Chain-length heterogeneity allows for the assembly of fatty acid vesicles in dilute solutions.

Abstract:

:A requirement for concentrated and chemically homogeneous pools of molecular building blocks would severely restrict plausible scenarios for the origin of life. In the case of membrane self-assembly, models of prebiotic lipid synthesis yield primarily short, single-chain amphiphiles that can form bilayer vesicles only at very high concentrations. These high critical aggregation concentrations (cacs) pose significant obstacles for the self-assembly of single-chain lipid membranes. Here, we examine membrane self-assembly in mixtures of fatty acids with varying chain lengths, an expected feature of any abiotic lipid synthesis. We derive theoretical predictions for the cac of mixtures by adapting thermodynamic models developed for the analogous phenomenon of mixed micelle self-assembly. We then use several complementary methods to characterize aggregation experimentally, and find cac values in close agreement with our theoretical predictions. These measurements establish that the cac of fatty acid mixtures is dramatically lowered by minor fractions of long-chain species, thereby providing a plausible route for protocell membrane assembly. Using an NMR-based approach to monitor aggregation of isotopically labeled samples, we demonstrate the incorporation of individual components into mixed vesicles. These experiments suggest that vesicles assembled in dilute, mixed solutions are depleted of the shorter-chain-length lipid species, a finding that carries implications for the composition of primitive cell membranes.

journal_name

Biophys J

journal_title

Biophysical journal

authors

Budin I,Prwyes N,Zhang N,Szostak JW

doi

10.1016/j.bpj.2014.07.067

subject

Has Abstract

pub_date

2014-10-07 00:00:00

pages

1582-90

issue

7

eissn

0006-3495

issn

1542-0086

pii

S0006-3495(14)00838-8

journal_volume

107

pub_type

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