technique, ultraviolet-visible spectroscopy, for comparison. It is evident that the P values obtained from both the techniques are comparable (within the experimental error of both techniques) under the same experimental conditions. This study constitutes the first report of the 1-NP permeability determination in this new vesicle. We want to highlight the importance of the introduction of a new method and the electrochemical response of the product generated through an enzymatic reaction that occurs in the inner aqueous phase of the vesicle, where the enzyme is placed.

Electrochemical and photophysical behavior of 1-naphthol in benzyl-n-hexadecyldimethylammonium 1,4-bis(2-ethylhexyl)sulfosuccinate large unilamellar vesicles.

In the present contribution, 1-naphthol is investigated in large unilamellar vesicles formed from a new catanionic surfactant, benzyl-n-hexadecyldimethylammonium 1,4-bis(2-ethylhexyl)sulfosuccinate, by electrochemical and spectroscopic techniques. The electrochemical results show that 1-naphthol experiences a partition process between the water phase and the large unilamellar vesicle bilayer phase, which is corroborated by absorption spectroscopic studies at pH = 6.40 and pH = 10.75. Interestingly, studies of 1-naphthol emission in benzyl-n-hexadecyldimethylammonium 1,4-bis(2-ethylhexyl)sulfosuccinate large unilamellar vesicles at pH = 10.75 and in sodium 1,4-bis(2-ethylhexyl)sulfosuccinate water solution show that when the 1,4-bis(2-ethylhexyl)sulfosuccinate moiety is part of the bilayer, the 1,4-bis(2-ethylhexyl)sulfosuccinate polar head interacts strongly with 1-naphthol, by favoring emission from the excited neutral species resulting in the appearance of a new band close to λ = 355 nm. It seems that the large unilamellar vesicle bilayer of the catanionic vesicle slows down the proton transfer process observed in water, where only emission from 1-naphtholate is detected.