Amino Acids from Icy Amines: A Radiation-Chemical Approach to Extraterrestrial Synthesis

Detections of amino acids in meteorites go back several decades, with at least 100 such compounds being reported for the Murchison meteorite alone. The presence of these extraterrestrial molecules raises questions as to their formation, abundance, thermal stability, racemization, and possible subsequent reactions. Although all of these topics have been studied in laboratories, such work often involves many variables and unknowns. This has led us to seek out model systems with which to uncover reaction products, test chemical predictions, and sited light on underlying reaction mechanisms. This presentation will describe one such study, focusing on amino-acid formation in ices

Nanoflow Separation of Amino Acids for the Analysis of Cosmic Dust

The delivery of amino acids to the early Earth by interplanetary dust particles, comets, and carbonaceous meteorites could have been a significant source of the early Earth's prebiotic organic inventory. Amino acids are central to modern terrestrial biochemistry as major components of proteins and enzymes and were probably vital in the origin of life. A variety of amino acids have been detected in the CM carbonaceous meteorite Murchison, many of which are exceptionally rare in the terrestrial biosphere including a-aminoisobutyric acid (AIB) and isovaline. AIB has also been detected in a small percentage of Antarctic micrometeorite grains believed to be related to the CM meteorites We report on progress in optimizing a nanoflow liquid chromatography separation system with dual detection via laser-induced-fluorescence time of flight mass spectrometry (nLC-LIF/ToF-MS) for the analysis of o-phthaldialdehydelN-acetyl-L-cysteine (OPA/NAC) labeled amino acids in cosmic dust grains. The very low flow rates (0.1 ml/min) combined with 4 orders of magnitude lower than traditional GC-MS techniques), and specificity (compounds identities are determined by both retention time and exact mass) makes this a compelling technique. However, the development of an analytical method to achieve separation of compounds as structurally similar as amino acid monomers and produce the sharp peaks required for maximum sensitivity is challenging

The Escherichia coli phage-shock-protein (psp) operon

The phage-shock-protein (psp) operon helps to ensure survival of Escherichia coli in tate stationary phase at alkaline pH, and protects the cell against dissipation of its proton-motive force against challenge. It is strongly induced by filamentous phage pIV and its bacterial homologues, and by mutant porins that don't localize properly, as well as by a number of other stresses. Transcription of the operon is dependent on sigma(54) and a constitutively active, autogenously controlled activator. psp-operon expression is controlled by one negatively and several positively acting regulators, none of which is a DNA-binding protein. The major product of the operon, PspA, may also serve as a negative regulator of an unusual porin, OmpG

The PspA protein of Escherichia coli is a negative regulator of sigma(54)-dependent transcription

In Eubacteria, expression of genes transcribed by an RNA polymerase holoenzyme containing the alternate sigma factor sigma(54) is positively regulated by proteins belonging to the family of enhancer-binding proteins (EBPs), These proteins bind to upstream activation sequences and are required for the initiation of transcription at the sigma(54)-dependent promoters. They are typically inactive until modified in their N-terminal regulatory domain either by specific phosphorylation or by the binding of a small effector molecule. EBPs lacking this domain, such as the PspF activator of the sigma(54)-dependent pspA promoter, are constitutively active. We describe here the in vivo and in vitro properties of the PspA protein of Escherichia coli, which negatively regulates expression of the pspA promoter without binding DNA directly

Analyses of Aliphatic Aldehydes and Ketones in Carbonaceous Chondrites

Aliphatic aldehydes and ketones are essential building blocks for the synthesis of more complex organic compounds. In spite of their potentially key role as precursors of astrobiologically-important molecules, such as amino acids and carboxylic acids, this family of compounds has scarcely been evaluated in carbonaceous chondrites. The paucity of such analyses likely derives from the low concentration of aldehydes and ketones in the meteorites, and from the currently used chromatographic methodologies that have not been optimized for meteorite analysis. In this work, we report the development of a novel analytical method to quantify the molecular distribution and compound-specific isotopic analysis of 29 aliphatic aldehydes and ketones. Using this method, we have investigated the molecular distribution and 13C-isotopic composition of aldehydes and ketones in ten carbonaceous chondrites from the CI, CM, CR and CV groups. The total concentration of carbonyl compounds ranged from 130 to 1000 nmolg-1 of meteorite, with formaldehyde, acetaldehyde, and acetone being the most abundant species in all investigated samples. The 13C-isotopic values ranged from 67 to +64 and we did not observe clear relationships between 13C-content and molecular weight. Accurately measuring the relative abundances, determining the molecular distribution, and isotopic composition of chondritic organic compounds is central in assessing both their formation chemistry and synthetic relationships

Pathways to Meteoritic Glycine and Methylamine

Glycine and methylamine are meteoritic water-soluble organic compounds that provide insights into the processes that occurred before, during, and after the formation of the Solar System. Both glycine and methylamine and many of their potential synthetic precursors have been studied in astrophysical environments via observations, laboratory experiments, and modeling. Despite these studies, the synthetic mechanisms for their formation leading to their occurrence in meteorites remain poorly understood. Typical 13C-isotopic values (13C) of meteoritic glycine and methylamine are 13C-enriched relative to their terrestrial counterparts; thus, analyses of their stable carbon isotopic compositions (13C/12C) may be used not only to assess terrestrial contamination in meteorites but also to provide information about their synthetic routes inside the parent body. Here, we examine potential synthetic routes of glycine and methylamine from a common set of precursors present in carbonaceous chondrite meteorites, using data from laboratory analyses of the well-studied CM2 Murchison meteorite. Several synthetic mechanisms for the origins of glycine and methylamine found in carbonaceous chondrites may be possible, and the prevalence of these mechanisms will largely depend on (a) the molecular abundance of the precursor molecules and (b) the levels of processing (aqueous and thermal) that occurred inside the parent body. In this work, we also aim to contextualize the current knowledge about gas-phase reactions and irradiated ice grain chemistry for the synthesis of these species through parent body processes. Our evaluation of various mechanisms for the origins of meteoritic glycine and methylamine from simple species shows what work is still needed to evaluate both the abundances and isotopic compositions of simpler precursor molecules from carbonaceous chondrites as well as the effects of parent body processes on those abundances and isotopic compositions. The analyses presented here combined with the indicated measurements will aid a better interpretation of quantitative analysis of reaction rates, molecular stability, and distribution of organic products from laboratory simulations of interstellar ices, astronomical observations, and theoretical modeling

Analysis of Volatile Organic Compounds in the Apollo Next Generation Sample Analysis (ANGSA) 73002 Core Sample

Understanding the organic content of lunar regolith was an early priority upon the return of Apollo samples, with amino acids being of special interest because of their importance to life on Earth and their astrobiological relevance. Many initial studies focused on the detection of amino acids in these samples and attempts to determine the origin of those compounds. Although no consensus on the origin of the amino acids was reached in those early studies, more recent work determined that the detected amino acids originated from both terrestrial contamination and meteoritic or cometary in fall to the lunar surface. A majority of the amino acids in the Apollo samples studied originated from precursor molecules, either indigenous to the lunar samples or contaminants, that reacted during the water extraction and acid hydrolysis process for analysis in the laboratory, but the identities of the amino acid precursors still remain poorly understood. Such precursors could include hydrogen cyanide (HCN) and other volatile organic compounds such as amines, carboxylic acids, or aldehydes and ketones. The identities of these compounds, as well as the effects of years of curation on their abundances in lunar regolith samples stored at ambient temperature under nitrogen gas purge, are not clear. The specially curated samples available through the Apollo Next Generation Sample Analysis (ANGSA) program provide a unique opportunity to use state-of- the-art analytical techniques to examine previously unstudied lunar materials. The ANGSA samples include three types of samples: 1) samples stored frozen since <1 month after Earth arrival; 2) samples stored under helium; and 3) a double drive tube collected by Apollo 17 astronauts, with the bottom portion of the drive tube sealed under vacuum on the Moon and never opened. In contrast to the typically curated Apollo samples that have been kept for decades at room temperature under flowing nitrogen purge that may have significantly reduced the abundance of volatiles, the vacuum-sealed and frozen samples may have enhanced preservation of these volatiles. Our initial investigation examines amino acids and their potential volatile precursors, including hydrogen cyanide (HCN), aldehydes, ketones, amines, and mono-carboxylic acids, in a sample from the top portion of the Apollo 17 double drive tube. These results will aid in understanding the lunar abundances of these molecules and will also be compared to future analyses of other drive tube and frozen ANGSA samples

Molecular Distribution, 13C-Isotope, and Enantiomeric Compositions of Carbonaceous Chondrite Monocarboxylic Acids

The watersoluble organic compounds in carbonaceous chondrite meteorites constitute a record of the synthetic reactions occurring at the birth of the solar system and those taking place during parent body alteration and may have been important for the later origins and development of life on Earth. In this present work, we have developed a novel methodology for the simultaneous analysis of the molecular distribution, compoundspecific 13C, and enantiomeric compositions of aliphatic monocarboxylic acids (MCA) extracted from the hotwater extracts of 16 carbonaceous chondrites from CM, CR, CO, CV, and CK groups. We observed high concentrations of meteoritic MCAs, with total carbon weight percentages which in some cases approached those of carbonates and insoluble organic matter. Moreover, we found that the concentration of MCAs in CR chondrites is higher than in the other meteorite groups, with acetic acid exhibiting the highest concentration in all samples. The abundance of MCAs decreased with increasing molecular weight and with increasing aqueous and/or thermal alteration experienced by the meteorite sample. The 13C isotopic values of MCAs ranged from 52 to +27, and aside from an inverse relationship between 13C value and carbon straightchain length for C3C6 MCAs in Murchison, the 13Cisotopic values did not correlate with the number of carbon atoms per molecule. We also observed racemic compositions of 2methylbutanoic acid in CM and CR chondrites. We used this novel analytical protocol and collective data to shed new light on the prebiotic origins of chondritic MCAs