Prebiotic membranes are one of the essential elements
of the origin
of life because they build compartments to keep genetic materials
and metabolic machinery safe. Since modern cell membranes are made
up of ethanolamine-based phospholipids, prebiotic membrane formation
with ethanolamine-based amphiphiles and phosphates might act as a
bridge between the prebiotic and contemporary eras. Here, we report
the prebiotic synthesis of O-lauroyl ethanolamine
(OLEA), O-lauroyl methyl ethanolamine (OLMEA), and O-lauroyl dimethylethanolamine (OLDMEA) under wet–dry
cycles. Turbidimetric, NMR, DLS, fluorescence, microscopy, and glucose
encapsulation studies highlighted that OLEA-ATP and OLMEA-ATP form
protocellular membranes in a 3:1 ratio, where ATP acts as a template.
OLDMEA with a dimethyl group did not form any membrane in the presence
of ATP. ADP can also template OLEA to form vesicles in a 2:1 ratio,
but the ADP-templated vesicles were smaller. This suggests the critical
role of the phosphate backbone in controlling the curvature of supramolecular
assembly. The mechanisms of hierarchical assembly and transient dissipative
assembly are discussed based on templated-complex formation via electrostatic,
hydrophobic, and H-bonding interactions. Our results suggest that N-methylethanolamine-based amphiphiles could be used to
form prebiotic vesicles, but the superior H-bonding ability of the
ethanolamine moiety likely provides an evolutionary advantage for
stable protocell formation during the fluctuating environments of
early earth.