“…The mechanism for the formation of amino acids from HCN polymerisation has not been described, but it has been suggested that the trimer (aminomalononitrile, AMN) or tetramer (diaminomaleonitrile, DAMN) of HCN might be involved in the synthesis. Studies of the formation of amino acids from AMN and DAMN were conducted by Matthews and co-worker [ 73 , 74 ] as well as Ferris and co-worker [ 64 ].…”
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.
“…The mechanism for the formation of amino acids from HCN polymerisation has not been described, but it has been suggested that the trimer (aminomalononitrile, AMN) or tetramer (diaminomaleonitrile, DAMN) of HCN might be involved in the synthesis. Studies of the formation of amino acids from AMN and DAMN were conducted by Matthews and co-worker [ 73 , 74 ] as well as Ferris and co-worker [ 64 ].…”
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.
“…The earliest experiments on the condensation of amino acids were conducted by simply heating the solutions of amino acids [7] and various thermal condensation and dehydration reactions between amino acids or amino acid precursors appeared in the literature [8, 9]. Subsequent, more sophisticated approaches included hydrolysis of HCN polymers [10], condensation on clay environments [11] and in the presence of different mineral surfaces [12], or by atmospheric gases [13, 14]. Modern methods, such as copper-catalyzed and salt-induced peptide synthesis [15, 16], or condensation of N -carboxyanhydrides [17] allow for formation of peptides that are longer (ca.…”
Section: Formation Of Peptide Bonds and Phosphodiester Bonds By Ormentioning
In this mini-review we present some experimental approaches to the important issue in the origin of life, namely the origin of nucleic acids and proteins with specific and functional sequences. The formation of macromolecules on prebiotic Earth faces practical and conceptual difficulties. From the chemical viewpoint, macromolecules are formed by chemical pathways leading to the condensation of building blocks (amino acids, or nucleotides) in long-chain copolymers (proteins and nucleic acids, respectively). The second difficulty deals with a conceptual problem, namely with the emergence of specific sequences among a vast array of possible ones, the huge “sequence space”, leading to the question “why these macromolecules, and not the others?”We have recently addressed these questions by using a chemical synthetic biology approach. In particular, we have tested the catalytic activity of small peptides, like Ser-His, with respect to peptide- and nucleotides-condensation, as a realistic model of primitive organocatalysis. We have also set up a strategy for exploring the sequence space of random proteins and RNAs (the so-called “never born biopolymer” project) with respect to the production of folded structures. Being still far from solved, the main aspects of these “open questions” are discussed here, by commenting on recent results obtained in our groups and by providing a unifying view on the problem and possible solutions. In particular, we propose a general scenario for macromolecule formation via fragment-condensation, as a scheme for the emergence of specific sequences based on molecular growth and selection.
“…Many methods have been proposed to synthesize HCN polymers. 19,[27][28][29][30][31][32][33] The protocols, which propose a direct polymerization of HCN, differ by the nature of the catalyst. As NH 3 is detected in numerous astrophysical media and particularly in comets, we choose to catalyze the HCN polymerization with ammonia.…”
HCN polymers are complex organic solids resulting from the polymerization of hydrogen cyanide (HCN) molecules. They have been suspected to contribute to the refractory carbonaceous component of comets as well as the distributed CN sources in cometary atmospheres. Titan's tholins are also organic compounds produced in a laboratory setting but result from the complex chemistry between N2 and CH4 induced by UV radiation or electric discharges. Some of these compounds have optical properties in the visible range fairly similar to those of Titan's aerosols or those of the reddish surfaces of many icy satellites and small bodies. It has been proposed that HCN polymers are constituents of tholins but this statement has never received any clear demonstration. We report here on the comparative analysis of tholins and HCN polymers in order to definitely establish if the molecules identified in the HCN polymers are present in the tholins as well. First, we present a global comparison of HCN polymers with three kinds of tholins, using elemental analysis measurements, infrared spectroscopy and very high resolution mass spectrometry of their soluble fraction. We show that the chemical composition of the HCN polymers is definitely simpler than that of any of the tholins studied. Second, we focus on six ions representative of the composition of HCN polymers and using mass spectrometry (HRMS and MS/HRMS), we determine that these tholins contain at best a minor fraction of this kind of HCN polymers.
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