Search

• Developed new analytical tool for the analysis of short homopeptides. • Analytical figures of merit experiments were performed to validate the method. • Achieved limits of quantitation upwards of ∼788x lower than existing methods. • Diamidophosphate readily abiotically oligomerized amino acids and peptides. • Homopeptide synthesis occurred easily in thermally mild, aqueous conditions. In the origins of life field understanding the abiotic polymerization of simple organic monomers (e.g., amino acids) into larger biomolecules (e.g., oligopeptides), remains a seminal challenge. Recently, preliminary observations showed a limited set of peptides formed in the presence of the plausible prebiotic phosphorylating agent, diamidophosphate (DAP), highlighting the need for an analytical tool to critically evaluate the ability of DAP to induce oligomerization of simple organics under aqueous conditions. However, performing accurate and precise, targeted analyses of short oligopeptides remains a distinct challenge in the analytical chemistry field. Here, we developed a new technique to detect and quantitate amino acids and their homopeptides in a single run using ultraperformance liquid chromatography-fluorescence detection/time of flight mass spectrometry. Over an 8-minute retention time window, 18 target analytes were identified and quantitated, 16 of which were chromatographically separated at, or near baseline resolution. Compound identity was confirmed by accurate mass analysis using a 10 ppm mass tolerance window. This method featured limits of detection < 5 nM (< 1 fmol on column) and limits of quantitation (LOQs) <15 nM (< 3 fmol on column). The LODs and LOQs were upwards of ∼28x and ∼788x lower, respectively, than previous methods for the same analytes, highlighting the quantifiable advantages of this new method. Both detectors provided good quantitative linearity (R2 > 0.985) for all analytes spanning concentration ranges ∼3 - 4 orders of magnitude. We performed a series of laboratory experiments to investigate DAP-mediated oligomerization of amino acids and peptides and analyzed experimental products with the new method. DAP readily polymerized amino acids and peptides under a range of simulated environmental conditions. This research underscores the potential of DAP to have generated oligopeptides on the primordial Earth, enhancing prebiotic chemical diversity and complexity at or near the origin of life. [ABSTRACT FROM AUTHOR]

Rationale: Extraterrestrial amines and ammonia are critical ingredients for the formation of astrobiologically important compounds such as amino acids and nucleobases. However, conventional methods for analyzing the composition and isotopic ratios of volatile amines suffer from lengthy derivatization and purification procedures, high sample mass consumption, and chromatographic interferences from derivatization reagents and non-target compounds., Methods: Here we demonstrate a highly efficient method to analyze the composition and compound specific isotopic ratios of C 1 to C 6 amines as well as ammonia based on solid phase micro-extraction (SPME) on-fiber derivatization. 2,3,4,5,6-pentafluorobenzyl chloroformate (PFBCF) adsorbed on a solid phase SPME fiber is subsequently exposed to the headspace of the water extract of the Murchison meteorite to selectively extract, derivatize and concentrate volatile amines and ammonia. PFBCF does not directly contact the aqueous solution containing other soluble organics., Results: An aliquot of volatile amines and ammonia in the headspace are selectively derivatized on the SPME fiber and subsequently thermally desorbed onto the GC injector for analysis. Only the amounts of amines required for either compositional or isotopic analysis are derivatized and consumed in the process, preserving the bulk fraction of amines and ammonia for other analyses, and the process does not affect other volatile compound classes. Carbon and hydrogen isotopic ratios of amines are obtained by isotopic mass balance., Conclusions: The exceptional selectivity and sensitivity of SPME on-fiber derivatization of volatile amines in carbonaceous chondrite extracts allow minimization of sample consumption. Carbon and hydrogen isotopic values of individual amines in the Murchison meteorite are consistent with their extraterrestrial origin, with a substantial fraction inherited from interstellar molecular clouds. SPME on-fiber derivatization is well suited for analyzing extraterrestrial materials, especially precious asteroid return samples., (© 2025 John Wiley & Sons Ltd.)

Understanding how organics degrade under galactic cosmic rays (GCRs) is critical as we search for traces of ancient life on Mars. Even if the planet harbored life early in its history, its surface rocks have been exposed to ionizing radiation for about four billion years, potentially destroying the vast majority of biosignatures. In this study, we investigated for the first time the impact of simulated GCRs (using gamma rays) on several types of lipid biosignatures (including hopane C 30 , sterane C 27 , alkanes, and fatty acids [FAs]) in both the presence and absence of salts (NaCl, KCl, and MgCl 2 ). We measured that the lipids degraded 6-20 times faster than amino acids in similar conditions; moreover, when irradiated in the presence of a salt substrate, degradation was at least 4-6 times faster than without salt, which suggests that salty environments that are often preferred targets for astrobiology warrant caution. We detected radiolytic by-products only for FAs-in the form of alkanes and aldehydes. These results expand our understanding of the degradation of organic molecules in Mars analog environments and underscore the urgent need to direct rover missions to sampling sites protected from GCRs, for example, sites on Mars that have been recently exposed by a wind scarp retreat or meteoritic impact.

Modern life is essentially homochiral, containing D-sugars in nucleic acid backbones and L-amino acids in proteins. Since coded proteins are theorized to have developed from a prebiotic RNA World, the homochirality of L-amino acids observed in all known life presumably resulted from chiral transfer from a homochiral D-RNA World. This transfer would have been mediated by aminoacyl-RNAs defining the genetic code. Previous work on aminoacyl transfer using tRNA mimics has suggested that aminoacylation using D-RNA may be inherently biased toward reactivity with L-amino acids, implying a deterministic path from a D-RNA World to L-proteins. Using a model system of self-aminoacylating D-ribozymes and epimerizable activated amino acid analogs, we test the chiral selectivity of 15 ribozymes derived from an exhaustive search of sequence space. All of the ribozymes exhibit detectable selectivity, and a substantial fraction react preferentially to produce the D-enantiomer of the product. Furthermore, chiral preference is conserved within sequence families. These results are consistent with the transfer of chiral information from RNA to proteins but do not support an intrinsic bias of D-RNA for L-amino acids. Different aminoacylation structures result in different directions of chiral selectivity, such that L-proteins need not emerge from a D-RNA World., (© 2024. The Author(s).)

Returned samples from the carbonaceous asteroid (162173) Ryugu provide pristine information on the original aqueous alteration history of the Solar System. Secondary precipitates, such as carbonates and phyllosilicates, reveal elemental partitioning of the major component ions linked to the primordial brine composition of the asteroid. Here, we report on the elemental partitioning and Mg isotopic composition ( 25 Mg/ 24 Mg) of breunnerite [(Mg, Fe, Mn)CO 3 ] from the Ryugu C0002 sample and the A0106 and C0107 aggregates by sequential leaching extraction of salts, exchangeable ions, carbonates, and silicates. Breunnerite was the sample most enriched in light Mg isotopes, and the 25 Mg/ 24 Mg value of the fluid had shifted lower by ~0.38‰ than the initial value (set to 0‰) before dolomite precipitation. As a simple model, the Mg 2+ first precipitated in phyllosilicates, followed by dolomite precipitation, at which time ~76-87% of Mg 2+ had been removed from the primordial brine. A minor amount of phyllosilicate precipitation continued after dolomite precipitation. The element composition profiles of the latest solution that interacted with the cation exchange pool of Ryugu were predominantly Na-rich. Na + acts as a bulk electrolyte and contributes to the stabilization of the negative surface charge of phyllosilicates and organic matter on Ryugu., (© 2024. The Author(s).)

We report primordial aqueous alteration signatures in water-soluble organic molecules from the carbonaceous asteroid (162173) Ryugu by the Hayabusa2 spacecraft of JAXA. Newly identified low-molecular-weight hydroxy acids (HO-R-COOH) and dicarboxylic acids (HOOC-R-COOH), such as glycolic acid, lactic acid, glyceric acid, oxalic acid, and succinic acid, are predominant in samples from the two touchdown locations at Ryugu. The quantitative and qualitative profiles for the hydrophilic molecules between the two sampling locations shows similar trends within the order of ppb (parts per billion) to ppm (parts per million). A wide variety of structural isomers, including α- and β-hydroxy acids, are observed among the hydrophilic molecules. We also identify pyruvic acid and dihydroxy and tricarboxylic acids, which are biochemically important intermediates relevant to molecular evolution, such as the primordial TCA (tricarboxylic acid) cycle. Here, we find evidence that the asteroid Ryugu samples underwent substantial aqueous alteration, as revealed by the presence of malonic acid during keto-enol tautomerism in the dicarboxylic acid profile. The comprehensive data suggest the presence of a series for water-soluble organic molecules in the regolith of Ryugu and evidence of signatures in coevolutionary aqueous alteration between water and organics in this carbonaceous asteroid., (© 2024. The Author(s).)

Mars has been exposed to ionizing radiation for several billion years, and as part of the search for life on the Red Planet, it is crucial to understand the impact of radiation on biosignature preservation. Several NASA and ESA missions are looking for evidence of ancient life in samples collected at depths shallow enough that they have been impacted by galactic cosmic rays (GCRs). In this study, we exposed a diverse set of Mars analog samples to 0.9 Megagray (MGy) of gamma radiation to mimic 15 million years of exposure on the Martian surface. We measured no significant impact of GCRs on the total organic carbon (TOC) and bulk stable C isotopes in samples with initial TOC concentration > 0.1 wt. %; however, diagnostic molecular biosignatures presented a wide range of degradation that didn't correlate to factors like mineralogy, TOC, water content, and surface area. Exposure dating suggests that the surface of Gale crater has been irradiated at more than five times our dose, yet using this relatively low dose and "best-case scenario" geologically recalcitrant biomarkers, large and variable losses were nevertheless evident. Our results empasize the importance of selecting sampling sites at depth or recently exposed at the Martian surface.

The sample from the near-Earth carbonaceous asteroid (162173) Ryugu is analyzed in the context of carbonaceous meteorites soluble organic matter. The analysis of soluble molecules of samples collected by the Hayabusa2 spacecraft shines light on an extremely high molecular diversity on the C-type asteroid. Sequential solvent extracts of increasing polarity of Ryugu samples are analyzed using mass spectrometry with complementary ionization methods and structural information confirmed by nuclear magnetic resonance spectroscopy. Here we show a continuum in the molecular size and polarity, and no organomagnesium molecules are detected, reflecting a low temperature and water-rich environment on the parent body approving earlier mineralogical and chemical data. High abundance of sulfidic and nitrogen rich compounds as well as high abundance of ammonium ions confirm the water processing. Polycyclic aromatic hydrocarbons are also detected in a structural continuum of carbon saturations and oxidations, implying multiple origins of the observed organic complexity, thus involving generic processes such as earlier carbonization and serpentinization with successive low temperature aqueous alteration., (© 2023. Springer Nature Limited.)

Samples from the carbonaceous asteroid (162173) Ryugu provide information on the chemical evolution of organic molecules in the early solar system. Here we show the element partitioning of the major component ions by sequential extractions of salts, carbonates, and phyllosilicate-bearing fractions to reveal primordial brine composition of the primitive asteroid. Sodium is the dominant electrolyte of the salt fraction extract. Anions and NH 4 + are more abundant in the salt fraction than in the carbonate and phyllosilicate fractions, with molar concentrations in the order SO 4 2-  > Cl -  > S 2 O 3 2-  > NO 3 -  > NH 4 + . The salt fraction extracts contain anionic soluble sulfur-bearing species such as S n -polythionic acids (n < 6), C n -alkylsulfonates, alkylthiosulfonates, hydroxyalkylsulfonates, and hydroxyalkylthiosulfonates (n < 7). The sulfur-bearing soluble compounds may have driven the molecular evolution of prebiotic organic material transforming simple organic molecules into hydrophilic, amphiphilic, and refractory S allotropes., (© 2023. Springer Nature Limited.)

The pristine sample from the near-Earth carbonaceous asteroid (162173) Ryugu collected by the Hayabusa2 spacecraft enabled us to analyze the pristine extraterrestrial material without uncontrolled exposure to the Earth's atmosphere and biosphere. The initial analysis team for the soluble organic matter reported the detection of wide variety of organic molecules including racemic amino acids in the Ryugu samples. Here we report the detection of uracil, one of the four nucleobases in ribonucleic acid, in aqueous extracts from Ryugu samples. In addition, nicotinic acid (niacin, a B 3 vitamer), its derivatives, and imidazoles were detected in search for nitrogen heterocyclic molecules. The observed difference in the concentration of uracil between A0106 and C0107 may be related to the possible differences in the degree of alteration induced by energetic particles such as ultraviolet photons and cosmic rays. The present study strongly suggests that such molecules of prebiotic interest commonly formed in carbonaceous asteroids including Ryugu and were delivered to the early Earth., (© 2023. The Author(s).)

The Hayabusa2 spacecraft collected samples from the surface of the carbonaceous near-Earth asteroid (162173) Ryugu and brought them to Earth. The samples were expected to contain organic molecules, which record processes that occurred in the early Solar System. We analyzed organic molecules extracted from the Ryugu surface samples. We identified a variety of molecules containing the atoms CHNOS, formed by methylation, hydration, hydroxylation, and sulfurization reactions. Amino acids, aliphatic amines, carboxylic acids, polycyclic aromatic hydrocarbons, and nitrogen-heterocyclic compounds were detected, which had properties consistent with an abiotic origin. These compounds likely arose from an aqueous reaction on Ryugu's parent body and are similar to the organics in Ivuna-type meteorites. These molecules can survive on the surfaces of asteroids and be transported throughout the Solar System.

Amino acids are fundamental to life as we know them as the monomers of proteins and enzymes. They are also readily synthesized under a variety of plausible prebiotic conditions and are common in carbon-rich meteorites. Thus, they represent a reasonable class of organics to target in the search for prebiotic chemistry or chemical evidence of life on Mars. However, regardless of their origin, amino acids and other organic molecules present in near-surface regolith and rocks on Mars can be degraded by exposure to cosmic rays that can penetrate to a depth of a few meters. We exposed several pure amino acids in dry and hydrated silicate mixtures and in mixtures of silicates with perchlorate salts to gamma radiation at various temperatures and radiation doses representative of the martian near-subsurface. We found that irradiation of amino acids mixed with dry silica powder increased the rate of amino acid radiolysis, with the radiolysis constants of amino acids in silicate mixtures at least a factor of 10 larger compared with the radiolysis constants of amino acids alone. The addition of perchlorate salts to the silicate samples or hydration of silicate samples further accelerated the rate of amino acid destruction during irradiation and increased the radiolysis constants by a factor of ∼1.5. Our results suggest that even low-molecular-weight amino acids could degrade in just ∼20 million years in the top 10 cm of the martian surface regolith and rock, and even faster if the material contains elevated abundances of hydrated silicate minerals or perchlorates. We did not detect evidence of amino acid racemization after gamma radiation exposure of the samples, which indicates that the chirality of some surviving amino acids may still be preserved. Our experimental results suggest serious challenges for the search of ancient amino acids and other potential organic biosignatures in the top 2 m of the martian surface.

The lack of pyrimidine diversity in meteorites remains a mystery since prebiotic chemical models and laboratory experiments have predicted that these compounds can also be produced from chemical precursors found in meteorites. Here we report the detection of nucleobases in three carbonaceous meteorites using state-of-the-art analytical techniques optimized for small-scale quantification of nucleobases down to the range of parts per trillion (ppt). In addition to previously detected purine nucleobases in meteorites such as guanine and adenine, we identify various pyrimidine nucleobases such as cytosine, uracil, and thymine, and their structural isomers such as isocytosine, imidazole-4-carboxylic acid, and 6-methyluracil, respectively. Given the similarity in the molecular distribution of pyrimidines in meteorites and those in photon-processed interstellar ice analogues, some of these derivatives could have been generated by photochemical reactions prevailing in the interstellar medium and later incorporated into asteroids during solar system formation. This study demonstrates that a diversity of meteoritic nucleobases could serve as building blocks of DNA and RNA on the early Earth., (© 2022. The Author(s).)

Amino acids and polycyclic aromatic hydrocarbons (PAHs) belong to the range of organic compounds detected in meteorites. In this study, we tested empirically and theoretically if PAHs are precursors for amino acids in carbonaceous chondrites, as previously suggested. We conducted experiments to synthesize amino acids from fluoranthene (PAH), with ammonium bicarbonate as a source for ammonia and carbon dioxide under mimicked asteroidal conditions. In our thermodynamic calculations, we extended our analysis to additional PAH-amino acid combinations. We explored 36 reactions involving the PAHs naphthalene, anthracene, fluoranthene, pyrene, triphenylene, and coronene and the amino acids glycine, alanine, valine, leucine, phenylalanine, and tyrosine. Our experiments do not show the formation of amino acids, whereas our theoretical results hint that PAHs could be precursors of amino acids in carbonaceous chondrites at low temperatures., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

The June 2, 2018, impact of asteroid 2018 LA over Botswana is only the second asteroid detected in space prior to impacting over land. Here, we report on the successful recovery of meteorites. Additional astrometric data refine the approach orbit and define the spin period and shape of the asteroid. Video observations of the fireball constrain the asteroid's position in its orbit and were used to triangulate the location of the fireball's main flare over the Central Kalahari Game Reserve. 23 meteorites were recovered. A consortium study of eight of these classifies Motopi Pan as a HED polymict breccia derived from howardite, cumulate and basaltic eucrite, and diogenite lithologies. Before impact, 2018 LA was a solid rock of ~156 cm diameter with high bulk density ~2.85 g/cm 3 , a relatively low albedo pv ~ 0.25, no significant opposition effect on the asteroid brightness, and an impact kinetic energy of ~0.2 kt. The orbit of 2018 LA is consistent with an origin at Vesta (or its Vestoids) and delivery into an Earth-impacting orbit via the v 6 resonance. The impact that ejected 2018 LA in an orbit towards Earth occurred 22.8 ± 3.8 Ma ago. Zircons record a concordant U-Pb age of 4563 ± 11 Ma and a consistent 207 Pb/ 206 Pb age of 4563 ± 6 Ma. A much younger Pb-Pb phosphate resetting age of 4234 ± 41 Ma was found. From this impact chronology, we discuss what is the possible source crater of Motopi Pan and the age of Vesta's Veneneia impact basin.

Despite extensive studies on the formation of organic molecules in various extraterrestrial environments, it still remains under debate when, where, and how such molecules were abiotically formed. A key molecule to solve the problem, hexamethylenetetramine (HMT) has not been confirmed in extraterrestrial materials despite extensive laboratory experimental evidence that it can be produced in interstellar or cometary environments. Here we report the first detection of HMT and functionalized HMT species in the carbonaceous chondrites Murchison, Murray, and Tagish Lake. While the part-per-billion level concentration of HMT in Murchison and Tagish Lake is comparable to other related soluble organic molecules like amino acids, these compounds may have eluded detection in previous studies due to the loss of HMT during the extraction processes. HMT, which can yield important molecules for prebiotic chemistry such as formaldehyde and ammonia upon degradation, is a likely precursor of meteoritic organic compounds of astrochemical and astrophysical interest.

The search for evidence of extraterrestrial life in our Solar System is currently guided by our understanding of terrestrial biology and its associated biosignatures. The observed homochirality in all life on Earth, that is, the predominance of "left-handed" or l-amino acids and "right-handed" or d-sugars, is a unique property of life that is crucial for molecular recognition, enzymatic function, information storage and structure and is thought to be a prerequisite for the origin or early evolution of life. Therefore, the detection of l- or d-enantiomeric excesses ( ee ) of chiral amino acids and sugars could be a powerful indicator for extant or extinct life on another world. However, studies of primitive meteorites have revealed they contain extraterrestrial amino acids and sugar acids (aldonic acids) with large enantiomeric excesses of the same chirality as terrestrial biology resulting from nonbiological processes, complicating the use of chiral asymmetry by itself as a definitive biosignature. Here we review our current knowledge of the distributions and enantiomeric and isotopic compositions of amino acids and polyols found in meteorites compared to terrestrial biology and propose a set of criteria for future life detection missions that can be used to help establish the origin of chiral asymmetry.

Aliphatic aldehydes and ketones are essential building blocks for the synthesis of more complex organic compounds. Despite 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 13 C-isotopic composition of aldehydes and ketones in 10 carbonaceous chondrites from the CI, CM, CR, and CV groups. The total concentration of carbonyl compounds ranged from 130 to 1000 nmol g -1 of meteorite with formaldehyde, acetaldehyde, and acetone being the most abundant species in all investigated samples. The 13 C-isotopic values ranged from -67 to +64‰ and we did not observe clear relationships between 13 C-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., Competing Interests: The authors declare no competing financial interest.

We evaluated the performance of the MinION DNA sequencer in-flight on the International Space Station (ISS), and benchmarked its performance off-Earth against the MinION, Illumina MiSeq, and PacBio RS II sequencing platforms in terrestrial laboratories. Samples contained equimolar mixtures of genomic DNA from lambda bacteriophage, Escherichia coli (strain K12, MG1655) and Mus musculus (female BALB/c mouse). Nine sequencing runs were performed aboard the ISS over a 6-month period, yielding a total of 276,882 reads with no apparent decrease in performance over time. From sequence data collected aboard the ISS, we constructed directed assemblies of the ~4.6 Mb E. coli genome, ~48.5 kb lambda genome, and a representative M. musculus sequence (the ~16.3 kb mitochondrial genome), at 100%, 100%, and 96.7% consensus pairwise identity, respectively; de novo assembly of the E. coli genome from raw reads yielded a single contig comprising 99.9% of the genome at 98.6% consensus pairwise identity. Simulated real-time analyses of in-flight sequence data using an automated bioinformatic pipeline and laptop-based genomic assembly demonstrated the feasibility of sequencing analysis and microbial identification aboard the ISS. These findings illustrate the potential for sequencing applications including disease diagnosis, environmental monitoring, and elucidating the molecular basis for how organisms respond to spaceflight.

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. In spite of these studies, the synthetic mechanisms for their formation leading to their occurrence in meteorites remain poorly understood. Typical 13 C-isotopic values (δ 13 C) of meteoritic glycine and methylamine are 13 C-enriched relative to their terrestrial counterparts; thus, analyses of their stable carbon isotopic compositions ( 13 C/ 12 C) 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 meteorite Murchison. 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.

On early Earth, a primitive polymer that could spontaneously form from likely available precursors may have preceded both RNA and DNA as the first genetic material. Here, we report that heated aqueous solutions containing 5-hydroxymethyluracil (HMU) result in oligomers of uracil, heated solutions containing 5-hydroxymethylcytosine (HMC) result in oligomers of cytosine, and heated solutions containing both HMU and HMC result in mixed oligomers of uracil and cytosine. Oligomerization of hydroxymethylated pyrimidines, which may have been abundant on the primitive Earth, might have been important in the development of simple informational polymers.

Proteins are responsible multiple biological functions, such as ligand binding, catalysis, and ion channeling. This functionality is enabled by proteins' three-dimensional structures that require long polypeptides. Since plausibly prebiotic synthesis of functional polypeptides has proven challenging in the laboratory, we propose that these functions may have been initially performed by alternative macromolecular constructs, namely hyperbranched polymers (HBPs), during early stages of chemical evolution. HBPs can be straightforwardly synthesized in one-pot processes, possess globular structures determined by their architecture as opposed to folding in proteins, and have documented ligand binding and catalytic properties. Our initial study focuses on glycerol-citric acid HBPs synthesized via moderate heating in the dry state. The polymerization products consisted of a mixture of isomeric structures of varying molar mass as evidenced by NMR, mass spectrometry and size-exclusion chromatography. Addition of divalent cations during polymerization resulted in increased incorporation of citric acid into the HBPs and the possible formation of cation-oligomer complexes. The chelating properties of citric acid govern the makeup of the resulting polymer, turning the polymerization system into a rudimentary smart material.

In the title compound, C5H9NO2·H2O, the amino acid is in the usual zwitterionic form involving the α-carboxyl-ate group. The cyclo-butane backbone of the amino acid is disordered over two conformations, with occupancies of 0.882 (7) and 0.118 (7). In the crystal, N-H⋯O and O-H⋯O hydrogen bonds link the zwitterions [with the water molecule involved as both acceptor (with the NH3 (+)) and donor (through a single carboxylate O from two different aminocyclobutane carb-oxylate moities)], resulting in a two-dimensional layered structure lying parallel to (100).

The title compound, C5H9NO4·H2O, is an isomer of the α-amino acid glutamic acid that crystallizes from water in its zwitterionic form as a monohydrate. It is not one of the 20 proteinogenic α-amino acids that are used in living systems and differs from the natural amino acids in that it has an α-methyl group rather than an α-H atom. In the crystal, an O-H⋯O hydrogen bond is present between the acid and water mol-ecules while extensive N-H⋯O and O-H⋯O hydrogen bonds link the components into a three-dimensional array.

Recent major discoveries in membrane biophysics hold the key to a modern understanding of the origin of life on Earth. Membrane bilayer vesicles have been shown to provide a multifaceted microenvironment in which protometabolic reactions could have developed. Cell-membrane-like aggregates of amphiphilic molecules capable of retaining encapsulated oligonucleotides have been successfully created in the laboratory. Sophisticated laboratory studies on the origin of life now show that elongation of the DNA primer takes place inside fatty acid vesicles when activated nucleotide nutrients are added to the external medium. These studies demonstrate that cell-like vesicles can be sufficiently permeable to allow for the intake of charged molecules such as activated nucleotides, which can then take part in copying templates in the protocell interior. In this Review we summarize recent experiments in this area and describe a possible scenario for the origin of primitive cells, with an emphasis on the elongation of encapsulated nucleotides.