Prebiotic Molecules Research Articles

Stability of solid-state formamide under Lyα irradiation

Context. Formamide (NH2CHO) plays a pivotal role as a crucial precursor to various prebiotic molecules, including sugars and nucleobases. To gain a deeper understanding of the chemical processes involving formamide formation in astrophysical settings, it becomes imperative to refine our comprehension through astrochemical models. These models necessitate not only the inclusion of pathways for formamide formation across diverse environments, but also the elucidation of mechanisms that lead to its degradation. Aims. The primary objective of this study is to scrutinize the influence of the underlying amorphous silicate substrate and the phase of formamide ice on the kinetics of its destruction and the resulting products upon exposure to Lyα (121.6 nm) radiation at 16 K. Methods. To achieve this, we conducted an examination of the photodestruction of NH2CHO ice, employing Fourier transform infrared spectroscopy. Results. Our findings reveal that, while the destruction rates of amorphous formamide ice remain consistent, regardless of the presence of an underlying amorphous olivine substrate, this substrate effectively reduces the formation of NH3, HNCO, and HCN within the ice following UV irradiation. On the other hand, contrary to common knowledge, crystalline formamide ice exhibits a considerably faster destruction rate, by an order of magnitude, than its amorphous counterpart under photo processing. Conclusions. In the interstellar medium, molecular ices often undergo phase changes depending on the environmental conditions. Our results indicate that crystalline formamide ice is more susceptible to rapid destruction than its amorphous counterpart, rendering it more elusive for detection within the lifetime of dense interstellar clouds. Furthermore, our findings emphasise the crucial significance of accounting for the influence of underlying dust grain surfaces in astrochemical models, as they have an effect on product formation during the degradation of molecular ices.

Accurate ab initio spectroscopic studies of promising interstellar ethanolamine iminic precursors

Context. The detection of NH2CH2CH2OH (ethanolamine) in molecular cloud G+0.693-0.027 adds an additional player to the pre-biotic molecules discovered so far in the interstellar medium (ISM). As this molecule might be formed through condensed-phase hydrogenation steps, detecting one or more of the molecules involved might help to elucidate the chemical pathway leading to its production. Aims. The chemical path involves the formation of four chemical species. In this work, we study the energies of the isomers involved, indicate the best candidates for detection purposes, and provide the distortion constants of the most energetically favoured isomers undetected so far. Methods. We used highly accurate CCSD(T)-F12/cc-pCVTZ-F12 computations to predict the lowest energy isomers as well as their spectroscopic constants, taking corrections for core electron correlation and scalar relativity into account. Results. We studied 14 isomers. We find that the lowest energy isomer proposed in previous studies is not the actual minimum. We provide a set of rotational and distortion constants of the two new most stable isomers together with their fundamental vibrational frequencies in order to guide the search for these important astrochemical precursors of prebiotic molecules in the ISM.

Delivery of Organic Matter to the Early Earth

The inner Solar System—including the planet Earth—was heavily bombarded by comets, asteroids, and their fragments (i.e., meteorites, micrometeorites, and interplanetary dust particles) from 4.56 to about 3.5 billion years ago. This bombardment resulted in a rich assortment of organics delivered to the Earth, as comets and many asteroids contain carbonaceous material. These organic compounds were likely further processed on the early Earth (e.g., by impact-shock reactions), providing a feedstock of prebiotic molecules to the crust and oceans. In this chapter, we review the mechanisms of organic matter delivery to the primitive Earth, further reactions and processing, and the importance of exogenous material in the evolution of our planet and life.

High-spatial resolution functional chemistry of nitrogen compounds in the observed UK meteorite fall Winchcombe

Organic matter in extraterrestrial samples is a complex material that might have played an important role in the delivery of prebiotic molecules to the early Earth. We report here on the identification of nitrogen-containing compounds such as amino acids and N-heterocycles within the recent observed meteorite fall Winchcombe by high-spatial resolution spectroscopy techniques. Although nitrogen contents of Winchcombe organic matter are low (N/C ~ 1–3%), we were able to detect the presence of these compounds using a low-noise direct electron detector. These biologically relevant molecules have therefore been tentatively found within a fresh, minimally processed meteorite sample by high spatial resolution techniques conserving the overall petrographic context. Carbon functional chemistry investigations show that sizes of aromatic domains are small and that abundances of carboxylic functional groups are low. Our observations demonstrate that Winchcombe represents an important addition to the collection of carbonaceous chondrites and still preserves pristine extraterrestrial organic matter.

Self-immolation Assisted Morphology Transformation of Prebiotic Lipidated-cationic Amino Acids: Electro-droplet Mediated C-C Coupling Reaction to Synthesize Macromolecules.

Compartmentalization protected biomolecules from the fluctuating environments of early Earth. Although contemporary cells mostly use phospholipid-based bilayer membranes, the utility of non-bilayer compartments was not ruled out during the prebiotic and modern eras. In the present study, we demonstrated the prebiotic synthesis of lipidated cationic amino acid-based amphiphiles [lauryl ester of lysine (LysL); ornithine (OrnL); and 2,4-diamino butyric acid (DabL)] using model dry-down reaction. These amphiphiles self-assemble into micellar membranes. However, the OrnL and DabL-based micelles undergo pH-responsive transformation to lipid droplet-like morphologies, a modelcompartment in the prebiotic Earth. These cationic droplets encapsulated prebiotic molecules (isoprene) and assisted electron transfer reaction to synthesize isoprenoid derivatives at primitive Earth conditions. The self-assembly of prebiotic amphiphiles, their transformation to droplet compartments, and droplet-assisted C-C bond formation reaction might have helped the evolution to synthesize various biomolecules required for the origin of life.

Growth mechanism of aromatic prebiotic molecules: insights from different processes of ion-molecule reactions in benzonitrile-ammonia and benzonitrile-methylamine clusters.

Benzonitrile (BN, C6H5CN) has been detected in the cold molecular cloud Taurus molecular cloud-1 (TMC-1) in 2018, which is suggested to be a precursor in the formation of more complex nitrogen-containing aromatic interstellar compounds. In this study, we utilized mass-selected infrared (IR) photodissociation spectroscopy and quantum chemical calculations to investigate the structures and gaseous ion-molecule reactions of benzonitrile-ammonia (BN-NH3) and benzonitrile-methylamine (BN-MA) clusters. The spectral observations indicate that the cyclic hydrogen bonding structure predominates in both neutral clusters. After VUV (118 nm) single-photon ionization, a new C-N covalent bond formed between BN and NH3 in the (BN-NH3)+ cluster. However, proton sharing constitutes the primary structure of the (BN-MA)+ cluster. The two nitrogen-containing interstellar molecules react with BN to yield distinct products due to difference in charge distribution and molecular polarity in the ionized clusters. The reactions of BN with other molecules contribute to our understanding of the growth mechanisms of complex interstellar molecules.

On the detectability of interstellar diaminomethane ((NH2)2CH2)

ABSTRACT The recent synthesis of diaminomethane ((NH2)2CH2) under simulated interstellar conditions implies that this molecule is likely present in the interstellar medium (ISM), and this work provides the highly accurate quantum chemically computed rotational constants and IR frequencies for comparison to experiment that may aid in its potential future detection. This simplest geminal diamine of prebiotic note has a transition for its ν18 fundamental frequency at 702.5 cm−1 (14.23 μm) with an intensity on level with that of the antisymmetric stretch in carbon dioxide. Additionally, its 1.72 D dipole moment for the most stable C2v conformer should make it detectable with radiotelescopes as well. The C2 conformer may also be detectable in similar regions where the C2v form is present, but only warmer or higher-energy regions will allow for possible observation of the C1 conformer. In any case, rotational constants for these other two conformers are also provided in addition to the full set of fundamental vibrational frequencies for the C2v conformer. These data will assist with further laboratory classification and possible interstellar detection of this prebiotic molecule.

Mapping Physical Conditions in Neighboring Hot Cores: NOEMA Studies of W3(H2O) and W3(OH)

The complex chemistry that occurs in star-forming regions can provide insight into the formation of prebiotic molecules at various evolutionary stages of star formation. To study this process, we present millimeter-wave interferometric observations of the neighboring hot cores W3(H2O) and W3(OH) carried out using the NOEMA interferometer. We have analyzed distributions of six molecules that account for most observed lines across both cores and have constructed physical parameter maps for rotational temperature, column density, and velocity field with corresponding uncertainties. We discuss the derived spatial distributions of these parameters in the context of the physical structure of the source. We propose the use of HCOOCH3 as a new temperature tracer in W3(H2O) and W3(OH) in addition to the more commonly used . By analyzing the physically derived parameters for each molecule across both W3(H2O) and W3(OH), the work presented herein further demonstrates the impact of physical environment on hot cores at different evolutionary stages.

Oxidation of iron by giant impact and its implication on the formation of reduced atmosphere in the early Earth

Giant impact–driven redox processes in the atmosphere and magma ocean played crucial roles in the evolution of Earth. However, because of the absence of rock records from that time, understanding these processes has proven challenging. Here, we present experimental results that simulate the giant impact–driven reactions between iron and volatiles (H 2 O and CO 2 ) using x-ray free electron laser (XFEL) as fast heat pump and structural probe. Under XFEL pump, iron is oxidized to wüstite (FeO), while volatiles are reduced to H 2 and CO. Furthermore, iron oxidation proceeds into formation of hydrides (γ-FeH x ) and siderite (FeCO 3 ), implying redox boundary near 300-km depth. Through quantitative analysis on reaction products, we estimate the volatile and FeO budgets in bulk silicate Earth, supporting the Theia hypothesis. Our findings shed light on the fast and short-lived process that led to reduced atmosphere, required for the emergence of prebiotic organic molecules in the early Earth.

Role of Low-Energy (

We demonstrate for the first time that Galactic cosmic rays with energies as high as ∼1010 eV can trigger a cascade of low-energy (<20 eV) secondary electrons that could be a significant contributor to the interstellar synthesis of prebiotic molecules whose delivery by comets, meteorites, and interplanetary dust particles may have kick-started life on Earth. For the energetic processing of interstellar ice mantles inside dark, dense molecular clouds, we explore the relative importance of low-energy (<20 eV) secondary electrons-agents of radiation chemistry-and low-energy (<10 eV), nonionizing photons-instigators of photochemistry. Our calculations indicate fluxes of ∼102 electrons cm-2 s-1 for low-energy secondary electrons produced within interstellar ices due to attenuated Galactic cosmic-ray protons. Consequently, in certain star-forming regions where internal high-energy radiation sources produce ionization rates that are observed to be a thousand times greater than the typical interstellar Galactic ionization rate, the flux of low-energy secondary electrons should far exceed that of nonionizing photons. Because reaction cross sections can be several orders of magnitude larger for electrons than for photons, even in the absence of such enhancement, our calculations indicate that secondary low-energy (<20 eV) electrons are at least as significant as low-energy (<10 eV) nonionizing photons in the interstellar synthesis of prebiotic molecules. Most importantly, our results demonstrate the pressing need for explicitly incorporating low-energy electrons in current and future astrochemical simulations of cosmic ices. Such models are critically important for interpreting James Webb Space Telescope infrared measurements, which are currently being used to probe the origins of life by studying complex organic molecules found in ices near star-forming regions.

Thermal Synthesis of Carbamic Acid and Its Dimer in Interstellar Ices: A Reservoir of Interstellar Amino Acids.

Reactions in interstellar ices are shown to be capable of producing key prebiotic molecules without energetic radiation that are necessary for the origins of life. When present in interstellar ices, carbamic acid (H2NCOOH) can serve as a condensed-phase source of the molecular building blocks for more complex proteinogenic amino acids. Here, Fourier transform infrared spectroscopy during heating of analogue interstellar ices composed of carbon dioxide and ammonia identifies the lower limit for thermal synthesis to be 62 ± 3 K for carbamic acid and 39 ± 4 K for its salt ammonium carbamate ([H2NCOO-][NH4+]). While solvation increases the rates of formation and decomposition of carbamic acid in ice, the absence of solvent effects after sublimation results in a significant barrier to dissociation and a stable gas-phase molecule. Photoionization reflectron time-of-flight mass spectrometry permits an unprecedented degree of sensitivity toward gaseous carbamic acid and demonstrates sublimation of carbamic acid from decomposition of ammonium carbamate and again at higher temperatures from carbamic acid dimers. Since the dimer is observed at temperatures up to 290 K, similar to the environment of a protoplanetary disk, this dimer is a promising reservoir of amino acids during the formation of stars and planets.

Bifidobacterium adolescentis - a beneficial microbe.

Bifidobacterium adolescentis is one of the most abundant bifidobacterial species in the human large intestine, and is prevalent in 60-80% of healthy human adults with cell densities ranging from 109-1010 cells/g of faeces. Lower abundance is found in children and in elderly individuals. The species is evolutionary adapted to fermenting plant-derived glycans and is equipped with an extensive sugar transporter and degradation enzymes repertoire. Consequently, the species is strongly affected by dietary carbohydrates and is able to utilize a wide range of prebiotic molecules. B. adolescentis is specialized in metabolizing resistant starch and is considered a primary starch degrader enabling growth of other beneficial bacteria by cross-feeding. The major metabolic output is acetate and lactate in a ratio of 3:2. Several health-beneficial properties have been demonstrated in certain strains of B. adolescentis in vitro and in rodent models, including enhancement of the intestinal barrier function, anti-inflammatory and immune-regulatory effects, and the production of neurotransmitters (GABA), and vitamins. Although causalities have not been established, reduced abundance of B. adolescentis as part of a dysbiotic colonic microbiota in human observational studies has been associated with inflammatory bowel diseases, irritable bowel syndrome, coeliac disease, cystic fibrosis, Helicobacter pylori infection, type 1 and 2 diabetes, metabolic syndrome, nonalcoholic steatohepatitis, and certain allergies. It is therefore reasonable to conceive B. adolescentis as a health-associated, or even health-promoting bacterial species in humans.

Electron impact ionization of prebiotic interstellar molecules

This article presents an investigation into the electron impact ionization of diverse prebiotic molecules that exist within the interstellar medium. Specifically, the molecules under consideration here include ethylene glycol, ethanolamine, glycolonitrile, aminoacetonitrile, acetamide, and glycolaldehyde. These molecules hold the potential to serve as precursor compounds, playing a critical role in the formation of essential building blocks necessary for life’s emergence. To understand the chemistry in these regions when such molecules interact with particles like electrons, we require reaction rates and cross sections. In this work, the electron impact ionization cross section is calculated using the robust optical potential approach and the complex scattering potential-ionization cross section method over a wide range of energies from 10 eV to 5000 eV on a fine grid. The incorporation of screening correction in this approach effectively addresses the superimposition of charge densities originating from distinct atoms within each molecule. Additionally, the binary-encounter Bethe ionization cross section is computed to facilitate comparison and validation of the presented data.

Can comets deliver prebiotic molecules to rocky exoplanets?

In this work, we consider the potential of cometary impacts to deliver complex organic molecules and the prebiotic building blocks required for life to rocky exoplanets. Numerical experiments have demonstrated that for these molecules to survive, impacts at very low velocities are required. This work shows that for comets scattered from beyond the snow-line into the habitable zone, the minimum impact velocity is always lower for planets orbiting Solar-type stars than M-dwarfs. Using both an analytical model and numerical N-body simulations, we show that the lowest velocity impacts occur onto planets in tightly packed planetary systems around high-mass (i.e. Solar-mass) stars, enabling the intact delivery of complex organic molecules. Impacts onto planets around low-mass stars are found to be very sensitive to the planetary architecture, with the survival of complex prebiotic molecules potentially impossible in loosely packed systems. Rocky planets around M-dwarfs also suffer significantly more high velocity impacts, potentially posing unique challenges for life on these planets. In the scenario that cometary delivery is important for the origins of life, this study predicts the presence of biosignatures will be correlated with (i) decreasing planetary mass (i.e. escape velocity), (ii) increasing stellar-mass and (iii) decreasing planetary separation (i.e. exoplanets in tightly-packed systems).

Synthesis of urea on the surface of interstellar water ice clusters. A quantum chemical study

Urea is a prebiotic molecule that has been detected in few sources of the interstellar medium (ISM) and in Murchison meteorite. Being stable against ultraviolet radiation and high-energy electron bombardment, urea is expected to be present in interstellar ices. Theoretical and experimental studies suggest that isocyanic acid (HNCO) and formamide (NH2CHO) are possible precursors of urea. However, uncertainties still exist regarding its formation routes. Previous computational works characterised urea formation in the gas phase or in presence of few water molecules by reaction of formamide with nitrogen-bearing species. In this work, we investigated the reaction of HNCO + NH3 on an 18 water molecules ice cluster model mimicking interstellar ice mantles by means of quantum chemical computations. We characterised different mechanisms involving both closed-shell and open-shell species at B3LYP-D3(BJ)/ma-def2-TZVP level of theory, in which the radical–radical H2NCO + NH2 coupling has been found to be the most favourable one due to being almost barrierless. In this path, the presence of the icy surfaces is crucial for acting as reactant concentrators/suppliers, as well as third bodies able to dissipate the energy liberated during the urea formation.

Theoretical study of amines containing molecules in the gas and water solvent

This study reports the infrared and electronic absorption spectra of amine-containing molecules. We investigate how these spectra differ for molecules in their neutral and ionic forms in gas and astrophysical H2O ice. Additionally, we analyze the pure rotational spectra of these molecules in the gas state. These are prebiotic molecules such as propargylamine (C3H5N), four isomers of C3H7N (1-aminopropene, 2-propenamine, allylamine, and cyclopropylamine), and two isomers of C3H9N (n-propyl amine and 2-aminpropane) considered for the study. We analyzed various properties of molecules in different states: gas phase, water solvent, and ionic states. We used the coupled-cluster method (CCSD) with a 6–311++G** basis set for our studies. The rotational constants obtained at this level of theory are well matching with the available experimental determinations. These constants are further used to calculate the rotational spectra and their transitions. The calculated vibrational frequencies of these molecules matched well with experimental results at this level of theory. To study the influence of solvent, we employed the IEFPCM model at the same level of theory. We used the equation of motion coupled cluster theory (EOM-CCSD) at the CCSD/6–311++G** level of theory to examine the electronic absorption spectra. We reported the HOMO-LUMO gap, electronic transitions, and oscillator strength of these transitions. We identified the best lines from microwave and infrared regions to observe these molecules in interstellar environments. All calculations were performed using the Gaussian 16 and PGOPHER program packages.

Single-Photon Ionization Induced New Covalent Bond Formation in Acrylonitrile(AN)-Pyrrole(Py) Clusters.

The formation of nitrogen-containing organic compounds is crucial for understanding chemical evolution and the origin of life in the interstellar medium (ISM). In this study, we explore whether acrylonitrile (AN) and pyrrole (Py) can form new nitrogen-containing compounds after single-photon ionization in their gaseous clusters by vacuum ultraviolet (VUV)-infrared (IR) spectroscopy and theoretical calculations. The results show that a strong linear H-bond is formed in neutral AN-Py, while cyclic or bicyclic H-bonded networks are formed in the neutral AN-Py2 cluster. It is found that the structure containing a new C-C covalent bond between two moieties in (AN-Py)+ is formed besides the formation of H-bonded structures after AN-Py is ionized by VUV light. In (AN-Py2)+ cluster cations, new C-C or C-N covalent bonds tend to be formed between two Py, with (Py)2+ as the core in the cluster. The results reveal that new covalent bonds are more likely to be formed between two Py species when AN and Py are present in the cationic clusters. These results provide spectroscopic evidence of the formation of new nitrogen-containing organic compounds from AN and Py induced by VUV, which are helpful for our understanding of the formation of diverse prebiotic molecules in interstellar space.

Origin-of-life Molecules in the Atmosphere after Big Impacts on the Early Earth

The origin of life on Earth would benefit from a prebiotic atmosphere that produced nitriles, like HCN, which enable ribonucleotide synthesis. However, geochemical evidence suggests that Hadean air was relatively oxidizing with negligible photochemical production of prebiotic molecules. These paradoxes are resolved by iron-rich asteroid impacts that transiently reduced the entire atmosphere, allowing nitriles to form in subsequent photochemistry. Here we investigate impact-generated reducing atmospheres using new time-dependent, coupled atmospheric chemistry and climate models that account for gas-phase reactions and surface catalysis. The resulting H2-, CH4-, and NH3-rich atmospheres persist for millions of years, until the hydrogen escapes to space. The HCN and HCCCN production and rainout to the surface can reach 109 molecules cm−2 s−1 in hazy atmospheres with a mole ratio of CH4/CO2 > 0.1. Smaller CH4/CO2 ratios produce HCN rainout rates of <105 molecules cm−2 s−1 and negligible HCCCN. The minimum impactor mass that creates atmospheric CH4/CO2 > 0.1 is 4 × 1020–5 × 1021 kg (570–1330 km diameter), depending on how efficiently iron reacts with a steam atmosphere, the extent of atmospheric equilibration with an impact-induced melt pond, and the surface area of nickel that catalyzes CH4 production. Alternatively, if steam permeates and deeply oxidizes the crust, impactors of ∼1020 kg could be effective. Atmospheres with copious nitriles have >360 K surface temperatures, perhaps posing a challenge for RNA longevity, although cloud albedo can produce cooler climates. Regardless, postimpact cyanide can be stockpiled and used in prebiotic schemes after hydrogen has escaped to space.

Advances in superconductor quantum and thermal detectors for analytical instruments

Analytical instruments or scientific instruments are indispensable for scientific research and industry. The analytical instruments require a detector that converts physical quantities to be measured (measurands) to electric signals. This Tutorial describes the basics of quantum and thermal detectors, the operation principles of superconductor detectors, and the ultimate performance of state-of-art analytical instruments with superconductivity. We still face fundamental issues, such as the classical Fano factor, the relation between energy gap and mean carrier creation energy, quasiparticle dynamics, and the intermediate state in the middle of superconducting transition; and engineering issues, such as the small sensitive area and the spatially nonuniform response. Nevertheless, enormous efforts have matured superconductor detectors, which enables us to solve the inherent problems of conventional analytical instruments. As an example of the analytical results, we describe x-ray spectroscopy and mass spectrometry at our institute by using three detector types: superconductor tunnel junction, transition edge sensor, and superconductor strip. Microwave kinetic inductance and metallic magnetic calorimetric types are also described. The analytical results may contribute to a wide range of fields, such as dentistry, molecular biology, energy-saving society, planetary science, and prebiotic organic molecules in space.

Structural and chemical insights into the prebiotic property of hemicellulosic polysaccharide from Santalum album L.

Hemicellulose was extracted by alkali treatment of de-pectinated cell wall material of Santalum album L. (sandalwood) suspension culture cells. The physicochemical properties and prebiotic activities of a purified major fraction of Hemicellulose-B, termed as HB-I, were investigated. GC analysis of hydrolyzed and derivatized HB-I showed the presence of arabinose (~64 %), galactose (~16 %) and glucose (~16 %) as major monosaccharide units along with minor amount of rhamnose. Methylation and NMR studies on the purified polysaccharide revealed the presence of 6-β-d-Glcp, β-d-Galp, 3,5-α-l-Araf, α-l-Araf, 5-α-l-Araf, 2,3-α-l-Araf and, α-l-Rhap residues, from which a proposed structure of repeating units was established. The growth of probiotic Lactobacillus spp. strains L. acidophilus, L. casei, L. plantarum and L. rhamnosus was promoted while that of Escherichia coli was suppressed significantly in presence of HB-I. Our results highlight valorization of sandalwood biomass and explore the role of mixed α, β-linked heteroglycan as a potential prebiotic molecule thus indicating the possibility of development of low-cost bioprocesses for production of functional food ingredients.