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Compatibility of Amino Acids in Ice Ih: Implications for the Origin of Life
Abstract
Icy environments may have been common on early Earth due to the faint young sun. Previous studies have proposed that the formation of large icy bodies in the early ocean could concentrate the building blocks of life in eutectic fluids and, therefore, facilitate the polymerization of monomers. This hypothesis is based on the untested assumption that organic molecules are virtually incompatible in ice Ih (hexagonal ice). In this study, we conducted freezing experiments to explore the partitioning behavior of selected amino acids (AAs; glycine, l-alanine, l-proline, and l-phenylalanine) between ice Ih and aqueous solutions analogous to seawater. We allowed ice crystals to grow slowly from a few seeds in equilibrium with the solution and used Raman spectroscopy to analyze in situ the relative concentrations of AAs in the ice and aqueous solution. During freezing, there was no precipitation of AA crystals, indicating that the concentrations in solution never reached their solubility limit, even when the droplet was mostly frozen. Analyses of the Raman spectra of the ice and eutectic solution suggested that considerable amounts of AAs existed in the ice phase with partition coefficients varying between 0.2 and 0.5. These observations imply little incompatibility of AAs in ice Ih during the freezing of the solutions, rendering the concentration hypothesis in a eutectic system unwarranted. However, incorporation into ice Ih could protect AAs from decomposition or racemization and significantly improve the efficiency of extraterrestrial transport of small organics. Therefore, this study supports the hypothesis of extraterrestrial delivery of organic molecules in icy comets and asteroids to the primitive Earth as suggested by an increasing number of independent observations. Key Words: Ice Ih-Partition coefficient-Amino acids-Polymerization-Extraterrestrial transport of organics. Astrobiology 18, 381-392.
... Recently, Hao et al. (2018) conducted freezing experiments that rebuke the generality of this eutectic assumption, by allowing ice Ih crystals to grow slowly from a few seeds in equilibrium with an aqueous solution analogous to seawater with certain nonpolar amino acids, and demonstrated that considerable amounts of the latter existed in the ice Ih phase. Ice Ih is also thermodynamically stable on the surface of Saturn's icy satellites (Hendrix et al., 2018). ...
The atomic-scale fragmentation processes involved in molecules undergoing hypervelocity impacts (HVIs; defined as >3 km/s) are challenging to investigate via experiments and still not well understood. This is particularly relevant for the consistency of biosignals from small-molecular-weight neutral organic molecules obtained during solar system robotic missions sampling atmospheres and plumes at hypervelocities. Experimental measurements to replicate HVI effects on neutral molecules are challenging, both in terms of accelerating uncharged species and isolating the multiple transition states over very rapid timescales (<1 ps). Nonequilibrium first-principles-based simulations extend the range of what is possible with experiments. We report on high-fidelity simulations of the fragmentation of small organic biosignature molecules over the range v = 1-12 km/s, and demonstrate that the fragmentation fraction is a sensitive function of velocity, impact angle, molecular structure, impact surface material, and the presence of surrounding ice shells. Furthermore, we generate interpretable fragmentation pathways and spectra for velocity values above the fragmentation thresholds and reveal how organic molecules encased in ice grains, as would likely be the case for those in "ocean worlds," are preserved at even higher velocities than bare molecules. Our results place ideal spacecraft encounter velocities between 3 and 5 km/s for bare amino and fatty acids and within 4-6 km/s for the same species encased in ice grains and predict the onset of organic fragmentation in ice grains at >5 km/s, both consistent with recent experiments exploring HVI effects using impact-induced ionization and analysis via mass spectrometry and from the analysis of Enceladus organics in Cassini Data. From nanometer-sized ice Ih clusters, we establish that HVI energy is dissipated by ice casings through thermal resistance to the impact shock wave and that an upper fragmentation velocity limit exists at which ultimately any organic contents will be cleaved by the surrounding ice-this provides a fundamental path to characterize micrometer-sized ice grains. Altogether, these results provide quantifiable insights to bracket future instrument design and mission parameters.
... Specifically, aspartic acid and arginine have been shown to decompose within thousands, to at most a few million years in oceanic water and any detection of these compounds in material from ocean worlds will be strong evidence for a very efficient, probably extant generation mechanism. Another study implies high compatibility of amino acids in ice Ih during the freezing of an aqueous solution and suggests that the ice matrix protects amino acids from decomposition or racemization (Hao et al., 2018). The LILBID experiments conducted so far (this work, and Klenner et al., 2020) show that such compounds can be reliably detected and identified at low concentrations, particularly arginine in a salt-poor matrix and aspartic acid in a salt-rich matrix. ...
Identifying and distinguishing between abiotic and biotic signatures of organic molecules such as amino acids and fatty acids is key to the search for life on extraterrestrial ocean worlds. Impact ionization mass spectrometers can potentially achieve this by sampling water ice grains formed from ocean water and ejected by moons such as Enceladus and Europa, thereby exploring the habitability of their subsurface oceans in spacecraft flybys. Here, we extend previous high-sensitivity laser-based analog experiments of biomolecules in pure water to investigate the mass spectra of amino acids and fatty acids at simulated abiotic and biotic relative abundances. To account for the complex background matrix expected to emerge from a salty Enceladean ocean that has been in extensive chemical exchange with a carbonaceous rocky core, other organic and inorganic constituents are added to the biosignature mixtures. We find that both amino acids and fatty acids produce sodiated molecular peaks in salty solutions. Under the soft ionization conditions expected for low-velocity (2-6 km/s) encounters of an orbiting spacecraft with ice grains, the unfragmented molecular spectral signatures of amino acids and fatty acids accurately reflect the original relative abundances of the parent molecules within the source solution, enabling characteristic abiotic and biotic relative abundance patterns to be identified. No critical interferences with other abiotic organic compounds were observed. Detection limits of the investigated biosignatures under Enceladus-like conditions are salinity dependent (decreasing sensitivity with increasing salinity), at the μM or nM level. The survivability and ionization efficiency of large organic molecules during impact ionization appears to be significantly improved when they are protected by a frozen water matrix. We infer from our experimental results that encounter velocities of 4-6 km/s are most appropriate for impact ionization mass spectrometers to detect and discriminate between abiotic and biotic signatures.
Short peptides with unique catalytic abilities are regarded as the simplest enzymes possessing great potential as primordial species to take part in the chemical origin of life. However, prebiotic acquisition pathways of catalytically active peptides remain unclear. In this study, a microwave reactor was used to simulate hydrothermal environments, such as hydrothermal vents, either submarine or subaerial environments. A refrigerator freezer was used to make ice pieces that mimic extra-terrestrial ice crystals. Serine (Ser) and histidine (His) were used as examples, and the formation of small functional peptides involving sodium trimetaphosphate (P3m) activation in an alkaline aqueous solution was investigated under the two typical prebiotic environments mentioned above. The obtained experimental results showed that the targeted small functional peptide Ser-His and its sequence isomer His-Ser could be formed in all simulated environments, even in the presence of disruptive amino acids, such as alanine (Ala), proline (Pro), and aspartic acid (Asp), in the reaction systems. Notably, Pro may have some effect on the chirality of the produced dipeptides by screening the configuration of the amino acids. Owing to the lack of disturbance of N-O migration in the CAPA (His) intermediate, the CAPA intermediate of His is more stable than that of Ser; therefore, His is more easily activated by P3m to form a dipeptide with His at the N-terminal. The yield of His-Ser is at least about four times that of Ser-His in the two simulated prebiotic environments. Additionally, our work suggests that more types of amino acids can be activated simultaneously by P3m to produce various dipeptides, which will provide abundant raw materials for the evolution of life molecules.
Shock experiments on an aqueous l-alanine solution were undertaken to examine the significance of cometary impacts in supplying prebiotic compounds to the early Earth. The shock pressures and temperatures ranged from 6.5 to 34.0 GPa and 516 to 963 K, respectively. Alanine in the shocked samples decreases in abundance and has higher d/l ratios as the shock temperature increases. The shocked sample at 963 K contained 33% of the starting alanine, which had a d/l value of 0.51. The shocked samples above 643 K all contained isomers of the alanine dimer Ala–Ala, including l-Ala–l-Ala, l-Ala–d-Ala, d-Ala–l-Ala, and d-Ala–d-Ala. A comparison of our study with previous studies indicates that water inhibits the decomposition of alanine and promotes racemization during shock compression. We calculated the shock temperatures at various impact velocities to determine the impact velocity at which alanine can survive when comets and meteorites impact the land or ocean at different impact angles. This impact velocity was much lower for comets than meteorites. The reduction in alanine decomposition caused by water is compensated for by the high shock temperature produced by the high porosity of comets. However, considering that comets are effectively decelerated by airburst and contain large amounts of organic materials, comets would be more important than meteorites in terms of delivering prebiotic compounds, including amino acid dimers with ll enantiomeric excesses, to the early Earth. Comets are likely to have played a key role in the biogeochemical evolution of the early Earth.
Significance
Approximately 3.5-Ga sedimentary rocks surveyed by the Mars Science Laboratory rover in Gale Crater, Mars, contain secondary mineral phases indicating aqueous alteration and release of cations from mafic minerals during sediment deposition in lakes. However, carbonate phases are not detected, and our model calculations indicate atmospheric CO 2 levels at the time of sediment deposition 10s to 100s of times lower than those required by climate models to warm early Mars enough to maintain surficial water. Our results offer a ground-based reference point for the evolution of martian atmospheric CO 2 and imply that other mechanisms of warming Hesperian Mars, or processes that allowed for confined hydrological activity under cold conditions, must be sought.
IR and Raman spectroscopic technology can be directly used to identify the occurrence of ferroelectric ice XI in laboratory or extraterrestrial settings. The performance of 16 different DFT methods applied on the ice Ih, VIII, IX, and XI crystal phases is evaluated. Based on a selected DFT computational scheme, the IR and Raman spectra of ice Ih and XI are derived and compared. When the spectra, both IR and Raman, of ice Ih and ice XI are compared, the librational vibrations are found to be the most affected by the proton ordering. The spectroscopic fingerprint of ice XI can be used to distinguish ferroelectric ice XI from ice Ih in the universe. Furthermore, the existence of only one kind of H-bond in ice Ih is demonstrated from the overlapping subspectra for different types of H-bonded pair configurations in 16 isomers of ice Ih, which provides an illustration to the historic debate on whether one or two kinds of H-bonds existed in ice.
Natural gas hydrates are solid hydrogen-bonded water crystals containing small molecular gases. The amount of natural gas stored as hydrates in permafrost and ocean sediments is twice that of all other fossil fuels combined. However, hydrate blockages also hinder oil/gas pipeline transportation, and, despite their huge potential as energy sources, our insufficient understanding of hydrates has limited their extraction. Here, we report how the presence of amino acids in water induces changes in its structure and thus interrupts the formation of methane and natural gas hydrates. The perturbation of the structure of water by amino acids and the resulting selective inhibition of hydrate cage formation were observed directly. A strong correlation was found between the inhibition efficiencies of amino acids and their physicochemical properties, which demonstrates the importance of their direct interactions with water and the resulting dissolution environment. The inhibition of methane and natural gas hydrate formation by amino acids has the potential to be highly beneficial in practical applications such as hydrate exploitation, oil/gas transportation, and flow assurance. Further, the interactions between amino acids and water are essential to the equilibria and dynamics of many physical, chemical, biological, and environmental processes.
The importance of comets for the origin of life on Earth has been advocated for many decades. Amino acids are key ingredients in chemistry, leading to life as we know it. Many primitive meteorites contain amino acids, and it is generally believed that these are formed by aqueous alterations. In the collector aerogel and foil samples of the Stardust mission after the flyby at comet Wild 2, the simplest form of amino acids, glycine, has been found together with precursor molecules methylamine and ethylamine. Because of contamination issues of the samples, a cometary origin was deduced from the (13)C isotopic signature. We report the presence of volatile glycine accompanied by methylamine and ethylamine in the coma of 67P/Churyumov-Gerasimenko measured by the ROSINA (Rosetta Orbiter Spectrometer for Ion and Neutral Analysis) mass spectrometer, confirming the Stardust results. Together with the detection of phosphorus and a multitude of organic molecules, this result demonstrates that comets could have played a crucial role in the emergence of life on Earth.
The destruction of solid glycine under irradiation with 2 keV electrons has been investigated by means of IR spectroscopy. Destruction cross sections, radiolysis yields, and half-life doses were determined for samples at 20, 40, 90, and 300 K. The thickness of the irradiated samples was kept below the estimated penetration depth of the electrons. No significant differences were obtained in the experiments below 90 K, but the destruction cross section at 300 K was larger by a factor of 2. The radiolysis yields and half-life doses are in good accordance with recent MeV proton experiments, which confirms that electrons in the keV range can be used to simulate the effects of cosmic rays if the whole sample is effectively irradiated. In the low temperature experiments, electron irradiation leads to the formation of residues. IR absorptions of these residues are assigned to the presence CO2, CO, OCN-, and CN- and possibly to amide bands I to III. The protection of glycine by water ice is also studied. A water ice film of ∼150 nm is found to provide efficient shielding against the bombardment of 2 keV electrons. The results of this study show also that current Monte Carlo predictions provide a good global description of electron penetration depths. The lifetimes estimated in this work for various environments ranging from the diffuse interstellar medium to the inner solar system, show that the survival of hypothetical primeval glycine from the solar nebula in present solar system bodies is not very likely. © 2015. The American Astronomical Society. All rights reserved.
A recent study by Ramirez et al. (2014) demonstrated that an atmosphere with
1.3-4 bar of CO2 and H2O, in addition to 5-20% H2, could have raised the mean
annual and global surface temperature of early Mars above the freezing point of
water. Such warm temperatures appear necessary to generate the rainfall (or
snowfall) amounts required to carve the ancient martian valleys. Here, we use
our best estimates for early martian outgassing rates, along with a 1-D
photochemical model, to assess the conversion efficiency of CO, CH4, and H2S to
CO2, SO2, and H2. Our outgassing estimates assume that Mars was actively
recycling volatiles between its crust and interior, as Earth does today. H2
production from serpentinization and deposition of banded iron-formations is
also considered. Under these assumptions, maintaining an H2 concentration of
~1-2% by volume is achievable, but reaching 5% H2 requires additional H2
sources or a slowing of the hydrogen escape rate below the diffusion limit. If
the early martian atmosphere was indeed H2-rich, we might be able to see
evidence of this in the rock record. The hypothesis proposed here is consistent
with new data from the Curiosity Rover, which show evidence for a long-lived
lake in Gale Crater near Mt. Sharp. It is also consistent with measured oxygen
fugacities of martian meteorites, which show evidence for progressive mantle
oxidation over time.
Serpentinization involves the hydrolysis and transformation of primary ferromagnesian minerals such as olivine ((Mg,Fe) 2 SiO 4) and pyroxenes ((Mg,Fe)SiO 3) to produce H 2-rich fluids and a variety of secondary minerals over a wide range of environmental conditions. The continual and elevated production of H 2 is capable of reducing carbon, thus initiating an inorganic pathway to produce organic compounds. The production of H 2 and H 2-dependent CH 4 in serpentinization systems has received significant interdisciplinary interest, especially with regard to the abiotic synthesis of organic compounds and the origins and maintenance of life in Earth's lithosphere and elsewhere in the Universe. Here, serpentinization with an emphasis on the formation of H 2 and CH 4 are reviewed within the context of the mineralogy, temperature/pressure, and fluid/gas chemistry present in planetary environments. Whether deep in Earth's interior or in Kuiper Belt Objects in space, serpentinization is a feasible process to invoke as a means of producing astrobiologically indispensable H 2 capable of reducing carbon to organic compounds. Key Words: Serpentinization—Fischer-Tropsch-type synthesis—Hydrogen formation—Methane formation—Ultramafic rocks. Astrobiology 15, xxx–xxx.
The outer Solar System may provide a potential habitat for extraterrestrial life. Remote sensing data from the Galileo spacecraft suggest that the jovian icy moons-Europa, Ganymede, and possibly Callisto-may harbor liquid water oceans underneath their icy crusts. Although compositional information required for the discussion of habitability is limited because of significantly restricted observation data, organic molecules are ubiquitous in the Universe. Recently, in situ spacecraft measurements and experiments suggest that amino acids can be formed abiotically on interstellar ices and comets. These amino acids could be continuously delivered by meteorite or comet impacts to icy moons. Here, we show that polymerization of organic monomers, in particular amino acids and nucleotides, could proceed spontaneously in the cold environment of icy moons, in particular the jovian icy moon Europa as a typical example, based on thermodynamic calculations, though kinetics of formation are not addressed. Observed surface temperature on Europa is 120 and 80 K in the equatorial region and polar region, respectively. At such low temperatures, Gibbs energies of polymerization become negative, and the estimated thermal structure of the icy crust should contain a shallow region (i.e., at a depth of only a few kilometers) favorable for polymerization. Investigation of the possibility of organic monomer polymerization on icy moons could provide good constraints on the origin and early evolution of extraterrestrial life. Key Words: Planetary science-Europa-Planetary habitability and biosignatures-Extraterrestrial life-Extraterrestrial organic compounds. Astrobiology 15, 430-441.
The presence of valleys on ancient terrains of Mars suggests that liquid water flowed on the martian surface 3.8Gyr ago or before. The above-freezing temperatures required to explain valley formation could have been transient, in response to the frequent large meteorite impacts on early Mars, or they could have been caused by long-lived greenhouse warming. Climate models that consider only the greenhouse gases carbon dioxide and water have been unable to recreate warm surface conditions, given the lower solar luminosity at that time. Here we use a one-dimensional climate model to demonstrate that an atmosphere containing 1.3-4bar of CO2 and water, in addition to 5-20% H2, could have raised the mean surface temperature of early Mars above the freezing point of water. Vigorous volcanic outgassing from a highly reduced early martian mantle is expected to provide sufficient atmospheric H2 and CO2--the latter from the photochemical oxidation of outgassed CH4 and CO--to form a CO2 and H2 greenhouse. Such a dense early martian atmosphere is consistent with independent estimates of surface pressure based on cratering data.
Comets are known to harbour simple ices and the organic precursors of the building blocks of proteins—amino acids—that are essential to life. Indeed, glycine, the simplest amino acid, was recently confirmed to be present on comet 81P/Wild-2 from samples returned by NASA’s Stardust spacecraft. Impacts of icy bodies (such as comets) onto rocky surfaces, and, equally, impacts of rocky bodies onto icy surfaces (such as the jovian and saturnian satellites), could have been responsible for the manufacture of these complex organic molecules through a process of shock synthesis. Here we present laboratory experiments in which we shocked ice mixtures analogous to those found in a comet with a steel projectile fired at high velocities in a light gas gun to test whether amino acids could be produced. We found that the hypervelocity impact shock of a typical comet ice mixture produced several amino acids after hydrolysis. These include equal amounts of D- and L-alanine, and the non-protein amino acids α-aminoisobutyric acid and isovaline as well as their precursors. Our findings suggest a pathway for the synthetic production of the components of proteins within our Solar System, and thus a potential pathway towards life through icy impacts.
Context. Glycine, the simplest of amino acids, has been found in several
carbonaceous meteorites collected on Earth, though its presence in the
interstellar medium (ISM) has never been confirmed as of today. It is
now considered that its synthesis took place in the icy mantles of
interstellar grains, but it remains unclear how glycine, once
synthesized and trapped in interplanetary particles, survives during the
transfer to the Earth. Aims: Assuming that glycine was
effectively formed in the ice, we address the question of its resistance
to a solar-like radiation field and look for the possible molecular
remnants that would be useful tracers of its former existence.
Methods: The search was conducted using an interdisciplinary approach
that mixes, on the one hand, irradiations in ultra high vacuum at 30 K
on the TEMPO beam line of the synchrotron SOLEIL, simultaneously with
near-edge X-ray absorption spectroscopy (NEXAFS) measurements, and on
the other hand, quantum calculations to determine the energetics of the
fragmentations and the relative stability of the different byproducts.
The last points were addressed by means of density functional theory
(DFT) simulations followed by high-level post Hartree-Fock calculations
when more accurate relative energies were necessary. The constraints of
an icy environment deserved special attention and the ice was modeled by
a polarizable continuum medium that relies on the dielectric constant of
water ice at 10-50 K. Results: Destruction of glycine is observed
in the first seconds of irradiation, and carbon dioxide (CO2)
and methylamine (CH3NH2) are formed. Carbon
monoxide (CO), methanimine (CH2NH) and hydrogen cyanide (HCN)
are also produced in secondary reactions. The amino acid destruction is
the same for pure glycine and glycine in ice, indicating that the OH
radicals released by the water matrix is barely involved in the
photolytic process; however, these radicals are involved in the
production of the secondary byproducts through dehydrogenation reactions
as shown by ab initio quantum chemical simulation presented in this
article along with the experimental results. Conclusions: The
experiments show that glycine is only partially destroyed. Its abundance
is found to stay at a level of ~30% of the initial concentration, for an
irradiation dose equivalent to three years of solar radiation (at a
distance of one astronomical unit). This result supports the hypothesis
that, if trapped in protected icy environments and/or in the interior of
interplanetary particles and meteorites, glycine may partly resist the
radiation field to which it is submitted and, accordingly, survives its
journey to the Earth.
As the foundation of energy industry moves towards gas, flow assurance technology preventing pipelines from hydrate blockages becomes increasingly significant. However, the principle of hydrate inhibition is still poorly understood. Here, we examined natural hydrophobic amino acids as novel kinetic hydrate inhibitors (KHIs), and investigated hydrate inhibition phenomena by using them as a model system. Amino acids with lower hydrophobicity were found to be better KHIs to delay nucleation and retard growth, working by disrupting the water hydrogen bond network, while those with higher hydrophobicity strengthened the local water structure. It was found that perturbation of the water structure around KHIs plays a critical role in hydrate inhibition. This suggestion of a new class of KHIs will aid development of KHIs with enhanced biodegradability, and the present findings will accelerate the improved control of hydrate formation for natural gas exploitation and the utilization of hydrates as next-generation gas capture media.
The crustal Urey cycle of CO2 involving silicate weathering and metamorphism acts as a dynamic climate buffer. In this cycle, warmer temperatures speed silicate weathering and carbonate formation, reducing atmospheric CO2 and thereby inducing global cooling. Over long periods of time, cycling of CO2 into and out of the mantle also dynamically buffers CO2. In the mantle cycle, CO2 is outgassed at ridge axes and island arcs, while subduction of carbonatized oceanic basalt and pelagic sediments returns CO2 to the mantle. Negative feedback is provided because the amount of basalt carbonatization depends on CO2 in seawater and therefore on CO2 in the air. On the early Earth, processes involving tectonics were more vigorous than at present, and the dynamic mantle buffer dominated over the crustal one. The mantle cycle would have maintained atmospheric and oceanic CO2 reservoirs at levels where the climate was cold in the Archean unless another greenhouse gas was important. Reaction of CO2 with impact ejecta and its eventual subduction produce even lower levels of atmospheric CO2 and small crustal carbonate reservoirs in the Hadean. Despite its name, the Hadean climate would have been freezing unless tempered by other greenhouse gases.
One of the best-known uses of methanol is as antifreeze. Methanol is used in large quantities in industrial applications to prevent methane clathrate hydrate blockages from forming in oil and gas pipelines. Methanol is also assigned a major role as antifreeze in giving icy planetary bodies (e.g., Titan) a liquid subsurface ocean and/or an atmosphere containing significant quantities of methane. In this work, we reveal a previously unverified role for methanol as a guest in clathrate hydrate cages. X-ray diffraction (XRD) and NMR experiments showed that at temperatures near 273 K, methanol is incorporated in the hydrate lattice along with other guest molecules. The amount of included methanol depends on the preparative method used. For instance, single-crystal XRD shows that at low temperatures, the methanol molecules are hydrogen-bonded in 4.4% of the small cages of tetrahydrofuran cubic structure II hydrate. At higher temperatures, NMR spectroscopy reveals a number of methanol species incorporated in hydrocarbon hydrate lattices. At temperatures characteristic of icy planetary bodies, vapor deposits of methanol, water, and methane or xenon show that the presence of methanol accelerates hydrate formation on annealing and that there is unusually complex phase behavior as revealed by powder XRD and NMR spectroscopy. The presence of cubic structure I hydrate was confirmed and a unique hydrate phase was postulated to account for the data. Molecular dynamics calculations confirmed the possibility of methanol incorporation into the hydrate lattice and show that methanol can favorably replace a number of methane guests.
Organic compounds observed in the interstellar medium and in solar system bodies are of particular importance for revealing the chemistry that may have led to life's origin. Among these compounds, amino acids may have played a crucial role since they are basic components of proteins, which are the essential constituents of all organisms. We present laboratory studies testing the stability of amino acids against ultraviolet (UV) photolysis. Two biological and two nonbiological amino acids have been irradiated in frozen Ar, N2, and H2O to simulate conditions in the interstellar gas and on interstellar grains. The experimental results can be interpreted to indicate that amino acids in the gas phase will likely be destroyed during the lifetime of a typical interstellar cloud. In regions with relatively low UV radiation, amino acids might be present as transient gas-phase species. Their survival in interstellar icy grain mantles and the surface layers of comets and planets is strongly limited in the presence of UV irradiation. The rate of destruction is rather insensitive to the amino acid structure and to the ice matrix. We consider the implications of these results for the survival and transfer of amino acids in space environments, and thus their possible availability for prebiotic chemistry.
The discoveries of amino acids of extraterrestrial origin in many meteorites over the last 50 years have revolutionized the Astrobiology field. A variety of non-terrestrial amino acids similar to those found in life on Earth have been detected in meteorites. A few amino acids have even been found with chiral excesses, suggesting that meteorites could have contributed to the origin of homochirality in life on Earth. In addition to amino acids, which have been productively studied for years, sugar-like molecules, activated phosphates, and nucleobases have also been determined to be indigenous to numerous meteorites. Because these molecules are essential for life as we know it, and meteorites have been delivering them to the Earth since accretion, it is plausible that the origin(s) of life on Earth were aided by extraterrestrially-synthesized molecules. Understanding the origins of life on Earth guides our search for life elsewhere, helping to answer the question of whether biology is unique to Earth. This tutorial review focuses on meteoritic amino acids and nucleobases, exploring modern analytical methods and possible formation mechanisms. We will also discuss the unique window that meteorites provide into the chemistry that preceded life on Earth, a chemical record we do not have access to on Earth due to geologic recycling of rocks and the pervasiveness of biology across the planet. Finally, we will address the future of meteorite research, including asteroid sample return missions.
For more than four decades, scientists have been trying to find an answer to
one of the most fundamental questions in paleoclimatology, the `faint young Sun
problem'. For the early Earth, models of stellar evolution predict a solar
energy input to the climate system which is about 25% lower than today. This
would result in a completely frozen world over the first two billion years in
the history of our planet, if all other parameters controlling Earth's climate
had been the same. Yet there is ample evidence for the presence of liquid
surface water and even life in the Archean (3.8 to 2.5 billion years before
present), so some effect (or effects) must have been compensating for the faint
young Sun. A wide range of possible solutions have been suggested and explored
during the last four decades, with most studies focusing on higher
concentrations of atmospheric greenhouse gases like carbon dioxide, methane or
ammonia. All of these solutions present considerable difficulties, however, so
the faint young Sun problem cannot be regarded as solved. Here I review
research on the subject, including the latest suggestions for solutions of the
faint young Sun problem and recent geochemical constraints on the composition
of Earth's early atmosphere. Furthermore, I will outline the most promising
directions for future research. In particular I would argue that both improved
geochemical constraints on the state of the Archean climate system and
numerical experiments with state-of-the-art climate models are required to
finally assess what kept the oceans on the Archean Earth from freezing over
completely.
Submarine hydrothermal vents above serpentinite produce chemical potential gradients of aqueous and ionic hydrogen, thus providing a very attractive venue for the origin of life. This environment was most favourable before Earth's massive CO(2) atmosphere was subducted into the mantle, which occurred tens to approximately 100 Myr after the moon-forming impact; thermophile to clement conditions persisted for several million years while atmospheric pCO(2) dropped from approximately 25 bar to below 1 bar. The ocean was weakly acid (pH ∼ 6), and a large pH gradient existed for nascent life with pH 9-11 fluids venting from serpentinite on the seafloor. Total CO(2) in water was significant so the vent environment was not carbon limited. Biologically important phosphate and Fe(II) were somewhat soluble during this period, which occurred well before the earliest record of preserved surface rocks approximately 3.8 billion years ago (Ga) when photosynthetic life teemed on the Earth and the oceanic pH was the modern value of approximately 8. Serpentinite existed by 3.9 Ga, but older rocks that might retain evidence of its presence have not been found. Earth's sequesters extensive evidence of Archaean and younger subducted biological material, but has yet to be exploited for the Hadean record.
Delivery of prebiotic compounds to early Earth from an impacting comet is thought to be an unlikely mechanism for the origins of life because of unfavourable chemical conditions on the planet and the high heat from impact. In contrast, we find that impact-induced shock compression of cometary ices followed by expansion to ambient conditions can produce complexes that resemble the amino acid glycine. Our ab initio molecular dynamics simulations show that shock waves drive the synthesis of transient C-N bonded oligomers at extreme pressures and temperatures. On post impact quenching to lower pressures, the oligomers break apart to form a metastable glycine-containing complex. We show that impact from cometary ice could possibly yield amino acids by a synthetic route independent of the pre-existing atmospheric conditions and materials on the planet.
Raman spectroscopy was used to study the NaCl aqueous solutions around the solid-liquid phase transition. Special attention was devoted to the modification induced by the salt on the OH stretching band of water. Investigations were carried out in the temperature range between -21 and 10 degrees C, for concentrations from 0 to 200 g/L. We demonstrated that micro-Raman spectroscopy can be used as a marker, allowing the determination of the salt concentration of an aqueous solution with an error close to +/-5%.
We address the first several hundred million years of Earth's history. The Moon-forming impact left Earth enveloped in a hot silicate atmosphere that cooled and condensed over similar to 1,000 yrs. As it cooled the Earth degassed its volatiles into the atmosphere. It took another similar to 2 Myrs for the magma ocean to freeze at the surface. The cooling rate was determined by atmospheric thermal blanketing. Tidal heating by the new Moon was a major energy source to the magma ocean. After the mantle solidified geothermal heat became climatologically insignificant, which allowed the steam atmosphere to condense, and left behind a similar to 100 bar, similar to 500 K CO2 atmosphere. Thereafter cooling was governed by how quickly CO2 was removed from the atmosphere. If subduction were efficient this could have taken as little as 10 million years. In this case the faint young Sun suggests that a lifeless Earth should have been cold and its oceans white with ice. But if carbonate subduction were inefficient the CO2 would have mostly stayed in the atmosphere, which would have kept the surface near similar to 500 K for many tens of millions of years. Hydrous minerals are harder to subduct than carbonates and there is a good chance that the Hadean mantle was dry. Hadean heat flow was locally high enough to ensure that any ice cover would have been thin (< 5 m) in places. Moreover hundreds or thousands of asteroid impacts would have been big enough to melt the ice triggering brief impact summers. We suggest that plate tectonics as it works now was inadequate to handle typical Hadean heat flows of 0.2-0.5 W/m(2). In its place we hypothesize a convecting mantle capped by a similar to 100 km deep basaltic mush that was relatively permeable to heat flow. Recycling and distillation of hydrous basalts produced granitic rocks very early, which is consistent with preserved > 4 Ga detrital zircons. If carbonates in oceanic crust subducted as quickly as they formed, Earth could have been habitable as early as 10-20 Myrs after the Moon-forming impact.
Granitoid gneisses and supracrustal rocks that are 3,800-4,000 Myr old are the oldest recognized exposures of continental crust. To obtain insight into conditions at the Earth's surface more than 4 Gyr ago requires the analysis of yet older rocks or their mineral remnants. Such an opportunity is presented by detrital zircons more than 4 Gyr old found within 3-Gyr-old quartzitic rocks in the Murchison District of Western Australia. Here we report in situ U-Pb and oxygen isotope results for such zircons that place constraints on the age and composition of their sources and may therefore provide information about the nature of the Earth's early surface. We find that 3,910-4,280 Myr old zircons have oxygen isotope (delta18O) values ranging from 5.4+/-0.6% to 15.0+/-0.4%. On the basis of these results, we postulate that the approximately 4,300-Myr-old zircons formed from magmas containing a significant component of re-worked continental crust that formed in the presence of water near the Earth's surface. These data are therefore consistent with the presence of a hydrosphere interacting with the crust by 4,300 Myr ago.
Making ribose in interstellar ices
Astrobiologists have long speculated on the origin of prebiotic molecules such as amino acids and sugars. Meinert et al. demonstrated that numerous prebiotic molecules can be formed in an interstellar-analog sample containing a mixture of simple ices of water, methanol, and ammonia. They irradiated the sample with ultraviolet light under conditions similar to those expected during the formation of the solar system. This yielded a wide variety of sugars, including ribose—a major constituent of ribonucleic acid (RNA).
Science , this issue p. 208
Water is an essential component of life processes. There are no plant or animal species that can exist in the complete absence of water1. This observation is apparent at both the macroscopic and atomic level. At the atomic level, proteins and nucleic acids lose their characteristic three-dimensional architecture and their biological function when water is removed. There is no question that the ubiquitous water molecule has an essential place in biological processes. From the hydrogen-bonding point of view, the water molecule is unique in having both double-donor and double-acceptor hydrogen-bond functionality, which is about one central atom, the oxygen. It is possible therefore for water molecules to exercise a wide range of orientational flexibility without substantial loss of hydrogen-bonding energy. It is this orientational freedom that makes it difficult to define the hydrogen-bond structure of an assembly of water molecules in the absence of precise information concerning the location of the hydrogen atoms and the dynamics of their motion.
The aftermath of the Moon-forming impact left Earth with a hot, CO2-rich steam atmosphere. Water oceans condensed from the steam after 2 Myr, but for some 10-100 Myr the surface stayed warm (similar to 500K), the length of time depending on how quickly the CO2 was removed into the mantle. Thereafter a lifeless Earth, heated only by the dim light of the young Sun, would have evolved into a bitterly cold ice world, The cooling trend was frequently interrupted by volcanic- or impact-induced thaws.
Gas hydrates are crystalline ice-like solid materials enclosing gas molecules inside. The possibility of the presence of gas hydrates with amino acids in the universe is of interest when revealing the potential existence of life as they are evidence of a source of water and organic precursors, respectively. However, little is known about how they can naturally coexist, and their crystallization behavior would become far more complex as both crystallize with formation of hydrogen bonds. Here, we report abnormal incorporation of amino acids into the gas hydrate crystal lattice that is contrary to the generally accepted crystallization mode, and this resulted in lattice distortion and expansion. The present findings imply the potential for their natural coexistence by sharing the crystal lattice, and will be helpful for understanding the role of additives in the gas hydrate crystallization.
Ion microprobe analyses of δ18O in 4400–3900 Ma igneous zircons from the Jack Hills, Western Australia, provide a record of the oxygen isotope composition of magmas in the earliest Archean. We have employed a detailed analysis protocol aimed at correlating spatially related micro-volumes of zircon concordant in U/Pb age with δ18O and internal zoning. Simultaneous analysis of 18O and 16O with dual Faraday cup detectors, combined with frequent standardization, has yielded data with improved accuracy and precision over prior studies, and resulted in a narrower range of what is interpreted as magmatic δ18O in > 3900 Ma zircons. Preserved magmatic δ18O values from individual zircons (Zrc) range from 5.3‰ to 7.3‰ (VSMOW), and increasingly deviate from the mantle range of 5.3 ± 0.3‰ as zircons decrease in age from 4400 to 4200 Ma. Elevated δ18O (Zrc) values up to 6.5‰ occur as early as 4325 Ma, which suggests that evolved rocks were incorporated into magmas within ∼230 Ma of Earth's accretion. Values of magmatic δ18O (Zrc) as high as 7.3‰ are recorded in zircons by 4200 Ma, and are common thereafter. The protoliths of the magmas these zircons crystallized in were altered by low temperature interaction with liquid water near Earth’s surface. These results provide the strongest evidence yet for the existence of liquid water oceans and supracrustal rocks by approximately 4200 Ma, and possibly as early as 4325 Ma. The range of magmatic δ18O values in the 4400–3900 Ma zircons is indistinguishable from Archean igneous zircons, suggesting similar magmatic processes occurred over the first two billion years of recorded Earth history. Zircons with sub-solidus alteration histories, identified by the presence of disturbed internal zoning patterns, record δ18O values both below (4.6‰) and above (10.3‰) the observed range for primary magmatic zircon, and are unreliable indicators of Early Archean magma chemistry.
Mars was warmer and wetter during the early to middle Noachian, before a hydrologic and climatic transition in the late Noachian led to a decrease in erosion rates, a change in valley network morphology, and a geochemical shift from phyllosilicate to sulfate formation that culminated in the formation of widespread sulfate-rich sedimentary deposits in Meridiani Planum and the surrounding Arabia Terra region. This secular evolution was overprinted by episodic and periodic variability, as recorded in the fluvial record, sedimentary layering, and erosional discontinuities. We investigate the temporal evolution of Martian groundwater hydrology during the Noachian and early Hesperian epochs using global-scale hydrological models. The results suggest that the more active hydrological cycle in the Noachian was a result of a greater total water inventory, causing a saturated near-surface and high precipitation rates. The late Noachian hydrologic, climatic, and geochemical transition can be explained by a fundamental shift in the hydrological regime driven by a net loss of water due to impact and solar wind erosion of the atmosphere. Following this transition, the water table retreated deep beneath the surface, except in isolated regions of focused groundwater upwelling and evaporation, producing the playa evaporites in Meridiani Planum and Arabia Terra. This long-term evolution was modulated by shorter-term climate forcing in the form of periodic and chaotic variations in the orbital parameters of Mars, resulting in changes in the volume of water sequestered in the polar caps and cryosphere. This shorter-term forcing can explain the observed periodic and bundled sedimentary layering, erosional unconformities, and evidence for a fluctuating water table at Meridiani Planum.
There are three principal lines of evidence from which we can infer the timing of the origin of life on Earth: stromatolites, microfossils, and carbon isotope data. All indicate that life emerged earlier than ∼3500 million years ago, but the details and exact timing of life's beginnings remain unknown.
Raman spectroscopy was used to study the liquid-solid water phase transition. Special attention was devoted to the OH-stretching band of the Raman spectrum, which shows monotonous changes in the temperature range between 10 and -15°C. The interpretation of this spectral change, as well as a careful analysis of its integrated scattered intensity, led to a spectral marker that allows the determination of the water phase (liquid or solid), and the efficient identification of the liquid-solid phase transition itself.
Inorganic acids or their alkali-metal or alkaline-earth salts are rather insoluble in ice. Ammonium ion, however, enhances the uptake of a variety of anions into the ice matrix. In the specific case of the fluoride this has been known for almost 50 years and attributed principally to isomorphism between the NH4F and ice crystal lattices. We report here that ammonium also enhances the solubility in ice of anions that do not fit easily into the ice structure. With the species pair HCl/NH4Cl we document specific effects of ammonium on anion uptake, static conductivity, and dielectric conductivity in ice. Other ion species for which comparable results have been obtained are mentioned. Possible implications for atmospheric processes are briefly discussed.
Time-resolved Raman spectroscopy is used to study vibrational energy redistribution after CH-stretch excitation, of glycine zwitterion in aqueous solution. Anti-Stokes Raman monitors the glycine vibrations and Stokes Raman monitors heating of the surrounding water, which acts as a molecular thermometer. A three-step mechanism is proposed for vibrational cooling (VC) that includes 0.8 ps decay of the parent CH-stretch, 1.0 ps relaxation of the midrange vibrations and 1.2 ps relaxation of the lower-energy vibrations. The overall VC process observed by the molecular thermometer is represented by a 1.8 ps time constant. Ó 2007 Elsevier B.V. All rights reserved.
The infrared, Raman and electronic spectra of alanine molecule have been studied in solid as well as in aqueous solution. The vibrational frequencies for the fundamental modes and the energies of low lying electronic states of alanine in neutral and its zwitterionic form have been calculated using AM1, RHF and DFT method with different basis sets. RHF/6-31G, DFT/6-31G, 6-31+G* and 6-311++G** calculations for vibrational frequencies of both l and d-alanine and zwitterionic alanine(zala) have been performed in both gas phase and in aqueous solution. It is concluded that while there is no significant difference between the corresponding frequencies of l- and d-alanine in gas phase but frequencies are changed for zala and alanine in water. A solvation model(PCM) for neutral alanine and zala at DFT/6-31+G* and 6-311++G** level has also been performed. Gas phase and solvation (PCM) model calculations for alanine and zala reveal that neutral alanine is more stable in gas phase while the reverse is true in aqueous medium. A comparison between the experimentally observed IR spectra of alanine in solid and water solution does not show much variation in corresponding frequencies but theoretically some changes are predicted. The rotational constants and dipole moments have also been calculated.
Results of extensive molecular dynamics simulations of freezing of neat water and aqueous sodium chloride solutions are reported. The process of water freezing in contact with an ice patch is analyzed at a molecular level and a robust simulation protocol within the employed force field is established. Upon addition of a small amount of NaCl brine rejection from the freezing salt solution is observed and the anti-freeze effect of the added salt is described. (c) 2006 Elsevier B.V. All rights reserved.
Abstract— A significant fraction of the Earth's prebiotic volatile inventory may have been delivered by asteroidal and cometary impacts during the period of heavy bombardment. The realization that comets are particularly rich in organic material seemed to strengthen this suggestion. Previous modeling studies, however, indicated that most organics would be entirely destroyed in large comet and asteroid impacts. The availability of new kinetic parameters for the thermal degradation of amino acids in the solid phase made it possible to readdress this question.
We present the results of new high-resolution hydrocode simulations of asteroid and comet impact coupled with recent experimental data for amino acid pyrolysis in the solid phase. Differences due to impact velocity as well as projectile material have been investigated. Effects of angle of impacts were also addressed. The results suggest that some amino acids would survive the shock heating of large (kilometer-radius) cometary impacts. At the time of the origins of life on Earth, the steady-state oceanic concentration of certain amino acids (like aspartic and glutamic acid) delivered by comets could have equaled or substantially exceeded concentrations due to Miller-Urey synthesis in a CO2-rich atmosphere. Furthermore, in the unlikely case of a grazing impact (impact angle ∼5° from the horizontal), an amount of some amino acids comparable to that due to the background steady-state production or delivery would be delivered to the early Earth.
The assumptions of standard solar evolution theory are mentioned briefly, and the principle conclusions drawn from them are described. The result is a rationalization of the present luminosity and radius of the Sun. Because there is some uncertainty about the interior composition of the Sun, a range of models is apparently acceptable.
To decide which model is the most accurate, other more sensitive comparisons with observations must be made. Recent measurements of frequencies of dynamical oscillations are particularly valuable in this respect. The most accurate observations are of the five-minute oscillations, which suggest that the solar composition is not atypical of other stars of the same age as the Sun.
The theory predicts that the solar luminosity has risen steadily from about 70% of its current value during the last 4.7 x 109yr. Superposed on this there might have been variations on shorter timescales. Variations lasting about 107yr and occurring at intervals of 108yr have been suggested as being the cause of terrestrial ice ages. Moreover, there may be other variations, associated with instabilities arising from the coupling between the convection zone and the radiative interior, that occur on a timescale of 105yr and which also have climatic consequences. These issues are quite uncertain.
We do know that the Sun varies magnetically with a period of about 22 yr, and that this oscillation is modulated irregularly on a timescale of centuries. This appears to be a phenomenon associated with the convection zone and its immediate neighbourhood, though control from a more deeply-seated mechanism is not out of the question. There is a small luminosity variation associated with this cycle, and the way by which this might come about is discussed in terms of certain theories of the solar dynamo.
Finally, there must be small surface flux variations associated with the dynamical oscillations mentioned above. Though the total luminosity variations are extremely small, the flux in any specific direction, and in particular that of the earth, may be measurable.
In laboratory experiments the interactions of ammonia with ice crystals were studied within the temperature range between
0 and −20°C. In a first series of experiments dendritic ice crystals were grown from water vapor in presence of ammonia gas
in various concentrations between 4 and 400ppbv. In a second series of experiments pure ice crystals were exposed to a humidified
ammonia–air mixture inside a horizontal flow tube. The influence of temperature, ammonia gas concentration (0.6, 1.5, and
10ppmv), exposure time, and the presence of impurities such as sulfate on the ammonia uptake by the ice surface was investigated
by determining the ammonium content in the melt water of the ice crystals by ion chromatography. During the growth of ice
crystals significant amounts of ammonia (around 200μg/l) were taken up even at small gas concentrations. In contrast, even
at high gas concentrations the uptake of ammonia by non-growing ice crystals was lower by approximately one order of magnitude.
The presence of sulfate on the ice surface affected an enhanced uptake of ammonia by a factor of 5–10. A model is presented
which describes the uptake of ammonia by ice considering the chemical processes occurring in the ice surface layer and simultaneous
diffusion of ammonia into bulk ice. Even the increased uptake of ammonia by growing ice is rather small compared to the uptake
by water droplets; thus, the major process for scavenging of ammonia from the atmosphere via the ice phase might not be the
direct uptake by ice crystals but the riming involving super-cooled droplets containing ammonia.
A crystalline ice matrix at subzero temperatures can maintain a liquid phase where organic solutes and salts concentrate to form eutectic solutions. This concentration effect converts the confined reactant solutions in the ice matrix, sometimes making condensation and polymerisation reactions occur more favourably. These reactions occur at significantly high rates from a prebiotic chemistry standpoint, and the labile products can be protected from degradation. The experimental study of the synthesis of nitrogen heterocycles at the ice-water system showed the efficiency of this scenario and could explain the origin of nucleobases in the inner Solar System bodies, including meteorites and extra-terrestrial ices, and on the early Earth. The same conditions can also favour the condensation of monomers to form ribonucleic acid and peptides. Together with the synthesis of these monomers, the ice world (i.e., the chemical evolution in the range between the freezing point of water and the limit of stability of liquid brines, 273 to 210 K) is an under-explored experimental model in prebiotic chemistry.
Scavenging of SO2 and NH3 during ice growth by deposition of water vapour by diffusion was studied in a diffusion chamber at T=−6°C and −15°C. At both temperatures, we observed within the ice an increase of sulphur compounds, expressed as S(VI), for SO2 gas concentrations up to about 3 ppmv. At higher concentrations, saturation was reached in the ice phase. Addition of O3 to the flowing air produced an increase of S(VI) within the ice, at lower SO2 concentrations only. In experiments with NH3, we obtained at T=−15°C nitrogen compound concentrations, expressed as NH4+, regardless of the NH3 concentration in the gas phase in the range of concentrations tested, while at T=−6°C, NH4+ increased with increasing NH3. Concentrations of NH4+ and SO42− turned out to be higher at T=−6°C, compared to −15°C. By considering mixed runs at T=−15°C and −6°C, we observed an increase in both NH4+ and SO42− in the ice phase, compared to experiments at the same temperature, but with separate gases.
The results of our new and earlier laboratory studies on the uptake of gases by ice crystals are summarized in terms of (1) the equilibrium phase diagram for a system gas/H2O, (2) the effect of these gases on the evaporation rate of ice crystals, and (3) in terms of the uptake of the gases by water drops. It is shown that the intrinsic quasi-liquid layer significantly affects the uptake of a gas by an ice surface in that, depending on the gas phase concentration, the layer thickness may be considerably increased by depressing the equilibrium freezing point causing additional surface melting. It is further shown that the evaporation rate of ice particles previously exposed to a gas may become significantly reduced in comparison to that of pure ice particles. Finally, it is shown that under atmospheric conditions the direct gas uptake by ice crystals may be neglected in comparison to the uptake of gases by water drops. In atmospheric clouds gases are therefore most likely taken up by ice crystals via the process of riming.
Our understanding of the evolution of organic molecules, and their voyage from molecular clouds to the early solar system and Earth, has changed dramatically. Incorporating recent observational results from the ground and space, as well as laboratory simulation experiments and new methods for theoretical modeling, this review recapitulates the inventory and distribution of organic molecules in different environments. The evolution, survival, transport, and transformation of organics is monitored, from molecular clouds and the diffuse interstellar medium to their incorporation into solar system material such as comets and meteorites. We constrain gas phase and grain surface formation pathways to organic molecules in dense interstellar clouds, using recent observations with the Infrared Space Observatory (ISO) and ground-based radiotelescopes. The main spectroscopic evidence for carbonaceous compounds in the diffuse interstellar medium is discussed (UV bump at 2200 Å, diffuse interstellar bands, extended red emission, and infrared absorption and emission bands). We critically review the signatures and unsolved problemsrelated to the main organic components suggested to be present in the diffuse gas, such as polycyclic aromatic hydrocarbons (PAHs), fullerenes, diamonds, and carbonaceous solids. We also briefly discuss the circumstellar formation of organics around late-typestars. In the solar system, space missions to comet Halley and observations of the bright comets Hyakutake and Hale-Bopp have recently allowed a reexamination of the organic chemistry of dust and volatiles in long-period comets. We review the advances in this area and also discuss progress being made in elucidating the complex organic inventory of carbonaceous meteorites. The knowledge of organic chemistry in molecular clouds, comets, and meteorites and their common link provides constraints for the processes that lead to the origin, evolution, and distribution of life in the Galaxy.
Amino acids are the basic "building blocks" that combine to form proteins and play an important physiological role in all life-forms. Amino acids can be used as models for the examination of the importance of intermolecular bonding in life processes. Raman spectra serve to obtain information regarding molecular conformation, giving valuable insights into the topology of more complex molecules (peptides and proteins). In this paper, amino acids and their aqueous solution have been studied by Raman spectroscopy. Comparisons of certain values for these frequencies in amino acids and their aqueous solutions are given. Spectra of solids when compared to those of the solute in solution are invariably much more complex and almost always sharper. We present a collection of Raman spectra of 18 kinds of amino acids (L-alanine, L-arginine, L-aspartic acid, cystine, L-glutamic acid, L-glycine, L-histidine, L-isoluecine, L-leucine, L-lysine, L-phenylalanine, L-methionone, L-proline, L-serine, L-threonine, L-tryptophan, L-tyrosine, L-valine) and their aqueous solutions that can serve as references for the interpretation of Raman spectra of proteins and biological materials.
We present a theoretical study of infrared and Raman line shapes of polycrystalline and single crystal ice Ih, for both water and heavy water, at 1, 125, and 245 K. Our calculations involve a mixed quantum/classical approach, a new water simulation model with explicit three-body interactions, transition frequency and dipole maps, and intramolecular and intermolecular vibrational coupling maps. Our theoretical spectra are in reasonable agreement with experimental spectra (available only near the two higher temperatures). We trace the origins of the different spectral peaks to weak and strong intermolecular couplings. We also discuss the delocalization of the vibrational eigenstates in terms of the competing effects of disorder and coupling.
To provide improved understanding of guest-host interactions in clathrate hydrates, we present some correlations between guest chemical structures and observations on the corresponding hydrate properties. From these correlations it is clear that directional interactions such as hydrogen bonding between guest and host are likely, although these have been ignored to greater or lesser degrees because there has been no direct structural evidence for such interactions. For the first time, single-crystal X-ray crystallography has been used to detect guest-host hydrogen bonding in structure II (sII) and structure H (sH) clathrate hydrates. The clathrates studied are the tert-butylamine (tBA) sII clathrate with H(2)S/Xe help gases and the pinacolone + H(2)S binary sH clathrate. X-ray structural analysis shows that the tBA nitrogen atom lies at a distance of 2.64 A from the closest clathrate hydrate water oxygen atom, whereas the pinacolone oxygen atom is determined to lie at a distance of 2.96 A from the closest water oxygen atom. These distances are compatible with guest-water hydrogen bonding. Results of molecular dynamics simulations on these systems are consistent with the X-ray crystallographic observations. The tBA guest shows long-lived guest-host hydrogen bonding with the nitrogen atom tethered to a water HO group that rotates towards the cage center to face the guest nitrogen atom. Pinacolone forms thermally activated guest-host hydrogen bonds with the lattice water molecules; these have been studied for temperatures in the range of 100-250 K. Guest-host hydrogen bonding leads to the formation of Bjerrum L-defects in the clathrate water lattice between two adjacent water molecules, and these are implicated in the stabilities of the hydrate lattices, the water dynamics, and the dielectric properties. The reported stable hydrogen-bonded guest-host structures also tend to blur the longstanding distinction between true clathrates and semiclathrates.
Clathrate hydrates (CHs) are inclusion compounds in which "tetrahedrally" bonded H(2)O forms a crystalline host lattice composed of a periodic array of cages. The structure is stabilized by guest particles which occupy the cages and interact with cage walls via van der Waals interactions. A host of atoms or small molecules can act as guests; here the focus is on guests that are capable of strong to intermediate H-bonding to water (small ethers, H(2)S, etc.) but nevertheless "choose" this hydrate crystal form in which H-bonding is absent from the equilibrium crystal structure. These CHs can form by exposure of ice to guest molecules at temperatures as low as 100-150 K, at the (low) guest saturation pressure. This is in contrast to the "normal" CHs whose formation typically requires temperatures well above 200 K and at least moderate pressures. The experimental part of this study addresses formation kinetics of CHs with H-bonding guests, as well as transformation kinetics between different CH forms, studied by CH infrared spectroscopy. The accompanying computational study suggests that the unique properties of this family of CHs are due to exceptional richness of the host lattice in point defects, caused by defect stabilization by H-bonding of water to the guests.
The rate of polymerization of hydrogen cyanide to aminomalononitrile and the tetramer, diaminomalonodinitrile, is quadratic in the total cyanide concentration. Since the reactions form part of a plausible prebiotic purine synthesis and since they compete with hydrolysis, concentration of cyanide may have been important. This may be achieved usefully by cooling to separate out ice.