Cyanamide mediated synthesis under plausible primitive earth conditions. VI. The synthesis of glycerol and glycerophosphates.

The formation of glycerol occurs when a solution of DL-glyceraldehyde is heated in the presence of hydrogen sulfide at room temperature. DL-glyceraldehyde and dihydroxyacetone treated with hydrazine, as well as DL-glyceraldehyde incubated with formaldehyde are also partially converted to glycerol. The yields of the above reactions are from approximately 1% to about 3%. The formation of glycerophosphates occurs when glycerol is heated with ammonium dihydrogen phosphate and either urea or cyanamide. The yield of glycerophosphates is about 30%, most of which is sn-glycero-1 (3)-phosphate. These findings indicate that glycerol and sn-glycero-3-phosphate, which are moieties of glycerolipids, could have been formed under conditions which may have prevailed on the primitive Earth.

Cyanamide mediated syntheses under plausible primitive earth conditions. III. Synthesis of peptides.

Peptides were formed in yields of 5%, 17% and 66%, respectively, when aqueous solutions of glycine, isoleucine or phenylalanine were dried and heated for 24 h at 90 degrees C with adenosine 5'-triphosphate, 4-amino-5-imidazolecarboxamide and cyanamide. Glycine and L-phenylalanine produced mixtures of di-, tri- and tetrapeptides, while L-isoleucine gave only the dipeptide in detectable quantities. The dipeptides of L-isoleucine and L-phenylalanine were identified by mass spectrometry and enzymatic and enzymatic degradation.

Aliphatic hydrocarbons and fatty acids of some marine and freshwater microorganisms.

Gas chromatography and combined gas chromatography-mass spectrometry have been used to study the fatty acids and hydrocarbons of a bacterium from the Pacific Ocean, Vibrio marinus, a freshwater blue-green alga, Anacystis nidulans, and algal mat communities from the Gulf of Mexico. Both types of microorganisms (bacteria and algae) showed relatively simple hydrocarbon and fatty acid patterns, the hydrocarbons predominating in the region of C-17 and the fatty acids in the range of C-14 to C-18. The patterns of V. marinus were more comparable to those of the algal populations than to patterns reported for other bacteria. An incomplete correlation between fatty acids and hydrocarbons in both types of organisms was observed, making it difficult to accept the concept that the biosynthesis of hydrocarbons follows a simple fatty acid decarboxylation process.

Paraffinic hydrocarbons in the Orgueil, Murray, Mokoia and other meteorites.

Small samples of the Orgueil (Wiik Type I), Murray (Wiik Type II), Mokoia (Wiik Type III) and other meteorites (Alais, Ivuna, Al Rais, Bells, Cold Bokkeveld, Mighei, Nogoya, Santa Cruz, Grosnaja, Kaba, Lance, Ornans, Chainpur, Karoonda, Warrenton, and St. Caprais) were extracted with organic solvents, fractionated by silica gel chromatography, and analyzed by gas chromatography and by a new gas chromatographic-mass spectrometric technique. Only the high molecular weight hydrocarbons eluted by n-heptane were analyzed. The following observations were made: All meteorites contain paraffinic hydrocarbons in varying amounts and with a certain distribution. Normal and isomeric alkanes from Cl5 to about C25 with a maximum at C19-C21 were found in the Orgueil, Murray and Mokoia meteorites. Pristane and phytane, two saturated polyisoprenoid hydrocarbons, known to be degradation products of chlorophyll, were found in all meteorites except the Ornans, although in several (Type I and Type III, except Mokoia) the amounts were very small. No predominance of odd over even carbon-number hydrocarbons was observed except in the C22-C27 normal alkane range of some samples of the Orgueil. The concentration of alkanes in certain samples of the Orgueil was found to be about one order of magnitude lower than in others indicating a significant heterogeneity in the distribution of hydrocarbons. Practically all the meteorites of Type II and some of Type III (Mokoia) gave an essentially identical or very similar hydrocarbon chromatographic pattern, indicating a common origin for the hydrocarbons. The distribution of paraffinic hydrocarbons, including pristane and phytane, in some of these meteorites was found similar to that of microfossil-bearing pre-Cambrian rocks 2 x 10(9) years old or older. The Orguiel was similar to the Gunflint chert and Type II meteorites were similar to the Soudan rock. It remains to be seen whether these hydrocarbons were formed on the earth-moon system as suggested by Urey, on the asteroids, in the solar nebula, or whether they may be the result of a unique terrestrial contamination process.