Alan W. Schwartz

Nitrogen-heterocyclic compounds in meteorites: significance and mechanisms of formation

Abstract Samples of the Murchison (C2), Murray (C2) and Orgueil (C1) carbonaceous meteorites were analyzed for nitrogen-heterocyclic compounds using gas chromatography, cation and anion exclusion liquid chromatography and mass spectrometry. The purines adenine, guanine, hypoxanthine and xanthine were identified in formic acid extracts of all samples, in concentrations ranging from 114–655 ppb. Purines have not previously been found in the Murray meteorite and adenine. hypoxanthine and xanthine have never simultaneously been detected in meteorite extracts. All four biologically significant purines, as well as the pyrimidine uracil have now been identified in these meteorites. A number of other, previously reported N -heterocyclic compounds such as certain hydroxypyrimidines and s -triazines could not be detected in any of the extracts. Laboratory data indicated that both these classes of compounds may be formed from structurally simple precursors (such as guanylurea in the case of s -triazines) during the extraction and analysis of meteorite extracts. We find that the suite of N -heterocyclic compounds identified in meteorites do not, at present, permit a clear distinction to be made between mechanisms of synthesis such as the Fischer-Tropsch type and other candidates. Secondary reactions and conversions in meteorite parent bodies, of HCN and other nitriles produced by Miller-Urey type reactions as well as by Fischer-Tropsch type reactions, must also be considered.

Search for purines and pyrimidines in the Murchison meteorite

Abstract A 1 g interior sample of the Murchison CII meteorite was examined for the presence of purines and pyrimidines by dual-column, ion-exclusion chromatography and ultraviolet spectroscopy. Xanthine, not previously reported in meteorites, was found to be the major purine liberated by extraction with formic acid, with a concentration corresponding to 2.3 μg/g of meteorite. Guanine (0.1 ppm) and hypoxanthine (0.04 ppm) were also tentatively identified. The presence of adenine could not be confirmed. No pyrimidines were detected at concentrations higher than the background level (0.01 ppm) in water, formic acid or strong acid extracts. Silylation of the water extract, however, resulted in the appearance of 4-hydroxypyrimidine, 4-hydroxy-2-methylpyrimidine and 4-hydroxy-6-methylpyrimidine. These compounds are-though to be formed during the silylation procedure from contaminants present in the reagent.

Phosphorus in prebiotic chemistry

The prebiotic synthesis of phosphorus-containing compounds—such as nucleotides and polynucleotides—would require both a geologically plausible source of the element and pathways for its incorporation into chemical systems on the primitive Earth. The mineral apatite, which is the only significant source of phosphate on Earth, has long been thought to be problematical in this respect due to its low solubility and reactivity. However, in the last decade or so, at least two pathways have been demonstrated which would circumvent these perceived problems. In addition, recent results would seem to suggest an additional, extraterrestrial source of reactive phosphorus. It appears that the ‘phosphorus problem’ is no longer the stumbling block which it was once thought to be.

The prebiotic synthesis of carbohydrates: A reassessment

SummaryQuestions concerning the significance of previous work on the formose reaction have led us to reexamine the question of the prebiotic synthesis of sugars. The results of new experiments lead to the following conclusions: The formose reaction is a geochemically plausible reaction which depends on neither basic conditions nor on the presence of trace amounts of carbohydrate impurities. However, this process is not a plausible source of ribose nor of any other individual sugar. In contrast to the nonspecific formation of complex mixtures of sugars via the formose reaction, the reduced sugar pentaerythritol is formed with great selectivity by the ultraviolet irradiation of 0.1 M formaldehyde. This compound may have played an important role in chemical evolution.

Basic nitrogen-heterocyclic compounds in the Murchison meteorite

Abstract A fragment of the Murchison (C2) carbonaceous meteorite was analyzed for basic, N- heterocyclic compounds, by dual detector capillary gas chromatography as well as capillary gas chromatography/mass spectrometry, using two columns of different polarity. In the formic acid extract 2,4,6-trimethylpyridine, quinoline, isoquinoline, 2-methylquinoline and 4-methylquinoline were positively identified. In addition, a suite of alkylpyridines and quinolines and/or isoquinolines was tentatively identified from their mass spectra. The (iso)quinolines were found to contain methyl substituents exclusively. The distribution of the pyridines observed reveals a similarity to that observed from catalytic reactions of ammonia and simple aldehydes under conditions similar to those applied in Fischer-Tropsch type reactions.

Chemical Reduction of Phosphate on the Primitive Earth

If phosphorus played a role in the origin of life, some means of concentrating micromolar levels of phosphate (derived from the calcium phosphate mineral apatite), must first have been available. Here we show that simulated (mini)lightning discharges in model prebiotic atmospheres, including only minimally reducing ones, reduce orthophosphates, including apatite, to produce substantial yields of phosphite. Electrical discharges associated with volcanic eruptions could have provided a particularly suitable environment for this process. Production of relatively soluble and reactive phosphite salts could have supplied a pathway by which the first phosphorus atoms were incorporated into (pre)biological systems.

Template-Directed Synthesis of Acyclic Oligonucleotide Analogues*

SummaryBis-phosphoimidazolides of an analogue of adenosine (in which ribose is replaced by an acyclic chain) and of two related analogues of guanosine undergo oligomerization in the presence of complementary polynucleotide templates. Data on the template- and nontemplate-directed reactions are presented, and the possible relevance to origins of life is discussed.

Uracil synthesisvia HCN oligomerization

Uracil is released from HCN oligomers upon acid hydrolysis in concentrations of 0.001% for 1M HCN solutions to 0.005% for 0.1M solutions. This yield is comparable with earlier reported, minor or nonbiological pyrimidines such as 5-hydroxyuracil and orotic acid. This is the first report of uracil itselfvia HCN oligomerization. Data are presented which establish that the observed uracil is not formed by decarboxylation of previously formed orotic acid, butvia acid hydrolysis of at least two other precursors.

Prebiotic adenine synthesis via HCN oligomerization in ice.

Adenine is produced (after hydrolysis) when 0.01 M solutions of HCN are adjusted to pH 9.2 with NH4OH and are frozen at -2 degrees C for 60-100 days. The addition of glycolonitrile (the cyanohydrin of formaldehyde) increases the yield of adenine under these conditions by about five-fold. These results confirm and extend an earlier suggestion that purine synthesis on the prebiotic Earth might have occurred in frozen, dilute solutions of HCN.

Reduction and Activation of Phosphate on the Primitive Earth

Electrical discharges in water-saturated N2 containing 1–10% CH4 were shown earlier toreduce phosphate to phosphite. This mechanism was suggestedas a possible source of water-soluble phosphorus-containing compounds in volcanic environments on the prebiotic Earth.We have now extended our investigations to gas mixtures inwhich CO2 and N2 are the main components, and studied the effect of introducing smallamounts of H2 and CO.We show that surprisingly high conversions to phosphite occurin reducing mixtures and thatseveral percent reduction of apatite occurs even in thepresence of as little as 1% each of H2 and CO. We were also able to confirm a previous report ofpolyphosphate production as a result of heating the mineral apatite in the presence of other minerals.