Low-Molecular-Weight Polyols as Key Factors in Sulfur- and Borate-Mediated Protomembrane Formation Before the RNA World.

The emergence of biological membranes was a critical step in the origin of cellular life because compartmentalization enabled molecular concentration, selective interactions, and increasingly complex chemical evolution. While fatty acids are widely considered the primary constituents of primitive membranes, the origin of the hydrophilic molecular scaffolds required for more stable amphiphilic systems remains unresolved. In this review, we propose a new conceptual framework in which low-molecular-weight polyols-including ethylene glycol, glycerol, tetritols, and related sugar alcohols-served as key molecular intermediates linking abiotic carbohydrate chemistry with the emergence of proto-lipids and protomembranes during a pre-phosphate stage of Earth history. Experimental and theoretical studies indicate that abiotic carbon chemistry can generate abundant polyols capable of esterification, etherification, hydrogen bonding, and reversible complexation with borate species. We hypothesize that borate-mediated stabilization of sugars and polyols promoted molecular selection, while sulfur-rich geochemical environments supplied chemically diverse amphiphiles and redox-active reaction networks. Building upon these observations, we propose a pH-dependent evolutionary model in which acidic sulfur-rich environments favored sulfo-protolipids, near-neutral environments promoted mixed polyol-fatty acid membranes, and alkaline boron-rich systems facilitated borate-associated amphiphiles and dynamic supramolecular membrane organization. We further suggest that borate-cross-linked polyol hydrogels acted as transitional soft-matter systems connecting molecular synthesis, membrane self-assembly, compartmentalization, and the emergence of proto-informational assemblies. Modern glycolipids, sulfolipids, archaeal ether lipids, and calditol-containing tetraether membranes are discussed as structural analogues, rather than direct evolutionary descendants, supporting the chemical versatility of polyol-based membrane architectures. Although the proposed evolutionary framework remains hypothetical, it integrates current knowledge from prebiotic organic chemistry, membrane biophysics, boron coordination chemistry, sulfur geochemistry, and systems chemistry into a unified and experimentally testable model for the evolution of proto-lipids, protomembranes, and early protocellular organization.