Etta Peterson

Racemization of Amino Acids in Bones

IT has been shown that the extent of racemization of amino acids in a fossil can be used with certain limitations to estimate the age of the specimen1–6. For this dating work it is necessary to understand the kinetics and mechanism of the reactions involved. Here we show, by kinetic studies using modern bovine bone fragments heated in sealed ampoules for various time periods at several elevated temperatures, that the order of racemization rates of amino acids in bone is aspartic acid>alanine=glutamic acid>isoleucine≅leucine. Fossil bones not contaminated with modern amino acids are shown to have the same sequence of racemization rates.

Peptide Synthesis from Amino Acids in Aqueous Solution

Four dipeptides and a tripeptide were formed when an aqueous solution of glycine and leucine was exposed to ultraviolet light in the presence of cyanamide.

Amino acids indigenous to the murray meteorite.

Analysis of the Murray meteorite, a type II carbonaceous chondrite, has led to the identification of 17 amino acids. For seven of the amino acids nearly equal amounts of the D and L isomers are present, and 11 of the amino acids are not found in protein. These results suggest that these amino acids, like the amino acids of the Murchison meteorite, are extraterrestrial in origin.

A SEARCH FOR C60 IN CARBONACEOUS CHONDRITES

Analysis of interior samples of the Murchison meteorite by two routes yielded an upper limit of 2 ppb for its C60 content, as compared to parts per million levels for individual polycyclic aromatic hydrocarbons (PAHs). Provided the samples contain an interstellar component, which is probable since Murchison hydrocarbons contain excess deuterium, this result argues against the ubiquitous presence of C60 in the interstellar medium. A possible explanation for the absence of C60 was found in experiments showing how PAHs replace fullerenes as stable end products when hydrogen is present during carbon condensation. As a secondary result we found high molecular weight PAHs in the Murchison and Allende meteorites. Coronene and its methyl derivatives are especially interesting since features in the coronene spectrum have been shown to match some of the unidentified interstellar infrared emission bands.

Racemization of Amino Acids in Sediments from Saanich Inlet, British Columbia

In sediments spanning the last 9000 years from Saanich Inlet L enantiomers of amino acids are most abundant, but the percentages of D enantiomers increase with age, apparently because of partial racemization. Of the amino acids measured, glutamic acid and alanine show the greatest degree of racemization; leucine, isoleucine, and valine show the least.

Racemization of amino acids in marine sediments determined by gas chromatography

Abstract Ratios of d - to l -amino acids in acid hydrolysates from foraminifera of two deep-sea cores from the Caribbean Sea and Atlantic Ocean increase with depth and consequently with age over a span from 40,000 to 2,000,000 yr. The changing ratios do not seem to follow first-order reversible rate laws. Valine, leucine and glutamic acid apparently racemize (isoleucine epimerizes) at slower rates than do phenylalanine, alanine, aspartic acid and proline. The general relative order for rates of racemization of total (free and bound) amino acids may depend on the electron-withdrawing capacity of the R substituents of the amino acids and on the rates with which the amino acids are naturally hydrolyzed. In contrast to the total amino acids, the free amino acids in these samples are more extensively racemized, probably as a result of various catalytic and hydrolytic reactions. Previous related work based on ion-exchange chromatography has considered only ratios of alloisoleucine to isoleucine. With the gas chromatographic method used here, d / l ratios of all common asymmetric amino acids can be estimated. Measurement of the extent of racemization of amino acids in marine sediments seems to provide the basis for a geochronological tool covering the last few million years.

Modification of amino acids at shock pressures of 3.5 to 32 GPa.

Amino acids were subjected to shock impact over a pressure range of 3.5 to 32 GPa both within and without meteoritic mineral matrices. The extent of amino acid destruction, racemization, and conversion to secondary amino acids was examined. Abundances of parent compounds decreased by a factor of 10(3) over this pressure range. Racemization also occurred, but some residual optical activity remained in the amino acids surviving shocks up to 32 GPa. Secondary amino acids formed in the high peak pressure range; those identified were beta-alanine, glycine, alanine, gamma-aminobutyric acid, and beta-aminoisobutyric acid. At 30 GPa, the abundances of these daughter compounds exceeded those of the remaining initial amino acids. As the concomitant effects of high mechanical stress and temperature accompanying shocks cannot be separated in this work, their relative contribution to the observed transformations cannot be estimated. The survival of amino acids in shock experiments suggests that, after formation or emplacement of amino acids in carbonaceous chondrite parent bodies, these objects never experienced impact velocities greater than 5 km/s, which suffices to generate 30 GPa for typical silicate/silicate impacts. These results also provide guidelines for choosing appropriate capture media for interplanetary dust particles on Earth-orbiting platforms.

The Strecker synthesis as a source of amino acids in carbonaceous chondrites: Deuterium retention during synthesis

Deuterium-enriched amino acids occur in the Murchison carbonaceous chondrite. Synthesis from D-enriched interstellar precursors by Strecker reactions during aqueous alteration of the parent body has been proposed. To test this hypothesis, we have measured the retention of deuterium in amino acids produced from HCN, NH3, and formaldehyde-D2, acetaldehyde-D4, and acetone-D6 in H2O. The isotopic label is 50% to 98% retained, with variations in retentivity depending on the amino acid and the reaction conditions. If amino acids, once formed on the parent body by the Strecker synthesis, lose no deuterium by subsequent exchange with water or H-bearing minerals, then the observed deuterium isotopic composition of Murchison amino acids represents as much as 50% or more of the enrichments inherited from their interstellar precursors. Imino diacids are prominent side products of the Strecker synthesis which have not been reported in carbonaceous chondrites. Under the conditions of the Strecker reaction using deuterium labeled aldehydes and ketones, unlabeled amino acids are also formed by an HCN polymerization route indicating multiple pathways for the synthesis of amino acids in meteorites.

Amino acids in carbonaceous chondrites.

For almost 20 years laboratory experiments have advanced the concepts of chemical evolution, particularly with regard to formation of the amino acids. What has been generally lacking is concrete natural evidence for this chemical evolution hypothesis. The recent development of sophisticated analytical techniques and availability of carbonaceous chondrites with a minimum of terrestrial contamination has resulted in the identification of amino acids which provide strong evidence for a natural extraterrestrial chemical synthesis. Since the initial find in the Murchison meteorite (a type II carbonaceous chondrite) of both protein and nonprotein amino acids and amino acids with nearly equal abundances of D and L isomers, further studies have been carried out. These studies have revealed the presence of at least 35 amino acids; the population consists of a wide variety of linear, cyclic and polyfunctional amino acids which shows a trend of decreasing concentration with increasing carbon number. Investigations of the Murray meteorite (a type II carbonaceous chondrite) has produced similar results, but studies of the Orgueil meteorite (a type I carbonaceous chondrite) show only a limited suite of amino acids, some of which appear to be indigenous while others appear to be terrestrial contaminants. A sample of the Murchison meteorite was extracted with D2O and in addition to ‘free’ amino acids, showing no deuterium incorporation, some amino acids showed the presence of deuterium suggesting either a ‘precursor(s)’ or hydrogendeuterium exchange which require(s) formation of carbon-hydrogen bonds.

Search for porphyrins in lunar dust.

Evidence for porphyrins was obtained in the Apollo 11 bulk sample of lunar dust by fluorescence spectrometry and analytical demetallation. The indicated porphyrins showed major fluorescence excitation at 390 nanometers. Abundance was about 10-10 gram of porphyrin per gram of dust. Similar pigments were found in exhaust products from tests of a lunar descent engine. The similarity of results suggests that most if not all of the indicated porphyrin aggregate of the lunar sample probably was synthesized from rocket fuel during the landing of the lunar module. These compounds may be the product of a novel high-temperature synthesis of cosmochemical interest.