Protocell Self-Assembly Driven by Sodium Trimetaphosphate.

The co-evolution of peptide formation and membrane self-assembly is considered an essential step in the origin of life. However, more research is required on both processes, particularly on the interaction between prebiotic simple fatty-acid membranes and peptide synthesis. In this study, the sodium trimetaphosphate (P3 m)-activated peptide formation reaction of phenylalanine (Phe) in an alkaline decanoic acid-decanol vesicle system was systematically investigated. The experimental results showed that peptide formation could competitively occur with N-acyl amino acid (NAA) formation. NAA formation did not follow the traditional P3 m-activated peptide formation reaction involving the intermediate cyclic acylphosphoramidate (CAPA). Decanoic acid was activated by P3 m to form a mixed anhydride, which then reacted with an amino acid to form the amide NAA. As a kind of membrane-forming amphiphile, NAA can form vesicles independently and reduce the critical vesicle concentration of the fatty-acid vesicles. Moreover, 11 other representative amino acids, namely alanine (Ala), aspartic acid (Asp), glutamic acid (Glu), glycine (Gly), isoleucine (Ile), leucine (Leu), proline (Pro), serine (Ser), threonine (Thr), valine (Val), and arginine (Arg), were selected for investigation. All of them reacted with decanoic acid to form NAA via the activation effect of P3 m. The abovementioned mechanism involving P3 m-activated carboxylic acid has not been reported in the literature. Our experimental results indicate that the participation of decanoic acid in the P3 m activation-based peptide formation reaction system plays a significant role in the emergence of functionalized protocells. The P3 m activation effect can provide diversified raw membrane materials to form and stabilize protocell membranes; moreover, the small peptides, such as Phe-Leu, formed in the same reaction system can induce the amplification of primitive cells. This implies that synergistic symbiosis between membrane and peptide can be realized via the P3 m activation effect.

Prebiotic Formation of Catalytically Active Dipeptides via Trimetaphosphate Activation.

Short peptides with unique catalytic abilities are regarded as the simplest enzymes possessing great potential as primordial species to take part in the chemical origin of life. However, prebiotic acquisition pathways of catalytically active peptides remain unclear. In this study, a microwave reactor was used to simulate hydrothermal environments, such as hydrothermal vents, either submarine or subaerial environments. A refrigerator freezer was used to make ice pieces that mimic extra-terrestrial ice crystals. Serine (Ser) and histidine (His) were used as examples, and the formation of small functional peptides involving sodium trimetaphosphate (P3 m) activation in an alkaline aqueous solution was investigated under the two typical prebiotic environments mentioned above. The obtained experimental results showed that the targeted small functional peptide Ser-His and its sequence isomer His-Ser could be formed in all simulated environments, even in the presence of disruptive amino acids, such as alanine (Ala), proline (Pro), and aspartic acid (Asp), in the reaction systems. Notably, Pro may have some effect on the chirality of the produced dipeptides by screening the configuration of the amino acids. Owing to the lack of disturbance of N-O migration in the CAPA (His) intermediate, the CAPA intermediate of His is more stable than that of Ser; therefore, His is more easily activated by P3 m to form a dipeptide with His at the N-terminal. The yield of His-Ser is at least about four times that of Ser-His in the two simulated prebiotic environments. Additionally, our work suggests that more types of amino acids can be activated simultaneously by P3 m to produce various dipeptides, which will provide abundant raw materials for the evolution of life molecules.

Diphenyl Diselenide-Catalyzed Synthesis of Triaryl Phosphites and Triaryl Phosphates from White Phosphorus.

Industrially important triaryl phosphites, traditionally prepared from PCl3, have been synthesized by a diphenyl diselenide-catalyzed one-step procedure involving white phosphorus and phenols, which provides a halogen- and transition metal-free way to these compounds. Subsequent oxidation of triaryl phosphites produces triaryl phosphates and triaryl thiophosphates. Phosphorotrithioates are also prepared efficiently from aromatic thiols and aliphatic thiols.