Formation of Carbon-Carbon Bonds in the Photochemical Alkylation of Polycyclic Aromatic Hydrocarbons

The reaction of polycyclic aromatic hydrocarbons (PAHs) withalkanes was examined in the presence of ultraviolet (UV) lightunder model prebiotic Earth and interstellar medium (ISM)conditions. We observed the formation of alkylated PAHs from avariety of PAHs and alkanes, which was caused by the absorptionof UV light by the PAH molecule. Photoalkylation occurred inPAHs and alkanes in solution, in thin films in contact withsimulated ocean water, and in matrices simulating ISMconditions. Photoalkylation occurred readily, with significantproduct yields within 5 h of irradiation. Because alkanes andPAHs are presumed to be part of the organic inventory in the ISMand on the early Earth, we propose that this photoalkylation reactionis a plausible pathway for the formation of carbon-carbon bondsin both these environments.     

Bioenergetics and Life's Origins

Bioenergetics is central to our understanding of living systems, yet has attracted relatively little attention in origins of life research. This article focuses on energy resources available to drive primitive metabolism and the synthesis of polymers that could be incorporated into molecular systems having properties associated with the living state. The compartmented systems are referred to as protocells, each different from all the rest and representing a kind of natural experiment. The origin of life was marked when a rare few protocells happened to have the ability to capture energy from the environment to initiate catalyzed heterotrophic growth directed by heritable genetic information in the polymers. This article examines potential sources of energy available to protocells, and mechanisms by which the energy could be used to drive polymer synthesis.Previous research on life''s origins has for the most part focused on the chemistry and energy sources required to produce the small molecules of life—amino acids, nucleobases, and amphiphiles—and to a lesser extent on condensation reactions by which the monomers can be linked into biologically relevant polymers. In modern living cells, polymers are synthesized from activated monomers such as the nucleoside triphosphates used by DNA and RNA polymerases, and the tRNA-amino acyl conjugates that supply ribosomes with activated amino acids. Activated monomers are essential because polymerization reactions occur in an aqueous medium and are therefore energetically uphill in the absence of activation.A central problem therefore concerns mechanisms by which prebiotic monomers could have been activated to assemble into polymers. Most biopolymers of life are synthesized when the equivalent of a water molecule is removed to form the ester bonds of nucleic acids, glycoside bonds of polysaccharides, and peptide bonds in proteins. In life today, the removal of water is performed upstream of the actual bond formation. This process involves the energetically downhill transfer of electrons, which is coupled to either substrate-level oxidation or generation of a proton gradient that in turn is the energy source for the synthesis of anhydride pyrophosphate bonds in ATP. The energy stored in the pyrophosphate bond is then distributed throughout the cell to drive most other energy‐dependent reactions. This is a complex and highly evolved process, so here we consider simpler ways in which energy could have been captured from the environment and made available for primitive versions of metabolism and polymer synthesis. Because the atmosphere of the primitive Earth did not contain appreciable oxygen, this review of primitive bioenergetics is limited to anaerobic sources of energy.     

Interaction of cytochrome c with lipid monolayers

Cytochrome c was permitted to react with several lipid monolayers in which surface pressure, lipid charge and unsaturation were varied. Cytochrome c interaction with the films caused increased surface pressures, and the magnitude and rate of surface pressure change were compared under a variety of experimental conditions. Large surface pressure changes were associated with more expanded films, whereas greater rates of surface pressure change were associated with favorable charge interaction between cytochrome c and the films. Under the most favorable conditions, rates of surface pressure change were limited principally by protein diffusion to the interface. From these data, it is suggested that unsaturation in lipids of biological membranes may help stabilise non-polar protein-lipid interactions, whereas charge interaction may facilitate and direct initial binding of protein to membranes.