Role of ferrocyanides in the prebiotic synthesis of α-amino acids.

We investigated the synthesis of α-amino acids under possible prebiotic terrestrial conditions in the presence of dissolved iron (II) in a simulated prebiotic ocean. An aerosol-liquid cycle with a prebiotic atmosphere is shown to produce amino acids via Strecker synthesis with relatively high yields. However, in the presence of iron, the HCN was captured in the form of a ferrocyanide, partially inhibiting the formation of amino acids. We showed how HCN captured as Prussian Blue (or another complex compound) may, in turn, have served as the HCN source when exposed to UV radiation, allowing for the sustained production of amino acids in conjunction with the production of oxyhydroxides that precipitate as by-products. We conclude that ferrocyanides and related compounds may have played a significant role as intermediate products in the prebiotic formation of amino acids and oxyhydroxides, such as those that are found in iron-containing soils and that the aerosol cycle of the primitive ocean may have enhanced the yield of the amino acid production.

New insights into the characterization of 'insoluble black HCN polymers'.

The data presented here provide a novel contribution to the understanding of the structural features of HCN polymers and could be useful in further development of models for prebiotic chemistry. The interpretation of spectroscopic and analytical data, along with previous results reported by other authors, allowed us to propose a mechanism for the aqueous polymerization of HCN from its primary and simplest isolated oligomer, the diaminomaleonitrile (DAMN) tetramer. We suggest that 'insoluble black HCN polymers' are formed by an unsaturated complex matrix, which retains a significant amount of H(2) O and important bioorganic compounds or their precursors. This polymeric matrix can be formed by various motifs of imidazoles and cyclic amides, among others. The robust formation of HCN polymers assayed under several conditions seems to explain the plausible ubiquity of these complex substances in space.

Prebiotic synthesis of protobiopolymers under alkaline ocean conditions.

Clasically, prebiotic chemistry has focused on the production and identification of simple organic molecules, many of them forming part of "intractable polymers" named tholins. In a previous work, we demonstrated that in experiments using an external energy source and inorganic carbon the aqueous aerosols improved the formation of hydrophilic tholins. Herein, we elucidate the role of pH (from 4 to 12) in prebiotic experiments using saline aqueous aerosols, spark discharges and an atmosphere containing CH(4). At all values of pH, the saline aqueous aerosols increased the production of a significant variety of carboxylic acids that could have been present in a primitive Krebs cycle. Moreover, the study for the first time of hydrophilic tholins by 2-D electrophoresis revealed that these are formed by a set of unexpected heavy polymeric species. The initial alkaline conditions significantly increased both the apparent molecular weight of polymeric species up to 80 kDa and their diversity. We propose the term of protobiopolymers to denote those polymeric species fractionated by 2-D electrophoresis since these are formed by biomolecules present in living systems and show diversity in length as well as in functional groups. Thus, aerosols formed in simulated alkaline ocean conditions could provide an optimal medium for the formation of the primeval materials that could be precursors to the emergence of life.

Synthesis of pyrimidines and triazines in ice: implications for the prebiotic chemistry of nucleobases.

Herein, we report the efficient synthesis of RNA bases and functionalized s-triazines from 0.1 M urea solutions in water after subjection to freeze-thaw cycles for three weeks. The icy solution was under a reductive, methane-based atmosphere, which was subjected to spark discharges as an energy source for the first 72 h of the experiment. Analysis of the products indicates the synthesis of the s-triazines cyanuric acid, ammeline, ammelide, and melamine, the pyrimidines cytosine, uracil, and 2,4-diaminopyrimidine, and the purine adenine. An experiment performed as a control at room temperature, with the urea solution in the liquid phase and with the same atmosphere and energy source, led to the synthesis of hydantoins and insoluble tholin, but there was no evidence of the synthesis of pyrimidines or triazines. The synthesis of pyrimidines from urea is possible under a methane/nitrogen atmosphere only at low temperature, in the solid phase. The generation of both pyrimidines and triazines in comparable yields from urea, together with a possible role for triazines as alternative nucleobases, opens new perspectives on the prebiotic chemistry of informational polymers.

Thermal wet decomposition of Prussian Blue: implications for prebiotic chemistry.

The complex salt named Prussian Blue, Fe4[Fe(CN)6]3 x 15 H2O, can release cyanide at pH > 10. From the point of view of the origin of life, this fact is of interest, since the oligomers of HCN, formed in the presence of ammonium or amines, leads to a variety of biomolecules. In this work, for the first time, the thermal wet decomposition of Prussian Blue was studied. To establish the influence of temperature and reaction time on the ability of Prussian Blue to release cyanide and to subsequently generate other compounds, suspensions of Prussian Blue were heated at temperatures from room temperature to 150 degrees at pH 12 in NH3 environment for several days. The NH3 wet decomposition of Prussian Blue generated hematite, alpha-Fe2O3, the soluble complex salt (NH4)4[Fe(CN6)] x 1.5 H2O, and several organic compounds, the nature and yield of which depend on the experimental conditions. Urea, lactic acid, 5,5-dimethylhydantoin, and several amino acids and carboxylic acids were identified by their trimethylsilyl (TMS) derivatives. HCN, cyanogen (C2N2), and formamide (HCONH2) were detected in the gas phase by GC/MS analysis.

Synthesis of polycyclic aromatic hydrocarbons and acetylene polymers in ice: a prebiotic scenario.

The recent evidences of presence of subsurface oceans of liquid water and ice on Saturn's moons, and the possible presence and astrobiological importance of polycyclic aromatic hydrocarbons (PAHs) in these environments, provide strong motivation for the exploration of the prebiotic chemistry in ice and to test if PAHs could be experimentally synthesized in ice surfaces under atmospheres containing methane as carbon source. In this work, we present a new design for prebiotic-chemistry experiments in ice matrix. Using this design, a mixture of products including PAHs, polar aromatic compounds, and hydrophilic acetylene-based polymers was obtained. We propose that acetylene generation in a methane/nitrogen atmosphere and subsequent polymerization to PAHs and polyynes could be a favored pathway in the presence of water freeze-melt cycles. These results shed light on the processes involved in PAH synthesis in icy environments and on the physical factors that drive the different competing pathways in methane/nitrogen atmospheres.

Simple Organics and Biomonomers Identified in HCN Polymers: An Overview.

Hydrogen cyanide (HCN) is a ubiquitous molecule in the Universe. It is a compound that is easily produced in significant yields in prebiotic simulation experiments using a reducing atmosphere. HCN can spontaneously polymerise under a wide set of experimental conditions. It has even been proposed that HCN polymers could be present in objects such as asteroids, moons, planets and, in particular, comets. Moreover, it has been suggested that these polymers could play an important role in the origin of life. In this review, the simple organics and biomonomers that have been detected in HCN polymers, the analytical techniques and procedures that have been used to detect and characterise these molecules and an exhaustive classification of the experimental/environmental conditions that favour the formation of HCN polymers are summarised. Nucleobases, amino acids, carboxylic acids, cofactor derivatives and other compounds have been identified in HCN polymers. The great molecular diversity found in HCN polymers encourages their placement at the central core of a plausible protobiological system.