Inducing Homochirality Through Intermediary Catalytic Species: A Stochastic Approach.

A new chiral amplification mechanism based on a stochastic approach is proposed. The mechanism includes five different chemical species, an achiral substrate (A), two chiral forms (L, D), and two intermediary species (LA, DA). The process occurs within a small, semipermeable compartment that can be diffusively coupled with the outside environment. The study considers two alternative primary sources for chiral species within the compartment, one chemical and the other diffusive. As a remarkable fact, the chiral amplification process occurs due to stochastic fluctuations of an intermediary catalytic species (LA, DA) produced in situ, given the interaction of the chiral species with the achiral substrate. The net process includes two different steps: the synthesis of the catalyst (LA and DA) and the catalytic production of new chiral species from the substrate. Stochastic simulations show that proper parameterization can induce a robust chiral state within the compartment regardless of whether the system is open or closed. We also show how an increase in the non-catalytic production of chiral species tends to negatively impact the homochirality degree of the system. By its conception, the proposed mechanism suggests a deeper connection with how most biochemical processes occur in living beings, a fact that could open new avenues for studying this fascinating phenomenon.

From a coenzyme-like mechanism to homochirality.

Inspired in a coenzyme-like behavior, an alternative mechanism to induce homochirality within a small vesicle is proposed. The system includes six different chemical species: an achiral substrate A, the enantiomeric forms L and D, a coenzyme E and two intermediate catalytic forms LE and DE. Whereas the coenzyme and the intermediate catalytic forms are trapped within the vesicle, the substrate and the two enantiomeric forms are able to diffuse selectively across the vesicle boundary. Instead of using autocatalysis, the production of new enantiomers includes two different steps, the production of intermediate catalytic species (LE, DE) and the catalytic production of new enantiomers from the substrate. Using a suitable parameterization, we found that the chiral evolution of the system is highly dependent on the total amount of coenzyme within the vesicle, regardless of whether the surrounding membrane is permeable or not. However, the existence of large flows from the outside can destabilize the homochiral state inside the vesicle. In general, homochiral states tend to arise when the amount of coenzyme is quite low, a value that can vary according to the parametrization. On the other hand, the system tends to decrease the enantiomeric excess when the coenzyme levels are high enough. In general, the appearance of homochirality is conditioned by stochastic fluctuations in coenzyme levels within the vesicle, an effect that is gradually amplified throughout the entire process of enantiomer synthesis.

The optimal size of protocells from simple entropic considerations.

Potential constraints on protocell size are developed from simple entropic considerations. To do that, two new different indexes as measures of their structural and dynamic order were developed and applied to an elemental model of the heterotrophic protocell. According to our results, cell size should be a key factor determining the potential of these primitive systems to evolve and consequently to support life. Our analyses also suggest that the size of the optimal vesicles could be constrained to have radii in the interval [Formula: see text], where the two extreme limits [Formula: see text] and [Formula: see text] represent the states of maximum structural order (largest accumulation of substrate inside the vesicle) and the maximum flux of entropy production, respectively. According to the above criteria, the size of the optimum vesicles falls, approximately, in the same spatial range estimated for biological living cells assuming plausible values for the second-order rate constant involved in the catabolic process. Furthermore, the existence of very small vesicles could be seriously affected by the limited efficiency, far from the theoretical limits, with which these catabolic processes may proceed in a prebiotic system.

Constraining the Prebiotic Cell Size Limits in Extremely Hostile Environments: A Dynamical Perspective.

The ability to support a replicator population in an extremely hostile environment is considered in a simple model of a prebiotic cell. We explore from a classical approach how the replicator viability changes as a function of the cell radius. The model includes the interaction between two different species: a substrate that flows from the exterior and a replicator that feeds on the substrate and is readily destroyed in the environment outside the cell. According to our results, replicators in the cell only exist when the radius exceeds some critical value [Formula: see text] being, in general, a function of the substrate concentration, the diffusion constant of the replicator species, and the reproduction rate coefficient. Additionally, the influence of other parameters on the replicator population is also considered. The viability of chemical replicators under such drastic conditions could be crucial in understanding the origin of the first primitive cells and the ulterior development of life on our planet. Key Words: Prebiotic cell-Chemical replicator-Environment-Reproduction rate. Astrobiology 18, 403-411.