Fast Transfer of Photoreleased Protons from Water to Lipid Membrane

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The transfer of protons between the surface of lipid membrane and water can be slowed down by the presence of a high potential barrier, which affects the functioning of proton-transporting proteins. To evaluate the rate of the proton transfer across the barrier, the photoactivatable compounds that can adsorb on the membrane boundary and release protons upon excitation are used. One of these compounds, which we studied earlier, sodium salt of 2-methoxy-5-nitrophenylsulfate (MNPS), was used in this work. The molecule of MNPS can adsorb on the bilayer lipid membrane (BLM) as anion and release sulfate and proton upon excitation with UV light, becoming an electroneutral product. Upon illumination of the BLM, on one side of which MNPS anions were adsorbed, changes in the electrostatic potential at the membrane–water interface were observed. The slow changes of the potential were measured by the intramembrane field compensation method and the fast changes, by the operational amplifier as an electrometer. When the light was switched on, the potential increased rapidly, and when the light was switched off, the potential slowly returned to its initial value. The rate of rapid potential increase depended on the lipid composition of BLM, buffer concentration, and pH of the medium. The dependence of this rate on pH was different for BLMs formed from phosphatidylcholine and its mixture with phosphatidylserine. With increasing buffer concentration, the rate decreased tens of times. The results obtained indicate that the reaction of proton release formed during the excitation of MNPS molecules occurs both on the membrane surface and in the water near it. The main contribution to the change in the electrostatic potential at the membrane boundary is given by protons bound at its surface from the reaction in water.

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V. Tashkin

Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences

Email: sokolovvs@mail.ru
俄罗斯联邦, Moscow, 119071

D. Zykova

Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences; Moscow Institute of Physics and Technology (National Research University)

Email: sokolovvs@mail.ru
俄罗斯联邦, Moscow, 119071; Dolgoprudny, 141700

L. Pozdeeva

Lomonosov Moscow State University

Email: sokolovvs@mail.ru
俄罗斯联邦, Moscow, 119991

V. Sokolov

Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences

编辑信件的主要联系方式.
Email: sokolovvs@mail.ru
俄罗斯联邦, Moscow, 119071

参考

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2. Fig. 1. Kinetics of the boundary potential change during MNPS adsorption on BLM and subsequent illumination. Measurements were performed on the same membrane by the FWC method (a, b) or with an electrometric amplifier (c). b - Change in potential upon illumination obtained from the graph (a) by shifting and stretching the time scale. Arrows with corresponding labels show the moments of MNPS addition (MNPS), light on (L) and light off (D). BLM was formed from PC. The solution contained 20 mM KCl, 0.2 mM Tris, HEPES, and citrate, pH 8.0. MNPS was added to the far compartment of the cell relative to the light source at a concentration of 600 μM, and illumination was performed with an LED (365 nm, electrical power 0.12 W).

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3. Fig. 2. Dependence of the rate of change of the boundary potential at the moment of illumination on the electric power of illumination. The experimental conditions are similar to those indicated in the caption to Fig. 1. a - Kinetics of the potential change measured by electrometer at switching on (L) and switching off (D) the light with different power indicated in the caption to the figure. The dotted line demonstrates the method of determining the parameter R for the illumination power of 0.34 W as the slope of the tangent to the blue curve at the point corresponding to the zero moment of time. b - Dependence of the parameter R on the illumination power P. The measurements were carried out by the FIR method (black circles) and by electrometer (empty circles).

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4. Fig. 3. Dependence of the rate of change of the boundary potential R measured by electrometer at the moment of illumination on the solution pH (a) and buffer C concentration (b). The solution contained 20 mM KCl, 0.2 mM Tris, MES, and citrate. MNPS was added to the cell compartment farthest away from the light source at a concentration of 600 μM. Illumination was conducted at 0.03-0.4 W. Buffer concentration was varied at pH 8 by adding Tris to the solutions on either side of the membrane, and at pH 6 by adding MES. The R values in graph a were normalized to the illumination power, in graph b - to the R value measured before increasing the buffer concentration in the solution.

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5. Fig. 4. a - Dependence of the boundary potential difference of BLM formed from PC+PS on the concentration of KCl on one side of the BLM. The initial solution contained 10 mM KCl and 1 mM HEPES, pH 7.0. The curve was drawn using the Gui-Chapman equation for a surface charge of -58 μCl/cm2. b - Dependence of the change in the BLM boundary potential caused by adsorption of MNPS added to the solution on one side of the BLM on its concentration in this solution. The solution contained 20 mM KCl, 2 mM HEPES, pH 7.0. BLM was formed from either PC (empty circles, data taken from [15]) or PC+PS (black circles).

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6. Fig. 5. Dependence of the variation of the boundary potential on pH in solution on one side of the BLM formed from PC or from PC+PS. The membrane was formed in a solution of 20 mM KCl, 2 mM citrate, HEPES and Tris. The pH value in the solution back of the membrane was 7 for BLM from PC and 8.5 for BLM from PC+PS. The potential values for the BLMs from PC were shifted by the z-potential, whose value at pH 7 was about -10 mV, and for the BLMs from PC+PS by the surface potential (-62 mV), calculated from the dependence of the change in the boundary potential on the KCl concentration in the solution on one side of the membrane in Fig. 3a. The data for BLM from PC are taken from [16].

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7. Fig. 6. Scheme of photochemical processes under MNPS excitation on the membrane surface and in the solution near it. The gray rectangle in the center is BLM, the circle and ovals indicate the protons and anions of MNPS involved in the reactions. The red line shows the shift of the boundary potential under illumination.

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