Infrared Spectral Intensities of Amine Ices, Precursors to Amino Acids.

Here, we address the paucity of infrared (IR) spectral data needed to quantify low-temperature experiments with amine ices, such as the formation of amino acids, by reporting new IR results on solid phases of methylamine (CH3NH2) and ethylamine (CH3CH2NH2), precursors to glycine and alanine, respectively. Mid-IR band strengths and absorption coefficients for CH3NH2 and CH3CH2NH2, in both amorphous and crystalline forms, are presented, along with measurements of a density and refractive index (670 nm) for each. For these same compounds, we also have calculated IR optical constants, and they are being made available in electronic form. Some applications of our new results are described along with proposals for future investigations. Suggestions are made related to the methods employed in such work, and particularly to the application of Beer's Law to the IR study of compounds of astrobiological interest. Comments are also included on the methods used, and the results presented in a recently published work on amino-acid IR intensities.

Radiolytic Destruction of Uracil in Interstellar and Solar System Ices.

Uracil is one of the four RNA nucleobases and a component of meteoritic organics. If delivered to the early Earth, uracil could have been involved in the origins of the first RNA-based life, and so this molecule could be a biomarker on other worlds. Therefore, it is important to understand uracil's survival to ionizing radiation in extraterrestrial environments. Here we present a study of the radiolytic destruction kinetics of uracil and mixtures of uracil diluted in H2O or CO2 ice. All samples were irradiated by protons with an energy of 0.9 MeV, and experiments were performed at 20 and 150 K to determine destruction rate constants at temperatures relevant to interstellar and Solar System environments. We show that uracil is destroyed much faster when H2O ice or CO2 ice is present than when these two ices are absent. Moreover, destruction is faster for CO2-dominated ices than for H2O-dominated ones and, to a lesser extent, at 150 K compared with 20 K. Extrapolation of our laboratory results to astronomical timescales shows that uracil will be preserved in ices with half-lives of up to ∼107 years on cold planetary bodies such as comets or Pluto. An important implication of our results is that for extraterrestrial environments, the application of laboratory data measured for the radiation-induced destruction of pure (neat) uracil samples can greatly underestimate the molecule's rate of destruction and significantly overestimate its lifetime, which can lead to errors of over 1000%.

Laboratory Studies of Astronomical Ices: Reaction Chemistry and Spectroscopy.

ConspectusScientists have had evidence for molecules in both comets and interstellar space since the 19th and early 20th centuries. Since then, extraterrestrial molecules ranging from simple diatomics to C70 to amino acids have been detected and identified through remote spectroscopy, spacecraft, and sample return missions. These achievements have been made through the efforts of astronomers and laboratory chemists collaborating to identify molecules in a myriad of exotic environments. It is now understood that even in the coldest depths of dense molecular clouds there is a wealth of chemistry to explore, much of it driven by exposure to radiation. As molecular clouds condense to protostellar disks and eventually form new planetary systems, chemical processes continue and evolve. An understanding of these processes is paramount for explaining the compositions of different bodies in our Solar System and may provide insight into the origins of life.In this Account, we describe the work of the Cosmic Ice Laboratory at NASA's Goddard Space Flight Center to characterize the composition of and understand the chemistry occurring in icy bodies in the Solar System and beyond. Our work has touched on a wide range of extraterrestrial environments, including icy interstellar grains, small bodies such as comets and asteroids, and planets and moons. We are especially interested in the chemical and physical changes that occur in ices as a result of thermal changes or exposure to radiation. To this end, we conduct experiments designed to simulate cold extraterrestrial environments and measure physical properties of single- and multicomponent ices. We expose ices to radiation (e.g., MeV protons or keV-MeV electrons) or high-energy (e.g., UV) photons to initiate physical and chemical changes. We conduct experiments using cryo-vacuum chambers equipped with analytical tools and radiation sources to make most of our measurements, including the collection of all spectroscopic data, in situ. When possible and appropriate, we also collect reaction products for further ex situ analysis. The work of the Cosmic Ice Lab provides critical data to astrochemists and others seeking to understand observations, make predictions, and plan future space missions.

The Radiation Stability of Thymine in Solid H2O.

Nucleobases are of significant importance to all known organisms, may be an important building block of life, and could be important biosignatures of current or past life. Given their potential significance to the field of astrobiology, it is important to understand the survival of these molecules when subjected to ionizing radiation as is present in a range of extraterrestrial environments. In this work, we present data on the kinetics of the radiolytic destruction of pure thymine and water + thymine ice mixtures at temperatures from 13 to 150 K. Rate constants were measured using in situ infrared spectroscopy, and radiolytic half-lives for thymine were computed for different planetary and interstellar environments. Our results demonstrate that the survival of thymine decreases as the dilution of thymine in water increases. Additionally, we find that thymine survival increases with ice temperature and that this decrease may be related to structure of the ice matrix.

Testing Densities and Refractive Indices of Extraterrestrial Ice Components Using Molecular Structures - Organic Compounds and Molar Refractions.

The use of infrared spectra to determine molecular abundances of icy astronomical objects and to study their chemistry requires laboratory measurements of reference spectra and related quantities, such as the index of refraction (n) and density (ρ) of candidate ices. Here we present new n and ρ measurements on ices involving over thirty C-, H-, and O-containing compounds, both acyclic and cyclic, representing seven chemical families. We examine the results in a way that is rare in the astrochemical literature, namely one in which data from an ice formed from molecules of a particular chemical family are compared to measurements on another member of the same family, such as of a homologous series or a pair of isomers. Apart from the intrinsic usefulness of the n and ρ data, a structure-based comparison can help establish trends and identify possibly spurious results. As liquid-phase data sometimes are used in low-temperature astrochemical work in the absence of solid-phase measurements, we compare our new ice results to those for the corresponding room-temperature liquids. We emphasize the use of our n and ρ data to compute the molar refraction (R M ) for each of our ices, and how the resulting R M values compare to those expected from molecular structures. The use of calculated RM values and measured n values to calculate ice densities, in the absence of direct measurements, also is addressed.

Millimeter/Submillimeter Spectroscopic Detection of Desorbed Ices: A New Technique in Laboratory Astrochemistry.

A new laboratory technique has been developed that utilizes gas-phase, direct-absorption millimeter and submillimeter spectroscopy to detect and identify desorbed species from interstellar and cometary ice analogues. Rotational spectroscopy is a powerful structure-specific technique for detecting isomers and other species possessing the same mass that are indistinguishable with mass spectrometry. Furthermore, the resultant laboratory spectra are directly comparable to observational data from far-infrared and millimeter telescopes. Here, we present the proof-of-concept measurements of the detection of thermally desorbed H2O, D2O, and CH3OH originating in a solid film created at low temperature (∼12 K). The surface binding energy of H2O is reported and compared to results from traditional techniques, including mass spectrometry and quartz-crystal microbalance measurements of mass loss. Lastly, we demonstrate that this technique can be used to derive thermodynamic values including the sublimation enthalpy and entropy of H2O.

IR spectra and properties of solid acetone, an interstellar and cometary molecule.

Mid-infrared spectra of amorphous and crystalline acetone are presented along with measurements of the refractive index and density for both forms of the compound. Infrared band strengths are reported for the first time for amorphous and crystalline acetone, along with IR optical constants. Vapor pressures and a sublimation enthalpy for crystalline acetone also are reported. Positions of 13C-labeled acetone are measured. Band strengths are compared to gas-phase values and to the results of a density-functional calculation. A 73% error in previous work is identified and corrected.

Metabolic precursors in astrophysical ice analogs: implications for meteorites and comets.

We report the synthesis of complex organic compounds including nicotinic and quinolinic acid, two members involved in the nicotinamide adenine dinucleotide (NAD) biosynthetic pathway, in irradiated astrophysical ice analogs. If delivered to Earth by meteorites and comets, these compounds may have contributed to the origin and early evolution of life.

Glycine's radiolytic destruction in ices: first in situ laboratory measurements for Mars.

We report new laboratory studies of the radiation-induced destruction of glycine-containing ices for a range of temperatures and compositions that allow extrapolation to martian conditions. In situ infrared spectroscopy was used to study glycine decay rates as a function of temperature (from 15 to 280 K) and initial glycine concentrations in six mixtures whose compositions ranged from dry glycine to H2O+glycine (300:1). Results are presented in several systems of units, with cautions concerning their use. The half-life of glycine under the surface of Mars is estimated as an extrapolation of this data set to martian conditions, and trends in decay rates are described as are applications to Mars' near-surface chemistry.