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Abstract:
Chirality at interfaces is a relevant topic in nanoscience, as well as a key point for prebiotic chemistry. Mixed Langmuir monolayers, composed of the anionic phospholipid dimyristoyl phosphatidic acid (DMPA) and the cationic amphiphilic quinoline derivative 2-methyl-1-octadecylquinoline (MQ) have been built at the air-water interface. Both DMPA and MQ molecules are miscible, thus the equimolar mixture yields homogeneous monolayers completely. Chiral domains have been formed by this monolayer and observed in situ by Brewster angle microscopy (BAM). These chiral domains display a large array of shapes and sizes. The chirality of the monolayers has been confirmed by circular dichroism spectroscopy. The ordered aggregation of the quinoline group into large chiral supramolecular structures is proposed as the molecular origin of the observed chirality. Theoretical simulations using molecular mechanics confirm the strong trend of the quinoline group to form chiral aggregates. The great diversity in the size and shape of the chiral domains has been found to be strongly influenced by the competition between two nuclei growth mechanisms. An experimental procedure allowing a minimized growth through one of these mechanism is proposed, achieving a homogeneous distribution of ring-shaped domains. An overshoot in the pi-A isotherms of this mixed monolayer appears at an intermediate surface pressure. This overshoot is interpreted as being due to the large difference between the surface pressure which starts the nuclei formation, pi(crit) and the superficial pressure in which the nuclei can grow, pi(e). The rather small pi(e) value compared to pi(crit) observed for this system must be attributed to the molecular interactions involved in the mixed monolayer, which facilitate the incorporation of molecules in preformed nuclei.
