Amino Acids In Meteorites Research Articles

High‐Pressure Torsion Processing of Serine and Glutamic Acid: Understanding Mechanochemical Behavior of Amino Acids under Astronomical Impacts

Astronomical impacts by small solar system bodies (meteoroids, asteroids, comets, and transitional objects) are considered a mechanism for delivering amino acids and their polymerization to proteins in early Earth conditions. High‐pressure torsion (HPT) is a new methodology to simulate such impacts and clarify the behavior of biomolecules. Herein, two amino acids, crystalline L‐serine and L‐glutamic acid that are detected in meteorites, are processed by HPT and examined by ex situ X‐ray diffraction, Raman spectroscopy, nuclear magnetic resonance, Fourier‐transform infrared spectroscopy, and in situ mechanical shear testing. No polymerization, chemical reactions, or phase transformations are detected after HPT, indicating that the stability and presence of these two amino acids in meteorites are quite reasonable. However, some microstructural and mechanical changes like crystal size reduction to the nanometer level, crystal defect formation, lattice expansion by vacancy formation, and shear strength enhancement to the steady state are found which are similar to the behaviors reported in metals and ceramics after HPT processing.

Chiroptical properties of membrane glycerophospholipids and their chiral backbones.

Glycerophospholipid membranes are one of the key cellular components. Still, their species-dependent composition and homochirality remain an elusive subject. In the context of the astrophysical circularly polarized light scenario likely involved in the generation of a chiral bias in meteoritic amino and sugar acids in space, and consequently in the origin of life's homochirality on Earth, this study reports the first measurements of circular dichroism and anisotropy spectra of a selection of glycerophospholipids, their chiral backbones and their analogs. The rather low asymmetry in the interaction of UV/VUV circularly polarized light with sn-glycerol-1/3-phosphate indicates that chiral photons would have been unlikely to directly induce symmetry breaking to membrane lipids. In contrast, the anisotropy spectra of d-3-phosphoglyceric acid and d-glyceraldehyde-3-phosphate unveil up to 20 and 100 times higher maximum anisotropy factor values, respectively. This first experimental report, targeted on investigating the origins of phospholipid symmetry breaking, opens up new avenues of research to explore alternative mechanisms leading to membrane lipid homochirality, while providing important clues for the search for chiral biosignatures of extant and/or extinct life in space, in particular for the ExoMars 2028 mission.

A search for tryptophan in the gas of the IC 348 star cluster of the Perseus molecular cloud

ABSTRACT We have used spectra of the Spitzer Space Telescope to conduct a search for the aromatic amino acid tryptophan in the interstellar gas of the young star cluster IC 348. For all the strongest mid-infrared (mid-IR) laboratory bands of tryptophan, we have found counterpart emission lines in the observed spectrum which are consistent in wavelength and strength with the laboratory measurements. Assuming that the detected emission lines are due to tryptophan and using the measured fluxes, we estimate a tryptophan column density in the line of sight of the core of IC 348 in the range 109–1011 cm−2. The observed emission lines are also found in the combined spectrum of >30 interstellar locations obtained in diverse unrelated star-forming regions observed by Spitzer. This could be an indication that the molecule causing the emission is widespread in interstellar space. Future high spectral resolution mid-IR searches for proteinogenic amino acids in protostars, protoplanetary discs, and in the interstellar medium will be key to study an exogenous origin of meteoritic amino acids and to understand how the pre-biotic conditions for life were set in the early Earth.

Insights into the formation and evolution of extraterrestrial amino acids from the asteroid Ryugu

All life on Earth contains amino acids and carbonaceous chondrite meteorites have been suggested as their source at the origin of life on Earth. While many meteoritic amino acids are considered indigenous, deciphering the extent of terrestrial contamination remains an issue. The Ryugu asteroid fragments (JAXA Hayabusa2 mission), represent the most uncontaminated primitive extraterrestrial material available. Here, the concentrations of amino acids from two particles from different touchdown sites (TD1 and TD2) are reported. The concentrations show that N,N-dimethylglycine (DMG) is the most abundant amino acid in the TD1 particle, but below detection limit in the other. The TD1 particle mineral components indicate it experienced more aqueous alteration. Furthermore, the relationships between the amino acids and the geochemistry suggest that DMG formed on the Ryugu progenitor body during aqueous alteration. The findings highlight the importance of aqueous chemistry for defining the ultimate concentrations of amino acids in primitive extraterrestrial samples.

Gas-phase synthesis of racemic helicenes and their potential role in the enantiomeric enrichment of sugars and amino acids in meteorites

The molecular origins of homochirality on Earth is not understood well, particularly how enantiomerically enriched molecules of astrobiological significance like sugars and amino acids might have been synthesized on icy grains in space preceding their delivery to Earth. Polycyclic aromatic hydrocarbons (PAHs) identified in carbonaceous chondrites could have been processed in molecular clouds by circularly polarized light prior to the depletion of enantiomerically enriched helicenes onto carbonaceous grains resulting in chiral islands. However, the fundamental low temperature reaction mechanisms leading to racemic helicenes are still unknown. Here, by exploiting synchrotron based molecular beam photoionization mass spectrometry combined with electronic structure calculations, we provide compelling testimony on barrierless, low temperature pathways leading to racemates of [5] and [6]helicene. Astrochemical modeling advocates that gas-phase reactions in molecular clouds lead to racemates of helicenes suggesting a pathway for future astronomical observation and providing a fundamental understanding for the origin of homochirality on early Earth.

Chiral selection, isotopic abundance shifts, and autocatalysis of meteoritic amino acids

The discovery of amino acids in meteorites has presented two clues to the origin of their processing subsequent to their formation: a slight preference for left-handedness in some of them, and isotopic anomalies in some of their constituent atoms. In this article we present theoretical results from the Supernova Neutrino Amino Acid Processing (SNAAP) model, which uses electron anti-neutrinos and the magnetic fields from source objects such as supernovae or colliding neutron stars to selectively destroy one amino acid chirality and to create isotopic abundance shifts. For plausible magnetic fields and electron anti-neutrino fluxes, non-zero, positive enantiomeric excesses, $ee$s, defined to be the relative left/right asymmetry in an amino acid population, are reviewed for two amino acids, and conditions are suggested that would produce $ee>0$ for all of the $\alpha$-amino acids. The relatively high energy anti-neutrinos that produce the $ee$s would inevitably also produce isotopic anomalies. A nuclear reaction network was developed to describe the reactions resulting from them and the nuclides in the meteorites. At similar anti-neutrino fluxes, assumed recombination of the detritus from the anti-neutrino interactions is shown to produce appreciable isotopic anomalies in qualitative agreement with those observed for D/$^1$H and $^{15}$N/$^{14}$N. The isotopic anomalies for $^{13}$C/$^{12}$C are predicted to be small, as are also observed. Autocatalysis may be necessary for any model to produce the largest $ee$s observed in meteorites. This allows the constraints of the original SNAAP model to be relaxed, increasing the probability of meteoroid survival in sites where amino acid processing is possible. These results have obvious implications for the origin of life on Earth.

Chiroptical activity of hydroxycarboxylic acids with implications for the origin of biological homochirality

Circularly polarised light (CPL) interacting with interstellar organic molecules might have imparted chiral bias and hence preluded prebiotic evolution of biomolecular homochirality. The l-enrichment of extra-terrestrial amino acids in meteorites, as opposed to no detectable excess in monocarboxylic acids and amines, has previously been attributed to their intrinsic interaction with stellar CPL revealed by substantial differences in their chiroptical signals. Recent analyses of meteoritic hydroxycarboxylic acids (HCAs) – potential co-building blocks of ancestral proto-peptides – indicated a chiral bias toward the l-enantiomer of lactic acid. Here we report on novel anisotropy spectra of several HCAs using a synchrotron radiation electronic circular dichroism spectrophotometer to support the re-evaluation of chiral biomarkers of extra-terrestrial origin in the context of absolute photochirogenesis. We found that irradiation by CPL which would yield l-excess in amino acids would also yield l-excess in aliphatic chain HCAs, including lactic acid and mandelic acid, in the examined conditions. Only tartaric acid would show “unnatural” d-enrichment, which makes it a suitable target compound for further assessing the relevance of the CPL scenario.

Meteoritic amino acids as chemical tracers of parent-body chemistries

ABSTRACT The analysis of the organic matter of meteorites made it possible to identify over 70 amino acids (AA), including 8 of those found in living organisms. However, their relative abundances vary drastically with the type of the carbonaceous chondrite, even for isomers of same chemical formula. In this report, we address the question whether this difference may have its origin in the relative stability of these isomers according to the conditions they experienced when they were formed and after. To this end, we rely on the fact that for most of the species observed so far in the interstellar medium (ISM), the most abundant isomer of a given generic chemical formula is the most stable one (minimum energy principle, MEP). Using quantum density functional theory (DFT) simulations, we investigate the relative stability of the lowest energy isomers of alanine (Ala) and amino butyric acid (ABA) in the neutral, protonated, and zwitterionic structures together with corresponding nitrile precursors. It is shown that β-alanine and γ-ABA are the most stable in a protonated form, whereas α-AA are the most stable in the zwitterionic and nitrile structures. The different composition of the carbonaceous chondrites CIs and CMs could be linked to the chemical context of the aqueous alterations of the parent bodies.

Explaining the Variations in Isotopic Ratios in Meteoritic Amino Acids

Measurements of the isotopic abundances in meteoritic amino acids have found enhancements of 2H/H, 15N/14N, and 13C/12C in the amino acids in the meteorites studied. We show that they are consistent with the processing of the constituents of the meteorites by electron antineutrinos that would be expected from a core-collapse supernova or neutron-star merger. Using theoretical electron antineutrino cross-sections, we are able to predict these isotopic ratio variations depending on the time-integrated antineutrino flux at the site where the amino acids were processed.

The Astrophysical Formation of Asymmetric Molecules and the Emergence of a Chiral Bias.

The biomolecular homochirality in living organisms has been investigated for decades, but its origin remains poorly understood. It has been shown that circular polarized light (CPL) and other energy sources are capable of inducing small enantiomeric excesses (ees) in some primary biomolecules, such as amino acids or sugars. Since the first findings of amino acids in carbonaceous meteorites, a scenario in which essential chiral biomolecules originate in space and are delivered by celestial bodies has arisen. Numerous studies have thus focused on their detection, identification, and enantiomeric excess calculations in extraterrestrial matrices. In this review we summarize the discoveries in amino acids, sugars, and organophosphorus compounds in meteorites, comets, and laboratory-simulated interstellar ices. Based on available analytical data, we also discuss their interactions with CPL in the ultraviolet (UV) and vacuum ultraviolet (VUV) regions, their abiotic chiral or achiral synthesis, and their enantiomeric distribution. Without doubt, further laboratory investigations and upcoming space missions are required to shed more light on our potential extraterrestrial molecular origins.

Hydrothermal Decomposition of Amino Acids and Origins of Prebiotic Meteoritic Organic Compounds.

The organic compounds found in carbonaceous chondrite meteorites provide insight into primordial solar system chemistry. Evaluating the formation and decomposition mechanisms of meteoritic amino acids may aid our understanding of the origins of life and homochirality on Earth. The amino acid glycine is widespread in meteorites and other extraterrestrial environments; other amino acids, such as isovaline, are found with enantiomeric excesses in some meteorites. The relationship between meteoritic amino acids and other compounds with similar molecular structures, such as aliphatic monoamines and monocarboxylic acids is unclear; experimental results evaluating the decomposition of amino acids have produced inconclusive results about the preferred pathways, reaction intermediates, and if the conditions applied may be compatible with those occurring inside meteoritic parent bodies. In this work, we performed extensive tandem metadynamics, umbrella sampling, and committor analysis to simulate the neutral mild hydrothermal decomposition mechanisms of glycine and isovaline and put them into context for the origins of meteoritic organic compounds. Our ab initio simulations aimed to determine free energy profiles and decomposition pathways for glycine and isovaline. We found that under our modeled conditions, methylammonium, glycolic acid, and sec-butylamine are the most likely decomposition products. These results suggest that meteoritic aliphatic monocarboxylic acids are not produced from decomposition of meteoritic amino acids. Our results also indicate that the decomposition of L-isovaline prefers an enantioselective pathway resulting in the production of (S)-sec-butylamine.

A new family of extraterrestrial amino acids in the Murchison meteorite

The occurrence of extraterrestrial organic compounds is a key for understanding prebiotic organic synthesis in the universe. In particular, amino acids have been studied in carbonaceous meteorites for almost 50 years. Here we report ten new amino acids identified in the Murchison meteorite, including a new family of nine hydroxy amino acids. The discovery of mostly C3 and C4 structural isomers of hydroxy amino acids provides insight into the mechanisms of extraterrestrial synthesis of organic compounds. A complementary experiment suggests that these compounds could be produced from aldehydes and ammonia on the meteorite parent body. This study indicates that the meteoritic amino acids could be synthesized by mechanisms in addition to the Strecker reaction, which has been proposed to be the main synthetic pathway to produce amino acids.

Magnetite plaquettes are naturally asymmetric materials in meteorites

Life on Earth shows preference toward the set of organics with particular spatial configurations. Enantiomeric excesses have been observed for α-methyl amino acids in meteorites, which suggests that chiral asymmetry might have an abiotic origin. A possible abiotic mechanism that could produce chiral asymmetry in meteoritic amino acids is their formation under the influence of asymmetric catalysts, as mineral crystallization can produce spatially asymmetric structures. Although magnetite plaquettes have been proposed to be a possible candidate for an asymmetric catalyst, based on the suggestion that they have a spiral structure, a comprehensive description of their morphology and interpretation of the mechanism associated with symmetry-breaking in biomolecules remain elusive. Here we report observations of magnetite plaquettes in carbonaceous chondrites (CC) that were made with scanning electron microscopy and synchrotron X-ray computed microtomography (SXRCT). We obtained the crystal orientation of the plaquettes using electron backscatter diffraction (EBSD) analysis. SXRCT permits visualization of the internal features of the plaquettes. It provides an unambiguous conclusion that the plaquettes are devoid of a spiral feature and, rather that they are stacks of individual magnetite disks that do not join to form a continuous spiral. Despite the lack of spiral features, our EBSD data show significant changes in crystal orientation between adjacent magnetite disks. The magnetite disks are displaced in a consistent relative direction that lead to an overall crystallographic rotational mechanism. This work offers an explicit understanding of the structures of magnetite plaquettes in CC, which provides a fundamental basis for future interpretation of the proposed symmetry-breaking mechanism.

Light on Chirality: Absolute Asymmetric Formation of Chiral Molecules Relevant in Prebiotic Evolution.

Homochirality is a distinct property of living matter manifested by the unichiral molecular units of genetic material and of proteins, namely, d-deoxyribose and l-amino acids. These molecular subunits or their precursors have been shown to form under various prebiotic conditions in racemic form. However, the nature of the chiral influence, which results in the first breakage of molecular symmetry, remains unclear. In this respect, the photochemical model of enantioselection has gained particular importance in recent years. In this model, the interaction of circularly polarized light with racemic molecules generated in the interstellar medium is considered to be the main driving force of enantiomeric discrimination in early prebiotic evolution. Cometary ice simulations, l-enantio-enriched amino acids in meteorites, and the detection of circularly polarized electromagnetic radiation in star-forming regions provide evidence for photochirogenesis. The recent discovery of aldehydes in the cometary nucleus of 67P/Churyumov-Gerasimenko by means of the Cometary Sampling and Composition (COSAC) experiment on board the Rosetta lander Philae, along with the detection of aldehydes and aldopentoses (including chiral ribose) in simulated interstellar ice analogues, provide a direct link between laboratory simulations and cometary composition. In the context of these new findings, this review will provide an overview of the role of chiral molecules in prebiotic evolution with special emphasis on their chiroptical properties and absolute asymmetric photosynthesis.

Aliphatic amines in Antarctic CR2, CM2, and CM1/2 carbonaceous chondrites

Meteoritic water-soluble organic compounds provide a unique record of the processes that occurred during the formation of the solar system and the chemistry preceding the origins of life on Earth. We have investigated the molecular distribution, compound-specific δ13C isotopic ratios and enantiomeric compositions of aliphatic monoamines present in the hot acid–water extracts of the carbonaceous chondrites LAP 02342 (CR2), GRA 95229 (CR2), LON 94101 (CM2), LEW 90500 (CM2), and ALH 83100 (CM1/2). Analyses of the concentration of monoamines in these meteorites revealed: (a) the CR2 chondrites studied here contain higher concentrations of monoamines relative to the analyzed CM2 chondrites; (b) the concentration of monoamines decreases with increasing carbon number; and (c) isopropylamine is the most abundant monoamine in these CR2 chondrites, while methylamine is the most abundant amine species in these CM2 and CM1/2 chondrites. The δ13C values of monoamines in CR2 chondrite do not correlate with the number of carbon atoms; however, in CM2 and CM1/2 chondrites, the 13C enrichment decreases with increasing monoamine carbon number. The δ13C values of methylamine in CR2 chondrites ranged from −1 to +10‰, while in CM2 and CM1/2 chondrites the δ13C values of methylamine ranged from +41 to +59‰. We also observed racemic compositions of sec-butylamine, 3-methyl-2-butylamine, and sec-pentylamine in the studied carbonaceous chondrites. Additionally, we compared the abundance and δ13C isotopic composition of monoamines to those of their structurally related amino acids. We found that monoamines are less abundant than amino acids in CR2 chondrites, with the opposite being true in CM2 and CM1/2 chondrites. We used these collective data to evaluate different primordial synthetic pathways for monoamines in carbonaceous chondrites and to understand the potential common origins these molecules may share with meteoritic amino acids.

Anisotropy-Guided Enantiomeric Enhancement in Alanine Using Far-UV Circularly Polarized Light.

All life on Earth is characterized by its asymmetry - both the genetic material and proteins are composed of homochiral monomers. Understanding how this molecular asymmetry initially arose is a key question related to the origins of life. Cometary ice simulations, L-enantiomeric enriched amino acids in meteorites and the detection of circularly polarized electromagnetic radiation in star-forming regions point to a possible interstellar/protostellar generation of stereochemical asymmetry. Based upon our recently recorded anisotropy spectra g(λ) of amino acids in the vacuum-UV range, we subjected amorphous films of racemic (13)C-alanine to far-UV circularly polarized synchrotron radiation to probe the asymmetric photon-molecule interaction under interstellar conditions. Optical purities of up to 4% were reached, which correlate with our theoretical predictions. Importantly, we show that chiral symmetry breaking using circularly polarized light is dependent on both the helicity and the wavelength of incident light. In order to predict such stereocontrol, time-dependent density functional theory was used to calculate anisotropy spectra. The calculated anisotropy spectra show good agreement with the experimental ones. The European Space Agency's Rosetta mission, which successfully landed Philae on comet 67P/Churyumov-Gerasimenko on 12 November 2014, will investigate the configuration of chiral compounds and thereby obtain data that are to be interpreted in the context of the results presented here.

Assessing the origins of aliphatic amines in the Murchison meteorite from their compound-specific carbon isotopic ratios and enantiomeric composition

The study of meteoritic organic compounds provides a unique window into the chemical inventory of the early Solar System and prebiotic chemistry that may have been important for the origin of life on Earth. Multiple families of organic compounds have been extracted from the Murchison meteorite, which is one of the most thoroughly studied carbonaceous chondrites. The amino acids extracted from Murchison have been extensively analyzed, including measurements of non-terrestrial stable isotopic ratios and discoveries of l-enantiomeric excesses for α-dialkyl amino acids, notably isovaline. However, although the isotopic signatures of bulk amine-containing fractions have been measured, the isotopic ratios and enantiomeric composition of individual aliphatic amines, compounds that are structurally related to amino acids, remain unknown. Here, we report a novel method for the extraction, separation, identification and quantitation of aliphatic monoamines extracted from the Murchison meteorite. Our results show a complete suite of structural isomers, with a larger concentration of methylamine and ethylamine and decreasing amine concentrations with increasing carbon number. The carbon isotopic compositions of fourteen meteoritic aliphatic monoamines were measured, with δ13C values ranging from +21‰ to +129‰, showing a decrease in 13C with increasing carbon number, a relationship that may be consistent with the chain elongation mechanism under kinetic control previously proposed for meteoritic amino acids. We also found the enantiomeric composition of sec-butylamine, a structural analog to isovaline, was racemic within error, while the isovaline extracted from the same Murchison piece showed an l-enantiomeric excess of 9.7%; this result suggested that processes leading to enantiomeric excess in the amino acid did not affect the amine. We used these collective data to assess the primordial synthetic origins of these meteoritic aliphatic amines and their potential linkage to meteoritic amino acids.

The effects of parent-body hydrothermal heating on amino acid abundances in CI-like chondrites

We determined the amino acid abundances and enantiomeric compositions of the Antarctic CI1 carbonaceous chondrites Yamato (Y)-86029 and Y-980115, as well as the Ivuna and Orgueil CI1 carbonaceous chondrites by liquid chromatography with fluorescence detection and time-of-flight mass spectrometry. Y-86029 and Y-980115 both show evidence of parent-body heating (500–600 °C) in addition to aqueous alteration, while Ivuna and Orgueil only show evidence for aqueous alteration. In contrast to Ivuna and Orgueil, which each contain ∼70 nmol/g of amino acids in acid-hydrolyzed, water extracts, both heated Yamato CI meteorites contain only low levels of amino acids that were primarily l-enantiomers of proteinogenic amino acids, indicating that they are likely to be terrestrial in origin. Because indigenous amino acids have been found in meteorites that have experienced metamorphic temperatures of >1000 °C with only minimal aqueous alteration, heating alone is not sufficient to explain the lack of amino acids in Y-86029 and Y-980115. Rather, our data suggest that the combination of heating and aqueous alteration has a profound destructive effect on amino acids in meteorites. This finding has implications for the origins of amino acids and other molecules in the early evolution of our solar system.

ENANTIOMERIC EXCESSES INDUCED IN AMINO ACIDS BY ULTRAVIOLET CIRCULARLY POLARIZED LIGHT IRRADIATION OF EXTRATERRESTRIAL ICE ANALOGS: A POSSIBLE SOURCE OF ASYMMETRY FOR PREBIOTIC CHEMISTRY

The discovery of meteoritic amino acids with enantiomeric excesses of the L-form (ee L) has suggested that extraterrestrial organic materials may have contributed to prebiotic chemistry and directed the initial occurrence of the ee L that further led to homochirality of amino acids on Earth. A proposed mechanism for the origin of ee L in meteorites involves an asymmetric photochemistry of extraterrestrial ices by UV circularly polarized light (CPL). We have performed the asymmetric synthesis of amino acids on achiral extraterrestrial ice analogs by VUV CPL, investigating the chiral asymmetry transfer at two different evolutionary stages at which the analogs were irradiated (regular ices and/or organic residues) and at two different photon energies (6.6 and 10.2 eV). We identify 16 distinct amino acids and precisely measure the L-enantiomeric excesses using the enantioselective GC × GC-TOFMS technique in five of them: α-alanine, 2,3-diaminopropionic acid, 2-aminobutyric acid, valine, and norvaline, with values ranging from ee L = –0.20% ± 0.14% to ee L = –2.54% ± 0.28%. The sign of the induced ee L depends on the helicity and the energy of CPL, but not on the evolutionary stage of the samples, and is the same for all five considered amino acids. Our results support an astrophysical scenario in which the solar system was formed in a high-mass star-forming region where icy grains were irradiated during the protoplanetary phase by an external source of CPL of a given helicity and a dominant energy, inducing a stereo-specific photochemistry.

NATURE'S STARSHIPS. I. OBSERVED ABUNDANCES AND RELATIVE FREQUENCIES OF AMINO ACIDS IN METEORITES

The class of meteorites called carbonaceous chondrites are examples of material from the solar system which have been relatively unchanged from the time of their initial formation. These meteorites have been classified according to the temperatures and physical conditions of their parent planetesimals. We collate available data on amino acid abundance in these meteorites and plot the concentrations of different amino acids for each meteorite within various meteorite subclasses. We plot average concentrations for various amino acids across meteorites separated by subclass and petrologic type. We see a predominance in the abundance and variety of amino acids in CM2 and CR2 meteorites. The range in temperature corresponding to these subclasses indicates high degrees of aqueous alteration, suggesting aqueous synthesis of amino acids. Within the CM2 and CR2 subclasses, we identify trends in relative frequencies of amino acids to investigate how common amino acids are as a function of their chemical complexity. These two trends (total abundance and relative frequencies) can be used to constrain formation parameters of amino acids within planetesimals. Our organization of the data supports an onion shell model for the temperature structure of planetesimals. The least altered meteorites (type 3) and their amino acids originated near cooler surface regions. The most active amino acid synthesis likely took place at intermediate depths (type 2). The most altered materials (type 1) originated furthest toward parent body cores. This region is likely too hot to either favor amino acid synthesis or for amino acids to be retained after synthesis.