Cornelia Meinert

Non-racemic Amino Acid Production by Ultraviolet Irradiation of Achiral Interstellar Ice Analogs with Circularly Polarized Light

The delivery of organic matter to the primitive Earth via comets and meteorites has long been hypothesized to be an important source for prebiotic compounds such as amino acids or their chemical precursors that contributed to the development of prebiotic chemistry leading, on Earth, to the emergence of life. Photochemistry of inter/circumstellar ices around protostellar objects is a potential process leading to complex organic species, although difficult to establish from limited infrared observations only. Here we report the first abiotic cosmic ice simulation experiments that produce species with enantiomeric excesses (e.e.s). Circularly polarized ultraviolet light (UV-CPL) from a synchrotron source induces asymmetric photochemistry on initially achiral inter/circumstellar ice analogs. Enantioselective multidimensional gas chromatography measurements show significant e.e.s of up to 1.34% for (13C)-alanine, for which the signs and absolute values are related to the helicity and number of CPL photons per deposited molecule. This result, directly comparable with some L excesses measured in meteorites, supports a scenario in which exogenous delivery of organics displaying a slight L excess, produced in an extraterrestrial environment by an asymmetric astrophysical process, is at the origin of biomolecular asymmetry on Earth. As a consequence, a fraction of the meteoritic organic material consisting of non-racemic compounds may well have been formed outside the solar system. Finally, following this hypothesis, we support the idea that the protosolar nebula has indeed been formed in a region of massive star formation, regions where UV-CPL of the same helicity is actually observed over large spatial areas.

Ribose and related sugars from ultraviolet irradiation of interstellar ice analogs

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 Prebiotic sugars, including ribose, can be made by irradiating simple ices under interstellar conditions. Ribose is the central molecular subunit in RNA, but the prebiotic origin of ribose remains unknown. We observed the formation of substantial quantities of ribose and a diversity of structurally related sugar molecules such as arabinose, xylose, and lyxose in the room-temperature organic residues of photo-processed interstellar ice analogs initially composed of H2O, CH3OH, and NH3. Our results suggest that the generation of numerous sugar molecules, including the aldopentose ribose, may be possible from photochemical and thermal treatment of cosmic ices in the late stages of the solar nebula. Our detection of ribose provides plausible insights into the chemical processes that could lead to formation of biologically relevant molecules in suitable planetary environments.

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 lifes precursor molecules were possibly built and how life selected the left-handed form of proteinogenic amino acids.

A New Dimension in Separation Science: Comprehensive Two‐Dimensional Gas Chromatography

The introduction and development of comprehensive two-dimensional gas chromatography offers greatly enhanced resolution and identification of organic analytes in complex mixtures compared to any one-dimensional separation technique. Initially promoted by the need to resolve highly complex petroleum samples, the techniques enormous separation power and enhanced ability to gather information has rapidly attracted the attention of analysts from all scientific fields. In this Minireview, we highlight the fundamental theory, recent advances, and future trends in the instrumentation and application of comprehensive two-dimensional column separation.

On the Origin of Primitive Cells: From Nutrient Intake to Elongation of Encapsulated Nucleotides

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

Aldehydes and sugars from evolved precometary ice analogs: Importance of ices in astrochemical and prebiotic evolution

Significance In molecular clouds out of which stars and planetary systems form, simple solid-state molecules made in large part of H2O, CO, CO2, CH3OH, and NH3 are abundantly present. In these environments, energetic and thermal processes on these ices, which can be simulated in the laboratory, lead to complex organic matter. Possibly at the origin of the organic matter in our Solar System and incorporated into planetesimals, this material may be considered as a potential source for prebiotic chemistry on telluric planets, following a process that may be quite universal. The composition of these laboratory-evolved ices includes potentially prebiotic species such as amino acids and, as presented in this paper, aldehydes and sugars. Evolved interstellar ices observed in dense protostellar molecular clouds may arguably be considered as part of precometary materials that will later fall on primitive telluric planets, bringing a wealth of complex organic compounds. In our laboratory, experiments reproducing the photo/thermochemical evolution of these ices are routinely performed. Following previous amino acid identifications in the resulting room temperature organic residues, we have searched for a different family of molecules of potential prebiotic interest. Using multidimensional gas chromatography coupled to time-of-flight mass spectrometry, we have detected 10 aldehydes, including the sugar-related glycolaldehyde and glyceraldehyde—two species considered as key prebiotic intermediates in the first steps toward the synthesis of ribonucleotides in a planetary environment. The presence of ammonia in water and methanol ice mixtures appears essential for the recovery of these aldehydes in the refractory organic residue at room temperature, although these products are free of nitrogen. We finally point out the importance of detecting aldehydes and sugars in extraterrestrial environments, in the gas phase of hot molecular clouds, and, more importantly, in comets and in primitive meteorites that have most probably seeded the Earth with organic material as early as 4.2 billion years ago.

ENANTIOMERIC EXCESSES INDUCED IN AMINO ACIDS BY ULTRAVIOLET CIRCULARLY POLARIZED LIGHT IRRADIATION OF EXTRATERRESTRIAL ICE ANALOGS: A POSSIBLE SOURCE OF ASYMMETRY FOR PREBIOTIC CHEMISTRY

The discovery of meteoritic amino acids with enantiomeric excesses of the L-form (ee L) has suggested that extraterrestrial organic materials may have contributed to prebiotic chemistry and directed the initial occurrence of the ee L that further led to homochirality of amino acids on Earth. A proposed mechanism for the origin of ee L in meteorites involves an asymmetric photochemistry of extraterrestrial ices by UV circularly polarized light (CPL). We have performed the asymmetric synthesis of amino acids on achiral extraterrestrial ice analogs by VUV CPL, investigating the chiral asymmetry transfer at two different evolutionary stages at which the analogs were irradiated (regular ices and/or organic residues) and at two different photon energies (6.6 and 10.2 eV). We identify 16 distinct amino acids and precisely measure the L-enantiomeric excesses using the enantioselective GC × GC-TOFMS technique in five of them: α-alanine, 2,3-diaminopropionic acid, 2-aminobutyric acid, valine, and norvaline, with values ranging from ee L = –0.20% ± 0.14% to ee L = –2.54% ± 0.28%. The sign of the induced ee L depends on the helicity and the energy of CPL, but not on the evolutionary stage of the samples, and is the same for all five considered amino acids. Our results support an astrophysical scenario in which the solar system was formed in a high-mass star-forming region where icy grains were irradiated during the protoplanetary phase by an external source of CPL of a given helicity and a dominant energy, inducing a stereo-specific photochemistry.

Circular Dichroism of Amino Acids in the Vacuum-Ultraviolet Region†

Biopolymers such as nucleic acids and proteins are composed of chiral monomers that show identical stereochemical configuration. Naturally occurring proteins are made up of l-amino acids. Hypotheses for the origin of symmetry breaking in biomolecules include the absolute asymmetric photochemistry model by which circularly polarized (CP) light induces an enantiomeric excess (ee) in chiral organic molecules. This model is supported by both the observation of CP light in the star-forming region of Orion and the occurrence of l-enantiomer-enriched amino acids in carbonaceous meteorites. However, the differential absorption of CP light by amino acid enantiomers, which determines the speed and intensity of enantioselective photolysis, is unknown over a large spectral range. Here we show that significant circular dichroic transitions in amino acids can be observed by extending circular dichroism (CD) spectroscopy to the vacuum-ultraviolet (UV) spectral range. a-H amino acids show the same CD magnitude and sign over a large wavelength range. In a given spectral window CP light is therefore capable of inducing enantiomeric excesses of the same handedness into the proteinogenic amino acids we have studied. Absolute asymmetric photochemistry might thus well have triggered the appearance of l-amino acid based life on Earth. Our results demonstrate that enantiomers of “meteoritic” a-methyl amino acids show dichroic absorption with equal magnitude, yet opposite sign to a-H amino acids. Therefore CP light cannot induce l enantiomeric excesses into a-methyl and a-H amino acids as found in meteorites. To explain the cause of symmetry breaking in biomolecules a well-known theory proposes that CP interstellar UV radiation—similar to that identified in the starforming region of Orion in the infrared—induced enantiomeric excesses into interstellar and circumstellar organic compounds by asymmetric photochemical reactions prior to their deposition on the early Earth. In support of this theory chiral amino acid structures were identified in interstellar ice analogues and a large number of l-enantiomer-enriched amino acids have been identified in the interior of the Murchison and Murray carbonaceous meteorites. To verify the absolute asymmetric photochemistry model the differential CP-light absorption of proteinogenic andmeteoritic amino acid enantiomers requires systematic examination. Until now, the popular and extensively used technique of CD spectroscopy has been used to record electronic CD for chiral molecules in aqueous solution above 190 nm. Water absorbs photons of l< 190 nm, making the vacuum-UV region inaccessible for CD spectroscopy in aqueous solution. By using a synchrotron radiation source for CP light and preparing isotropic amorphous solid-state samples immobilized on MgF2 windows, we have extended electronic CD measurements to the vacuum-UV spectral range. We observed intense CD-active transitions of amino acids between 140 and 190 nm (Figure 1), which are much more intense than the previously known CD bands between 190 and 330 nm. Figure 1a shows the CD spectra for dand l-alanine. As expected, the enantiomers of alanine show dichroic absorption of equal magnitude but opposite sign; the nice mirroring effect shows the high quality of the data. The CD spectra of l-alanine, l-valine, and l-leucine are characterized by maxima between 180 and 190 nm (Figure 1b), l-valine and l-leucine show minima between 160 and 170 nm, and l-serine and l-2-aminobutyric acid show maxima at 165– [*] Prof. Dr. U. J. Meierhenrich Laboratoire des Mol cules Bioactives et des Ar mes UMR 6001 CNRS-UNSA, Universit de Nice-Sophia Antipolis Facult des Sciences, Parc Valrose, 06108 Nice (France) Fax: (+33)4-9207-6151 E-mail: uwe.meierhenrich@unice.fr Homepage: http://www.unice.fr/lcmba/meierhenrich/

Photonenergy‐Controlled Symmetry Breaking with Circularly Polarized Light

Circularly polarized light (CPL) is known to be a true chiral entity capable of generating absolute molecular asymmetry. However, the degree of inducible optical activity depends on the λ of the incident CPL. Exposure of amorphous films of rac-alanine to tunable CPL led to enantiomeric excesses (ee) which not only follow the helicity but also the energy of driving electromagnetic radiation. Postirradiation analyses using enantioselective multidimensional GC revealed energy-controlled ee values of up to 4.2 %, which correlate with theoretical predictions based on newly recorded anisotropy spectra g(λ). The tunability of asymmetric photochemical induction implies that both magnitude and sign can be fully controlled by CPL. Such stereocontrol provides novel insights into the wavelength and polarization dependence of asymmetric photochemical reactions and are highly relevant for absolute asymmetric molecular synthesis and for understanding the origins of homochirality in living matter.

Application of preparative capillary gas chromatography (pcGC), automated structure generation and mutagenicity prediction to improve effect-directed analysis of genotoxicants in a contaminated groundwater

Background, aim and scopeThe importance of groundwater for human life cannot be overemphasised. Besides fulfilling essential ecological functions, it is a major source of drinking water. However, in the industrial area of Bitterfeld, it is contaminated with a multitude of harmful chemicals, including genotoxicants. Therefore, recently developed methodologies including preparative capillary gas chromatography (pcGC), MOLGEN-MS structure generation and mutagenicity prediction were applied within effect-directed analysis (EDA) to reduce sample complexity and to identify candidate mutagens in the samples. A major focus was put on the added value of these tools compared to conventional EDA combining reversed-phase liquid chromatography (RP-LC) followed by GC/MS analysis and MS library search.Materials and methodsWe combined genotoxicity testing with umuC and RP-LC with pcGC fractionation to isolate genotoxic compounds from a contaminated groundwater sample. Spectral library information from the NIST05 database was combined with a computer-based structure generation tool called MOLGEN-MS for structure elucidation of unknowns. Finally, we applied a computer model for mutagenicity prediction (ChemProp) to identify candidate mutagens and genotoxicants.Results and discussionA total of 62 components were tentatively identified in genotoxic fractions. Ten of these components were predicted to be potentially mutagenic, whilst 2,4,6-trichlorophenol, 2,4-dichloro-6-methylphenol and 4-chlorobenzoic acid were confirmed as genotoxicants.Conclusions and perspectivesThe results suggest pcGC as a high-resolution fractionation tool and MOLGEN-MS to improve structure elucidation, whilst mutagenicity prediction failed in our study to predict identified genotoxicants. Genotoxicity, mutagenicity and carcinogenicity caused by chemicals are complex processes, and prediction from chemical structure still appears to be quite difficult. Progress in this field would significantly support EDA and risk assessment of environmental mixtures.