Electron-induced hydroamination of ethane as compared to ethene: implications for the reaction mechanism.

The properties of carbonaceous materials with respect to various applications are enhanced by incorporation of nitrogen-containing moieties like, for instance, amino groups. Therefore, processes that allow the introduction of such functional groups into hydrocarbon compounds are of utmost interest. Previous studies have demonstrated that hydroamination reactions which couple amines to unsaturated sites within hydrocarbon molecules do not only proceed in the presence of suitably tailored catalysts but can also be induced and controlled by electron irradiation. However, studies on electron-induced hydroaminations so far were guided by the hypothesis that unsaturated hydrocarbons are required for the reaction while the reaction would be much less efficient in the case of saturated hydrocarbons. The present work evaluates the validity of this hypothesis by post-irradiation thermal desorption experiments that monitor the electron energy-dependent yield of ethylamine after electron irradiation of mixed C2H4:NH3 and C2H6:NH3 ices with the same composition and thickness. The results reveal that, in contrast to the initial assumption, ethylamine is formed with similar efficiency in both mixed ices. From the dependence of the product yields on the electron energy, we conclude that the reaction in both cases is predominantly driven by electron ionization of NH3. Ethylamine is formed via alternative reaction mechanisms by which the resulting NH2˙ radicals add to C2H4 and C2H6, respectively. The similar efficiency of amine formation in unsaturated and saturated hydrocarbons demonstrates that electron irradiation in the presence of NH3 is a more versatile tool for introducing nitrogen into carbonaceous materials than previously anticipated.

COSAC's Only Gas Chromatogram Taken on Comet 67P/Churyumov-Gerasimenko.

The Philae lander of the Rosetta space mission made a non-nominal landing on comet 67P/Churyumov-Gerasimenko on November 12, 2014. Shortly after, using the limited power available from Philae's batteries, the COSAC instrument performed a single 18-minutes gas chromatogram, which has remained unpublished until now due to the lack of identifiable elution. This work shows that, despite the unsuccessful drilling of the comet and deposition of surface material in the SD2 ovens, the measurements from the COSAC instrument were executed nominally. We describe an automated search for extremely small deviations from noise and discuss the possibility of a signal from ethylene glycol at m/z 31. Arguments for and against this detection are listed, but the results remain inconclusive. Still, the successful operations of an analytical chemistry laboratory on a cometary nucleus gives great hope for the future of space exploration.

ESA's Cometary Mission Rosetta-Re-Characterization of the COSAC Mass Spectrometry Results.

The most pristine material of the Solar System is assumed to be preserved in comets in the form of dust and ice as refractory matter. ESA's mission Rosetta and its lander Philae had been developed to investigate the nucleus of comet 67P/Churyumov-Gerasimenko in situ. Twenty-five minutes after the initial touchdown of Philae on the surface of comet 67P in November 2014, a mass spectrum was recorded by the time-of-flight mass spectrometer COSAC onboard Philae. The new characterization of this mass spectrum through non-negative least squares fitting and Monte Carlo simulations reveals the chemical composition of comet 67P. A suite of 12 organic molecules, 9 of which also found in the original analysis of this data, exhibit high statistical probability to be present in the grains sampled from the cometary nucleus. These volatile molecules are among the most abundant in the comet's chemical composition and represent an inventory of the first raw materials present in the early Solar System.

COMETARY SCIENCE. Organic compounds on comet 67P/Churyumov-Gerasimenko revealed by COSAC mass spectrometry.

Comets harbor the most pristine material in our solar system in the form of ice, dust, silicates, and refractory organic material with some interstellar heritage. The evolved gas analyzer Cometary Sampling and Composition (COSAC) experiment aboard Rosetta's Philae lander was designed for in situ analysis of organic molecules on comet 67P/Churyumov-Gerasimenko. Twenty-five minutes after Philae's initial comet touchdown, the COSAC mass spectrometer took a spectrum in sniffing mode, which displayed a suite of 16 organic compounds, including many nitrogen-bearing species but no sulfur-bearing species, and four compounds­methyl isocyanate, acetone, propionaldehyde, and acetamide­that had not previously been reported in comets.

Electron-induced hydration of an alkene: alternative reaction pathways.

Electron-induced reactions in condensed mixtures of ethylene and water lead to the synthesis of ethanol, as shown by post-irradiation thermal desorption spectrometry (TDS). Interestingly, this synthesis is not only induced by soft electron impact ionization similar to a previously observed electron-induced hydroamination but also, at low electron energy, by electron attachment to ethylene and a subsequent acid/base reaction with water.

Understanding photochirogenesis: solvent effects on circular dichroism and anisotropy spectroscopy.

The basic units that constitute essential biopolymers (proteins and nucleic acids) are enantiomerically biased. Proteins are constructed from L-amino acids and nucleic acids possess a backbone composed exclusively of D-sugars. Photochirogenesis has been postulated to be the source of this homochirality of biomolecules: Asymmetric photochemical reactions were catalyzed by circularly polarized light (cpl) in interstellar environments and generated the first chiral prebiotic precursors. Enantiomers absorb cpl differently and this difference can dictate the kinetics of asymmetric photochemical reactions. These differences in absorption can be studied using circular dichroism (CD) and anisotropy spectroscopy. Rather than measuring the CD spectrum alone, the anisotropy factor g is recorded (CD divided by absorption). This factor g is directly related to the maximum achievable enantiomeric excess. We now report on the substantial influence of solvent and molecular surroundings on CD and anisotropy spectroscopy. This shows for the first time that CD and anisotropy signals depend just as much on the molecular surroundings of a molecule as on the nature of the molecule itself. CD and g spectra of amino acids in different solvents and in the solid state are presented here and the influence of these different surroundings on the spectra is discussed.

Photochirogenesis: photochemical models on the absolute asymmetric formation of amino acids in interstellar space.

Proteins of all living organisms including plants, animals, and humans are made up of amino acid monomers that show identical stereochemical L-configuration. Hypotheses for the origin of this symmetry breaking in biomolecules include the absolute asymmetric photochemistry model by which interstellar ultraviolet (UV) circularly polarized light (CPL) induces an enantiomeric excess in chiral organic molecules in the interstellar/circumstellar media. This scenario is supported by a) the detection of amino acids in the organic residues of UV-photo-processed interstellar ice analogues, b) the occurrence of L-enantiomer-enriched amino acids in carbonaceous meteorites, and c) the observation of CPL of the same helicity over large distance scales in the massive star-forming region of Orion. These topics are of high importance in topical biophysical research and will be discussed in this review. Further evidence that amino acids and other molecules of prebiotic interest are asymmetrically formed in space comes from studies on the enantioselective photolysis of amino acids by UV-CPL. Also, experiments have been performed on the absolute asymmetric photochemical synthesis of enantiomer-enriched amino acids from mixtures of astrophysically relevant achiral precursor molecules using UV-circularly polarized photons. Both approaches are based on circular dichroic transitions of amino acids that will be highlighted here as well. These results have strong implications on our current understanding of how life's precursor molecules were possibly built and how life selected the left-handed form of proteinogenic amino acids.

Photolysis of rac-leucine with circularly polarized synchrotron radiation.

Amino acids that pass the RNA machinery in living organisms occur in L-configuration. The question on the evolutionary origin of this biomolecular asymmetry remains unanswered to this day. Amino acids were detected in artificially produced interstellar ices, and L-enantiomer-enriched amino acids were identified in CM-type meteorites. This hints at a possible interstellar/circumstellar origin of the amino acids themselves as well as their stereochemical asymmetry. Based upon the current knowledge about the occurrence of circularly-polarized electromagnetic radiation in interstellar environments, we subjected rac-leucine to far-UV circularly-polarized synchrotron radiation. Asymmetric photolysis was followed by an analysis in an enantioselective GC/MS system. Here, we report on an advanced photolysis rate of more than 99% for leucine. The results indicate that high photolysis rates can occur under the chosen conditions, favoring enantioselective photolysis. In 2014, the obtained results will be reexamined by cometary mission Rosetta.

Urea, glycolic acid, and glycerol in an organic residue produced by ultraviolet irradiation of interstellar/pre-cometary ice analogs.

More than 50 stable organic molecules have been detected in the interstellar medium (ISM), from ground-based and onboard-satellite astronomical observations, in the gas and solid phases. Some of these organics may be prebiotic compounds that were delivered to early Earth by comets and meteorites and may have triggered the first chemical reactions involved in the origin of life. Ultraviolet irradiation of ices simulating photoprocesses of cold solid matter in astrophysical environments have shown that photochemistry can lead to the formation of amino acids and related compounds. In this work, we experimentally searched for other organic molecules of prebiotic interest, namely, oxidized acid labile compounds. In a setup that simulates conditions relevant to the ISM and Solar System icy bodies such as comets, a condensed CH(3)OH:NH(3) = 1:1 ice mixture was UV irradiated at approximately 80 K. The molecular constituents of the nonvolatile organic residue that remained at room temperature were separated by capillary gas chromatography and identified by mass spectrometry. Urea, glycolic acid, and glycerol were detected in this residue, as well as hydroxyacetamide, glycerolic acid, and glycerol amide. These organics are interesting target molecules to be searched for in space. Finally, tentative mechanisms of formation for these compounds under interstellar/pre-cometary conditions are proposed.

Chiroptical properties of diamino carboxylic acids.

Diamino carboxylic acids have recently come to the attention of scientists working in the field of early life and its development. These are the monomers of a hypothetic early form of genetic material, the so-called Peptide Nucleic Acid (PNA) (Nielson et al., Proc Natl Acad Sci USA 2000;97:3868-3871). Since all biopolymers rely on a specific handedness of their building blocks, the question of symmetry breaking occurs in diamino acids and PNA in the same way as in amino acids and proteins. One possible mechanism for triggering this, is asymmetric photochemistry in interstellar/circumstellar matter by means of circularly polarized light (Bailey et al., Science 2005;281:672-674; Bailey, Orig Life Evol Biosphere 2001;21:167-183; Buschermöhle, Astrophys J 2005;624:821-826; Meierhenrich, Angew Chem Int Ed Engl 2005;44:5630-5634). Here we have measured the CD-spectra of four chiral diamino carboxylic acids, three of which were found in the Murchison meteorite (Meierhenrich, Proc Natl Acad Sci USA 2004;101:9182-9186). The spectra show a uniform peak at 200 nm. These results and additional quantum mechanical calculations of the involved molecular orbitals support the assumption that the process of symmetry breaking in diamino acids does not depend significantly on the length of the side chain. This means that one process alone could suffice to lead to symmetry breaking in all four measured diamino carboxylic acids and might even to some extent be transferable to monoamino acids, the monomers of proteins.

Identification of diamino acids in the Murchison meteorite.

Amino acids identified in the Murchison chondritic meteorite by molecular and isotopic analysis are thought to have been delivered to the early Earth by asteroids, comets, and interplanetary dust particles where they may have triggered the appearance of life by assisting in the synthesis of proteins via prebiotic polycondensation reactions [Oró, J. (1961) Nature 190, 389-390; Chyba, C. F. & Sagan, C. (1992) Nature 355, 125-132]. We report the identification of diamino acids in the Murchison meteorite by new enantioselective GC-MS analyses. dl-2,3-diaminopropanoic acid, dl-2,4-diaminobutanoic acid, 4,4'-diaminoisopentanoic acid, 3,3'-diaminoisobutanoic acid, and 2,3-diaminobutanoic acid were detected in the parts per billion range after chemical transformation into N,N-diethoxycarbonyl ethyl ester derivatives. The chiral diamino acids show a racemic ratio. Laboratory data indicate that diamino acids support the formation of polypeptide structures under primitive Earth conditions [Brack, A. & Orgel, L. E. (1975) Nature 256, 383-387] and suggest polycondensation reactions of diamino acids into early peptide nucleic acid material as one feasible pathway for the prebiotic evolution of DNA and RNA genomes [Joyce, G. F. (2002) Nature 418, 214-221]. The results obtained in this study favor the assumption that not only amino acids (as the required monomers of proteins) form in interstellar/circumstellar environments, but also the family of diamino monocarboxylic acids, which might have been relevant in prebiotic chemistry.