Gas chromatography for in situ analysis of a cometary nucleus V. Study of capillary columns' robustness submitted to long-term reduced environmental pressure conditions.

With the European Space Agency's Rosetta space mission to comet 67P/Churyumov-Gerasimenko, a gas chromatograph, part of the COmetary Sampling And Composition (COSAC) experiment, travelled for about 10 years in the interplanetary medium before operating at the surface of the cometary nucleus in November 2014. During its journey in space, the instrument was exposed to the constraining conditions of the interplanetary medium, including reduced environmental pressures. In order to estimate the potential influence of this severe condition on the chromatographic capillary columns, their stationary phase and the subsequent separation capability, a set of flight spare columns were kept under reduced environmental pressure in the laboratory for the same duration as the probe sent to the comet. The columns' analytical performances were evaluated recently and compared to the original ones obtained just before the launch of the Rosetta probe. The results presented here show that the chromatographic performances of the spare chromatographic columns were not altered in time. From this result, it can be expected that the flight instrument will perform nominally for the analysis of the first cometary nucleus sample to be collected ever, and that the preparation of the interpretation of the data to be taken at the cometary surface nucleus can be done through calibration of these spare columns, and other spare components of the instrument.

Anisotropy spectra for enantiomeric differentiation of biomolecular building blocks.

All biopolymers are composed of homochiral building blocks, and both D-sugars and L-amino acids uniquely constitute life on Earth. These monomers were originally enantiomerically differentiated under prebiotic conditions. Particular progress has recently been made in support of the photochemical model for this differentiation: the interaction of circularly polarized light with racemic molecules is currently thought to have been the original source for life's biological homochirality. The differential asymmetric photoreactivity of particular small molecules can be characterized by both circular dichroism and anisotropy spectroscopy. Anisotropy spectroscopy, a novel derivative of circular dichroism spectroscopy, records the anisotropy factor g = Δε/ε as a function of the wavelength. Anisotropy spectroscopy promisingly affords the wavelength-dependent determination of the enantiomeric excess (ee) inducible into chiral organic molecules by photochemical irradiation with circularly polarized light. Anisotropy spectra of small molecules therefore provide unique means for characterizing the different photochemical behaviors between enantiomers upon exposure to various wavelengths of circularly polarized light. This chapter will: (1) present the theory and configuration of anisotropy spectroscopy; (2) explain experimentally recorded anisotropy spectra of selected chiral biomolecules such as amino acids; and (3) discuss the relevance of these spectra for the investigation of the origin of the molecular homochirality observed in living organisms. This review describes a new chiroptical technique that is of significance for advances in asymmetric photochemistry and that is also highly relevant for the European Space Agency Rosetta Mission, which will determine enantiomeric excesses (ees) in chiral organic molecules in cometary ices when it lands on Comet 67P/Churyumov-Gerasimenko in November 2014.

Gas chromatography for in situ analysis of a cometary nucleus. IV. Study of capillary column robustness for space application.

As part of the development of the European Space Agency Rosetta space mission to investigate a cometary nucleus, the selection of columns dedicated to the gas chromatographic subsystem of the Cometary Sampling and Composition (COSAC) experiment was achieved. Once the space probe launched, these columns will be exposed to the harsh environmental constraints of space missions: vibrations, radiation (by photons or energetic particles), space vacuum, and large temperature range. In order to test the resistance of the flight columns and their stationary phases, the columns were exposed to these rough conditions reproduced in the laboratory. The comparison of the analytical performances of the columns, evaluated prior and after the environmental tests, demonstrated that all the columns withstand space constraints, and that their analytical properties were preserved. Therefore, all the selected capillary columns, even having porous layer or chiral stationary phases, were qualified for space exploration.

Amino acids from ultraviolet irradiation of interstellar ice analogues.

Amino acids are the essential molecular components of living organisms on Earth, but the proposed mechanisms for their spontaneous generation have been unable to account for their presence in Earth's early history. The delivery of extraterrestrial organic compounds has been proposed as an alternative to generation on Earth, and some amino acids have been found in several meteorites. Here we report the detection of amino acids in the room-temperature residue of an interstellar ice analogue that was ultraviolet-irradiated in a high vacuum at 12 K. We identified 16 amino acids; the chiral ones showed enantiomeric separation. Some of the identified amino acids are also found in meteorites. Our results demonstrate that the spontaneous generation of amino acids in the interstellar medium is possible, supporting the suggestion that prebiotic molecules could have been delivered to the early Earth by cometary dust, meteorites or interplanetary dust particles.

Conception of the 'Chirality-Experiment' on ESA's mission ROSETTA to comet P46/Wirtanen.

In the last years extraterrestrial scenarios for the origin of homochirality in biological structures received considerable attention in the topical literature: Rubenstein and Bonner postulated a rapidly rotating neutron star emitting circularly polarised synchrotron radiation responsible for the first asymmetric synthesis; the group of Bailey published the observation of circular polarisation caused by Mie scattering from aligned dust grains in the Orion OMC-1 star-formation region that might provide an enantioselective effect on prochiral or racemic organic molecules. Rikken and Raupach observed a magnetochiral effect and considered extraterrestrial magnetic fields of sufficient strengths to introduce biomoleculars parity violation. With the aim to investigate these hypotheses among other theories describing the origin of biological asymmetry, our laboratory participates in the conception and development of ROSETTA's COSAC Experiment, that is designed to identify organic molecules in the cometary matter in situ. Within COSAC's 'Chirality Module' enantiomers will be separated gas chromatographically with the help of capillary columns coated with chirally active liquid films. This technique will allow the separation of specific chiral organic compounds out of the analysed cometary matter into their enantiomeric constituents. Both thermo conductivity and mass spectrometric detectors will be used to determine each enantiomer's amount and therefore the corresponding enantiomeric excesses. As a consequence of COSAC's 'Chirality-Experiment' far-reaching results are expected to investigate the various hypotheses about the first asymmetric synthesis.

Simulated cometary matter as a test for enantiomer separating chromatography for use on comet 46P/Wirtanen.

The Cometary Sampling and Composition Experiment on board of European Space Agency's cornerstone mission ROSETTA is designed to identify organic molecules in cometary matter in situ by a combined pyrolysis gas chromatographic and mass spectrometric technique. Its capillary columns coated with chiral stationary phases received considerable attention, because they are designed for separations of non-complex enantiomers to allow the determination of enantiomeric ratios of cometary chiral organic compounds and consequently to provide information about the origin of molecular parity violation in biomolecules. To get gas chromatographic access to organic compounds on the comet, where macromolecules and complex organic polymers of low volatility are expected to make up the main organic ingredients, the combination of two injection techniques will be applied. The pyrolysis technique performed by heating cometary samples stepwise to defined temperatures in specific ovens resulting in thermochemolysis reactions of polymers and a chemical derivatization technique, in which the reagent dimethylformamide dimethylacetal assists pyrolysis derivatization reactions in producing methyl esters of polar monomers. The combination of the reagent assisted pyrolysis gas chromatographic technique with enantiomer separating chromatography was tested with laboratory-produced simulated cometary matter.

Stereochemical investigation of cometary matter onboard the Rosetta Lander.

At present the European Space Agency is working on one of its Cornerstone Missions, named "Rosetta", to be launched in January 2003 for a visit to comet 46P/Wirtanen2 in 2011. The Rosetta spacecraft will carry a small subsatellite, the Rosetta Lander3 (RoLand), to be detached from the orbiter and land on the surface of the comet's nucleus. One of our main scientific interests is to find out whether chiral organic compounds in cometary matter brought to the Earth by cometary impacts might have had, due to corresponding enantiomeric excesses, a seed function in determining the handedness which is characteristic of homochiral compounds employed by life on Earth. For this reason we have developed an Experiment for the ROSETTA mission, named Cometary Sampling and Composition Experiment (COSAC).

Enantiomer separation of hydrocarbons in preparation for ROSETTA's "chirality-experiment".

Until now the favored method for separating racemic pairs of underivatized alcohols, diols, and phenylsubstituted amines has been gas chromatography on cyclodextrin phases. However, certain enantiomers of saturated chiral hydrocarbons could not be resolved in this way because they lack the functional groups necessary to undergo "intensive" diastereomeric interactions with the cyclodextrins. The present study describes a gas-chromatographic technique for resolution of saturated aliphatic hydrocarbons into their enantiomers and presents a brief discussion of the possible applications. The (enantiomer) separations were performed in preparation for the Cometary Sampling and Composition Experiment on board the cometary lander RoLand, part of ESA's cornerstone mission ROSETTA. This experiment has been designed to investigate the hypotheses that biomolecular asymmetry has an interstellar origin and to separate and identify a wide range of organic enantiomers in situ on the surface of a comet's nucleus.