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What was the minimum requirement for prebiotic life ? on Tue Aug 18, 2009 1:02 pm
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Books :
he spark of life: Darwin and the primeval soup By Christopher Wills, Jeffrey Bada
Life's origin: the beginnings of biological evolution By J. William Schopf
Origins of life on the earth and in the cosmos By Geoffrey L. Zubay
Prebiotic cytosine synthesis: A critical analysis and implications for the origin of life Robert Shapiro*
Abstract
Among the most commonly encountered ideas concerning the origin of life is the one that it involved an “RNA world” at an early stage (1). The term was coined by Gilbert (2), who also stated “The first stage of evolution proceeeds, then, by RNA molecules performing the catalytic activities necessary to assemble themselves out of a nucleotide soup.” The existence of such a soup has generally been taken for granted. For example, Eigen and Schuster (3) wrote “The building blocks of polynucleotides—the four bases, ribose and phosphate were available too under prebiotic conditions. Material was available from steadily refilling pools for the formation of polymers, among them polypeptides and polynucleotides.” The experimental evidence to date, however, does not appear to support such claims.
Many problems have arisen with both the prebiotic synthesis and the stability of ribose (4–9). To avoid the need for ribose, some authors have preferred to invoke an RNA-like polymer, with a simpler or more accessible backbone, at the start of life (6, 10–16). A pre-RNA world would have come first, during which some substance of this type carried out the genetic functions later taken over by RNA. In the great majority of these theories, Watson–Crick pairing of A with U and of G with C is retained as the basis of genetic template recognition.
These suggestions still presume that the bases adenine, cytosine, guanine, and uracil were readily available on early Earth. I have argued that this presumption is not supported by the existing knowledge of the basic chemistry of these substances (4, 17). If the availability of the Watson–Crick pairs at the start of life appears implausible, then more attention must be given to theories that employ a very different replicator or no replicator at all.
To provide a firm basis for this conclusion, I have undertaken a series of reviews in which I consider in detail the chemical evidence for the availability of the Watson–Crick bases at the start of life. In a previous paper, however, I concluded that current information concerning the availability and chemical properties of adenine did not support the idea that it was used in a replicator at the start of life (17). In this publication, I wish to consider the prebiotic syntheses and the stability of cytosine.
RESULTS AND DISCUSSION
Absence of Cytosine in Meteorites and Electrical Spark Discharge Experiments. The isolation of adenine and guanine from meteorites has been cited as evidence that these substances might have been available as “raw material” on prebiotic Earth (18). However, acid hydrolyses have been needed to release these materials, and the amounts isolated have been low (17–19). Traces of uracil have also been reported in such analyses (20), but no cytosine at all.
The formation of a substance in an electric spark discharge conducted in a simulated early atmosphere has also been regarded as a positive indication of its prebiotic availability (21). Again, low yields of adenine and guanine have been reported in such reactions, but no cytosine (22). The failure to isolate even traces of cytosine in these procedures signals the presence of some problem with its synthesis and/or stability.
Proposed Prebiotic Cytosine Syntheses. As bonds from carbon to a hetero atom are more readily constructed than carbon–carbon bonds, cytosine syntheses have usually combined a three-carbon fragment with another bearing a urea-like carbon. The most prominent C-3 fragments used have been cyanoacetylene and its hydrolysis product, cyanoacetaldehyde. These processes are discussed separately below.
Syntheses based on cyanoacetylene. As shown in Fig. 1(Fig. 1), Ferris et al. (23) reported that 0.2 M cyanoacetylene (I) and 2 M cyanate (II) reacted together readily at 30°C to give trans-cyanovinylurea (III) and unidentified products. Conversion of trans-cyanovinylurea to cytosine (with the cis isomer as a likely intermediate) took place readily at pH 11 or greater. In a more direct preparation, cyanate and cyanoacetylene were heated together at 100°C for 24 hr. In a typical run at low concentration, 0.025 M cyanoacetylene and 0.05 M cyanate (the stoichiometry requires two cyanates per cyanoacetylene) afforded 6% cytosine. The maximum yield observed over all circumstances was 19%.
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Figure 1 Principal proposed prebiotic routes to cytosine. The hydrolysis products of the reactants and of cytosine are included in the scheme.
Questions arise, however, concerning the availability of the reactants on early Earth. Cyanoacetylene can be produced in a spark discharge in a CH4/N2 mixture as the second most prevalent product (up to a maximum of 8.4% of the principal product, HCN) (23, 24). This mixture, which introduces carbon in reduced form but excludes ammonia and water, is an unlikely candidate for Earth’s atmosphere at the time of the origin of life. That atmosphere was “… probably dominated by CO2 and N2, with traces of CO, H2, and reduced sulfur gases”, unless a volcanic source of methane and ammonia was present (25). By contrast, when ammonia (24) or hydrogen sulfide (26) are included in spark discharge experiments, little cyanoacetylene is produced. The aspartic acid and asparagine that are formed under those conditions arise to some extent from the reaction of cyanoacetylene with HCN and ammonia (27).