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In this work biomimetic monolayers of a MGDG, monogalactosyldiacylglycerol, and DGDG, digalactosyldiacylglycerol mixture (MD), in a ratio close to that of the thylakoid membranes of oxygenic photosynthetic organisms, have been prepared. The lipid mixture incorporates plastoquinone-9 (PQ), that is the electron and proton shuttle of the photosynthetic reaction centres. The MD:PQ mixtures have been firstly studied using surface pressure-area isotherms. Langmuir-Blodgett (LB) films of those mixtures have been transferred onto a substrate forming a monolayer that mimics one of the bilayer sides of the thylakoid membranes. These monolayers have been characterized topographically and electrochemically. The results show the influence of PQ in the MD matrix and its partial expulsion when increasing the surface pressure, obtaining two main PQ positions in the MD matrix. The calculated apparent electron transfer rate constants indicate a different kinetic control for the reduction and the oxidation of the PQ/PQH 2 couple, being k Rapp (I) = 0.7 · 10 − 6 s − 1 , k Rapp (II) = 2.2 · 10 − 9 s − 1 , k Oapp (I) = 7.4 · 10 − 4 s − 1 and k Oapp (II) = 5.2 · 10 − 5 s − 1 , respectively. The comparison of the different galactolipid:PQ systems that our group has studied is also presented, concluding that the PQ position in the galactolipid matrix can be tuned according to several controlled variables. [ABSTRACT FROM AUTHOR]

The electrochemical behaviour of biomimetic monolayers of monogalactosyldiacylglycerol (MGDG) incorporating ubiquinone-10 (UQ) has been investigated. MGDG is the principal component in the thylakoid membrane and UQ seems a good substitute for plastoquinone-9, involved in photosynthesis chain. The monolayers have been performed using the Langmuir and Langmuir–Blodgett (LB) techniques and the redox behaviour of the LB films, transferred at several surface pressures on a glass covered with indium–tin oxide (ITO), has been characterized by cyclic voltammetry. The cyclic voltammograms show that UQ molecules present two redox processes (I and II) at high UQ content and high surface pressures, and only one redox process (I) at low UQ content and low surface pressures. The apparent rate constants calculated for processes I and II indicate a different kinetic control for the reduction and the oxidation of UQ/UQH 2 redox couple, being k Rapp (I) = 2.2 · 10 − 5 s − 1 , k Rapp (II) = 5.1 · 10 − 14 k Oapp (I) = 3.3 · 10 − 3 s − 1 and k Oapp (II) = 6.1 · 10 − 6 s − 1 , respectively. The correlation of the redox response with the physical states of the LB films allows determining the positions of the UQ molecules in the biomimetic monolayer, which change with the surface pressure and the UQ content. These positions are known as diving and swimming. [ABSTRACT FROM AUTHOR]

The photosynthesis is the process used by plants and bacteria cells to convert inorganic matter in organic thanks to the light energy. This process consist on several steps, being one of them the electronic transport from the photosystem II to the cytochrome thanks to plastoquinone-9 (PQ). Here we prepare membranes that mimic the characteristics and composition of natural photosynthetic cell membranes and we characterize them in order to obtain the PQ molecules position in the membrane and their electrochemical behaviour. The selected galactolipid is digalactosyldiacylglycerol (DGDG) that represents the 30% of the thylakoid membrane lipid content. The results obtained are worthful for several science fields due to the relevance of galactolipids as anti-algal, anti-viral, anti-tumor and anti-inflammatory agents and the antioxidant and free radical scavenger properties of prenylquinones. Both pure components (DGDG and PQ) and the DGDG:PQ mixtures have been studied using surface pressure–area isotherms. These isotherms give information about the film stability and indicate the thermodynamic behaviour of the mixture and their physical state. The Langmuir–Blodgett (LB) film has been transferred forming a monolayer that mimics the bottom layer of the biological membranes. This monolayer on mica has been topographically characterized using AFM and both the height and the physical state that they present have been obtained. Moreover, these monolayers have been transferred onto ITO that is a hydrophilic substrate with good optical and electrical features, so that, it is suitable for studying the electrochemical behaviour of these systems and it is a good candidate for energy producing devices. [ABSTRACT FROM AUTHOR]

Abstract: The structure and the electrochemical behaviour of Langmuir and Langmuir–Blodgett (LB) films of the biological ubiquinone-10 (UQ) and a mixture of dipalmytoilphosphatidylcholine (DPPC) and UQ at the molar ratios DPPC:UQ 5:1 and 10:1 have been investigated. The surface pressure-area isotherms of the Langmuir films and the AFM images of the LB films show the formation of a monolayer in the DPPC:UQ mixture till a certain surface pressure is attained, and then at higher surface pressures the UQ is progressively expelled. The cyclic voltammograms of DPPC:UQ LB films formed on indium tin oxide, ITO, at different surface pressures show one reduction and one oxidation peak at low surface pressures, but two or even more reduction and oxidations peaks at medium and high surface pressures. The electrochemical behaviour is correlated with the film structure. [Copyright &y& Elsevier]