Crude phosphorylation mixtures containing racemic lipid amphiphiles self-assemble to give stable primitive compartments

Dimitri Fayolle (1) , Emiliano Altamura , Alice d'Onofrio (1) , Warren Madanamothoo (2) , Bernard Fenet (3, 4) , Fabio Mavelli , René Buchet (5) , Pasquale Stano (6) , Michele Fiore (1) , Peter Strazewski (1)

1 CO2GLYCO - Chimie Organique 2-Glycochimie
2 ICBMS - Institut de Chimie et Biochimie Moléculaires et Supramoléculaires
3 C2P2 - Laboratoire de Chimie, Catalyse, Polymères et Procédés, R 5265
4 CCRMN - Centre Commun de Résonance Magnétique Nucléaire, Université Lyon1
5 MEM² - Métabolisme, Enzymes et Mécanismes Moléculaires
6 ROMA TRE - Università degli Studi Roma Tre = Roma Tre University

It is an open question how the chemical structure of prebiotic vesicle-forming amphiphiles complexified to produce robust primitive compartments that could safely host foreign molecules. Previous work suggests that comparingly labile vesicles composed of plausibly prebiotic fatty acids were eventually chemically transformed with glycerol and a suitable phosphate source into phospholipids that would form robust vesicles. Here we show that phosphatidic acid (PA) and phosphatidylethanolamine (PE) lipids can be obtained from racemic dioleoyl glycerol under plausibly prebiotic phosphorylation conditions. Upon in situ hydration of the crude phosphorylation mixtures only those that contained rac-DOPA (not rac-DOPE) generated stable giant vesicles that were capable of encapsulating water-soluble probes, as evidenced by confocal microscopy and flow cytometry. Chemical reaction side-products (identified by IR and MS and quantified by 1 H NMR) acted as co-surfactants and facilitated vesicle formation. To mimic the compositional variation of such primitive lipid mixtures, self-assembly of a combinatorial set of the above amphiphiles was tested, revealing that too high dioleoyl glycerol contents inhibited vesicle formation. We conclude that a decisive driving force for the gradual transition from unstable fatty acid vesicles to robust diacylglyceryl phosphate vesicles was to avoid the accumulation of unphosphorylated diacylglycerols in primitive vesicle membranes.

Domains: Chemical Sciences; Organic chemistry

Dimitri Fayolle, Emiliano Altamura, Alice d'Onofrio, Warren Madanamothoo, Bernard Fenet, et al.. Crude phosphorylation mixtures containing racemic lipid amphiphiles self-assemble to give stable primitive compartments. Scientific Reports, 2017, 7 (1), ⟨10.1038/s41598-017-18053-y⟩. ⟨hal-02122490⟩