Interstellar Ices as a Source of CN-Bearing Molecules in Protoplanetary Disks

A reliable model for the composition and evolution of interstellar ices inregions of active star formation is fundamental to our quest to determinethe organic inventory of planetesimals in the early Solar System. This hasbecome a realistic goal since the launch of the Infrared Space Observatory,which provides a facility for infrared spectroscopy unhindered by telluricabsorption over the entire spectral range of vibrational modes in solids ofexobiological interest. Interstellar molecules detected in the solid phaseto date include H_{_2O}, NH₃, CO, CO₂,CH₃OH, CH₄, H₂CO, OCS andHCOOH, together with a CN-bonded absorber generically termed`XCN'. In this article, we focus on cosmic synthesis of CN-bearing species,as this important class of prebiotic molecules may not have formedendogenously in significant quantities on early Earth if conditions were nothighly reducing. Experiments in which interstellar ice analogs are subjectto UV photolysis or energetic ion bombardment yield CN-rich residues with aspectral signature that matches a corresponding feature observed in youngprotostars enshrouded in dust and gas. CN-bearing species are also presentin cometary ices, with a combined abundance comparable to the lower end of therange observed in protostars. Energetic processing of interstellar ices isthus a viable and potentially significant source of CN compounds inprotoplanetary disks.     

CIRCUMSTELLAR AND INTERSTELLAR SYNTHESIS OF ORGANIC MOLECULES

We review the formation and evolution of complex circumstellar and interstellar molecules. A number of promising chemical routes are discussed which may lead to the formation of polycyclic aromatic hydrocarbon molecules, fullerenes, and unsaturated hydrocarbon chains in the outflows from stars. Some of the problems with these chemical schemes are pointed out as well. We also review the role of grains in the formation of complex molecules in interstellar molecular clouds. This starts with the formation of simple molecules in an ice grain mantle. UV photolysis and/or thermal polymerization can convert some of these simple molecules into more complex polymeric structures. Some of these species may be released to the gas phase, particularly in the warm regions around newly formed stars. Methanol and formaldehyde seem to play an important role in this drive towards molecular complexity and their chemistry is traced in some detail.     

Photochemical reactions in interstellar grains photolysis of co,NH3, and H2O

A simulation of the organic layer accreted onto interstellar dust particles was prepared by slow deposition of a CO:NH₃:H₂O gas mixture on an Al block at 10K, with concomitant irradiation with vacuum UV. The residues were analyzed by GC-MS, HPLC, and near IR; a reaction pathway leading from NH₃ to complex alcohol, fatty acid, and amide products in 27 stages is postulated. The astronomical relevance and significance of the observations are discussed.     

Interstellar molecules

Summary The study of interstellar molecules broadly includes two areas of interest. One area uses the unique ability of molecules to act as probes of the physical conditions in the cold, dense, visually opaque component of the interstellar medium. The physical properties of this and other components of the interstellar medium are summarized. The other area deals with the chemistry of interstellar molecules, recent aspects of which are emphasized in this review. Gas-phase chemistry, shock chemistry, and grain surface chemistry are discussed in the context of recent observations. No present observations suggest that surface reactions are relevant, but neither can they be ruled out. Ion-molecule reactions are clearly operative, at least for the simpler species. Chemical isotope fractionation is reviewed, andd it is concluded that the complexities of the chemistry allow no cosmological conclusions to be drawn from observations of deuterium in interstellar molecules, while the presence of¹³C in interstellar molecules permits an estimate of the¹²C/¹³C ratio which is consistent with the current concepts of the nucleosynthesis history of the Galaxy. Possible connections between interstellar molecules and the early molecular history of the solar system are discussed.This is the first of a series of papers which will appear in the Synthesis section of the Journal of Molecular Evolution pertaining to the topic Organic Molecules in the Solar System and Beyond.Operated by Associated Universitites, Inc., under contract with the National Science Foundation     

Extraterrestrial Organic Matter: A review

We review the nature of the widespread organic material present in the Milky Way Galaxy and in the Solar System. Attention is given to the links between these environments and between primitive Solar System objects and the early Earth, indicating the preservation of organic material as an interstellar cloud collapsed to form the Solar System and as the Earth accreted such material from asteroids, comets and interplanetary dust particles. In the interstellar medium of the Milky Way Galaxy more than 100 molecular species, the bulk of them organic, have been securely identified, primarily through spectroscopy at the highest radio frequencies. There is considerable evidence for significantly heavier organic molecules, particularly polycyclic aromatics, although precise identification of individual species has not yet been obtained. The so-called diffuse interstellar bands are probably important in this context. The low temperature kinetics in interstellar clouds leads to very large isotopic fractionation, particularly for hydrogen, and this signature is present in organic components preserved in carbonaceous chondritic meteorites. Outer belt asteroids are the probable parent bodies of the carbonaceous chondrites, which may contain as much as 5% organic material, including a rich variety of amino acids, purines, pyrimidines, and other species of potential prebiotic interest. Richer in volatiles and hence less thermally processed are the comets, whose organic matter is abundant and poorly characterized. Cometary volatiles, observed after sublimation into the coma, include many species also present in the interstellar medium. There is evidence that most of the Earth's volatiles may have been supplied by a late bombardment of comets and carbonaceous meteorites, scattered into the inner Solar System following the formation of the giant planets. How much in the way of intact organic molecules of potential prebiotic interest survived delivery to the Earth has become an increasingly debated topic over the last several years. The principal source for such intact organics was probably accretion of interplanetary dust particles of cometary origin.     

DETECTION OF ORGANIC MATTER IN INTERSTELLAR GRAINS

Star formation and the subsequent evolution of planetary systems occurs in dense molecular clouds, which are comprised, in part, of interstellar dust grains gathered from the diffuse interstellar medium (DISM). Radio observations of the interstellar medium reveal the presence of organic molecules in the gas phase and infrared observational studies provide details concerning the solid-state features in dust grains. In particular, a series of absorption bands have been observed near 3.4~2940 cm^–1) towards brightinfrared objects which are seen through large column densities of interstellar dust. Comparisons of organic residues, produced under a variety of laboratory conditions, to the diffuse interstellar medium observations have shown that aliphatic hydrocarbon grains are responsible for the spectral absorption features observed near 3.4 ~2940cm^–1). These hydrocarbons appear to carry the –CH₂– and –CH₃ functional groups in the abundance ratio CH₂/CH₃ ~ 2.5, and theamount of carbon tied up in this component is greater than 4% of the cosmic carbon available. On a galacticscale, the strength of the 3.4 band does notscale linearly with visual extinction, but instead increases more rapidly for objects near the Galactic Center. A similar trend is noted in the strength of the Si–O absorption band near 9.7. The similarbehavior of the C–H and Si–O stretching bands suggests that these two components may be coupled, perhaps in the form of grains with silicate cores and refractory organic mantles. The ubiquity of the hydrocarbon features seen in the near infrared near 3.4throughout our Galaxy and in other galaxies demonstrates the widespread availability of such material for incorporation into the many newly forming planetary systems. The similarity of the 3.4features in any organic material with aliphatic hydrocarbons underscores the need for complete astronomical observational coverage in the 2–30 region, oflines of sight which sample dust in both dense and diffuse interstellar clouds, in order to uniquely specify the composition of interstellar organics. This paper reviews the information available from ground-based observations, although currently the Infrared Satellite Observatory is adding to our body of knowledge on this subject by providing more extensive wavelength coverage. The Murchison carbonaceous meteorite has also been used as an analog to the interstellar observations and has revealed a striking similarity between the light hydrocarbons in the meteorite and the ISM; therefore this review includes comparisons with the meteoritic analog as well as with relevant laboratory residues. Fundamental to the evolution of the biogenic molecules, to the process of planetary system formation, and perhaps to the origin of life, is the connection between the organic material found in the interstellar medium and that incorporated in the most primitive solar system bodies.     

Alpha particle chemistry. On the formation of stable complexes between He2+ and other simple species: implications for atmospheric and interstellar chemistry

The possibility that stable complexes may be formed between alpha particles (He²⁺) and small molecules is investigated using QCISD quantum mechanical calculations. Implications for their presence in the terrestrial atmosphere and/or in interstellar space are discussed. Figure Optimized structure of a stable H₂OHe²⁺ complex     

Chemical evolution in space

The bulk of complex molecules in the space between the stars is probably contained in small frozen interstellar dust grains. A typical grain is about as old as the earth and has, as a result of photochemical processing, converted a large fraction of its oxygen, carbon and nitrogen bearing mantle into large organic molecules whose maximum molecular weights are limited only by the grain size of about 0.1 m. Laboratory and theoretical methods provide the basis for explaining the evolution of interstellar grains from the time they are formed as seedlings in the atmospheres of cool evolved stars to the time they are destroyed by being incorporated into the material of new stars. The organic dust constitutes about one tenth of a percent of the total mass of the Milky Way and far outweighs any estimates of the total mass of all the planets. A planet like the earth is continually and directly accreting interstellar dust from space. Primitive carbonaceous meteorites show evidence of containing interstellar dust. Since comets are possibly almost pure aggregated interstellar dust they also provide a source of interstellar organic material on the earth.     

INTERSTELLAR ICES STUDIED WITH THE INFRARED SPACE OBSERVATORY

The Infrared Space Observatory (ISO) was launched by the European Space Agency on 17 November 1995. The availability of spectra from the Short Wavelength Spectrometer (SWS) on ISO is a landmark in the study of interstellar ices and organics; they provide a wealth of data in the 2–20µ region of the spectrum covering the principal solid state resonances of condensed matter in interstellar clouds. We thus have the opportunity to study many species likely to be relevant to the inventory of CNO-bearing interstellar material present at the formation of our own and other planetary systems. This paper presents a brief overview of what has been learned from the data available so far. A comparison is made between the compositions of ices in molecular clouds, protostellar condensations and comets. Key areas of uncertainty are highlighted as a basis for future research.     

A search for interstellar oxiranecarbonitrile (C3H3NO)

We report a search in cold, quiescent and in hot core type interstellar molecular clouds for the small cyclic molecule oxiranecarbonitrile (C₃H₃NO), which has been suggested as a precursor of important prebiotic molecules. We have determined upper limits to the column density and fractional abundance for the observed sources and find that, typically, the fractional abundance by number relative to molecular hydrogen of C₃H₃NO is less than a few times 10^–10. This limit is one to two orders of magnitude less than the measured abundance of such similarly complex species as CH₃CH₂CN and HCOOCH₃ in well-studied hot cores. A number of astrochemical discoveries were made, including the first detection of the species CH₃CH₂CN in the massive star-forming clouds G34.3+0.2 and W51M and the first astronomical detections of some eight rotational transitions of CH₃CH₂CN, CH₃CCH, and HCOOCH₃. In addition, we found 8 emission lines in the 89 GHz region and 18 in the 102 GHz region which we were unable to assign.     

Genetic diversity and structure of the endemic Caesalpinia hintonii complex (Leguminosae: Caesalpinioideae) in Mexico

The Caesalpinia hintonii complex is formed by five endemic species (C. hintonii, C. laxa, C. macvaughii, C. melanadenia and C. epifanioi) occurring in central Mexico. This species complex is under incipient genetic divergence as by-product of local adaptations in reproductive and morphological traits to different habitats. We estimate the genetic variation and structure of populations of this species complex to assess the extent of genetic differentiation among populations and related species along its geographic distribution. Estimations of genetic diversity and structure were done based on ten enzymes and 18 loci. Mean number of alleles per locus ranged from 1.5 to 1.9. Polymorphic loci ranged from 42.1 to 68.4. Observed (H_o: range 0.191–0.275) and expected (H_e: range 0.205–0.317) heterozygosities in this complex were higher compared with other endemic and legume species. Neis genetic diversity estimates showed that most genetic variation was found within (H_S = 0.325) rather than among populations (D_ST = 0.085). Populations of the species C. hintonii showed a considerable genetic differentiation (F_ST = 0.207). The results of genetic diversity and structure within and among populations are in accord with the great morphological differentiation described for this species complex.     

The Diffuse Interstellar Bands: A Tracer For Organics In The Diffuse Interstellar Medium?

The diffuse interstellar bands (DIBs) are absorption bands seen in the spectra of stars obscured by interstellar dust. DIBs are recognized as a tracer for free, organic molecules in the diffuse interstellar medium (ISM). The potential molecular carriers for the DIBs are discussed with an emphasis on neutral and ionized polycyclic aromatic hydrocarbons (PAHs) for which the most focused effort has been made to date. From the combined astronomical, laboratory and theoretical study, it is concluded that a distribution of free neutral and ionized complex organics (PAHs, fullerenes, unsaturated hydrocarbons) represents the most promising class of candidates to account for the DIBs. The case for aromatic hydrocarbons appears particularly strong. The implied widespread distribution of complex organics in the diffuse ISM bears profound implications for our understanding of the chemical complexity of the ISM, the evolution of prebiotic molecules and its impact on the origin and the evolution of life on early Earth through the exogenous delivery (cometary encounters and metoritic bombardments) of prebiotic organics.     

Sex chromosome pairing during male meiosis in marsupials

The pairing of the sex chromosomes at pachytene has been examined in twenty-two species of Australian marsupials, including four with complex sex chromosome systems. The axial elements of the sex chromosomes associate in all but one species. However, no synaptonemal complex has been observed between the axes of the X and Y chromosome in any of the examined species. Both the type of association between the sex chromosome axes, and the structural modifications of these axes are conserved within taxonomic groupings. In three species with complex sex chromosome systems, the t(XA), Y, A trivalents do not have a favoured relative orientation of the axes of the Y and A chromosomes, whereas in a fourth species with a t(XA₁), t(A₂YA₂), A₂ system the t(XA₁) and A₂ axes are in a cis arrangement with each other.     

On the chemical constitution of cometary nuclei

The observed properties of comets and the experiments of Anderset al. suggest that during the condensation of the outer parts of the solar system from the solar nebula-assumed to contain most of the C in the form of CO, the remaining O mostly in the form of H₂O, and the excess H as H₂ molecules-besides the most stable hydrocarbon (CH₄) also considerable quantities of heavier hydrocarbon were formed. When the surface of the nucleus is warmed up in re-approaching the sun, part of the solar quanta having sufficient energy for dissociating such molecules, exothermic reactions, for instance such leading, to the observed C₂ and C₃ molecules may be expected; an inhomogeneous and porous structure of the nucleus would explain the observed occurrence of short-lived discrete jets, in which a small fraction of the CO could be ionized. Since also N must be present in some quantity (observed mainly was CN and N₂ ⁺), the formation of more complex organic molecules must also have taken place. To which extent complex interstellar molecules can have survived the formation of the solar system is hard to say on the basis of present knowledge of the origin of the solar system.     

Mechanism of bleomycin action: in vitro studies

The cytotoxic activity of bleomucin results from DNA cleavage, which is also accomplished $\text{in vitro}$ by reaction mixtures containing Fe(II), drug and O₂. Bleomycin forms a complex with Fe(II) and O₂ in the presence or absence of DNA. The species attacking DNA forms rapidly from this complex. The nature of the attacking species and of the primary lesion(s) to DNA are not yet known, but two major insults to DNA have been characterized. They are the release of free bases from their glycosidic linkages and, at other residues, the cleavage of the polymer backbone at the deoxyribose C3-C4 bond.     

Laboratory simulation of organic grain mantles

The most relevant conditions in interstellar space for grain mantle evolution are being simulated at Laboratory Astrophysics. In particular we have photoproduced in the laboratory a material resembling the organic refractory mantle on interstellar grains. These organic refractory samples are being analyzed by several methods, and they have been found to consist of a very complex mixture of long chains, cross-linked and probably aromatic carbon molecules.Presented at the Session Water in the Solar System and Its Role in Exobiology during the 26th General Assembly of the European Geophysical Society, 22–26 April 1991 in Wiesbaden, Germany.     

Energetics and possible mechanisms of ion-beam protein tritiation based on ab initio potential surfaces

Ab initio self-consistent field potential energy surfaces for the approach of T. T₂. T⁺. T⁺₃ and HeT⁺ to glycine in the gas phase have been determined and this data used to obtain insight into mechanisms of experimental ion-beam protein tritiation processes. Results of these calculations show that the ionic species T⁺, T⁺₃ and HeT⁺ can form stable adducts with glycine (Gly) and that each functions as a tritiation agent forming the complex GlyT⁺. Neutral T and T₂ experience a purely repulsive interaction with Gly and do not form an intermediate complex. These neutral species are expected to be less effective tritiation agents than the respective ions, in agreement with experimental observations. The fate of the stable GlyT⁺ complex is discussed and it is proposed that this species is neutralized by electron capture to give GlyT which spontaneously dissociates to either Gly+T or tritiated glycine (Gly^*)+H, with the latter reaction product channel favored statistically. The most likely site of exchange is predicted to be at the amine nitrogen although significance exchange is expected to occur at the α-carbon site by a somewhat more complex reaction mechanism.     

Delivery of Complex Organic Compounds from Evolved Stars to the Solar System

Stars in the late stages of evolution are able to synthesize complex organic compounds with aromatic and aliphatic structures over very short time scales. These compounds are ejected into the interstellar medium and distributed throughout the Galaxy. The structures of these compounds are similar to the insoluble organic matter found in meteorites. In this paper, we discuss to what extent stellar organics has enriched the primordial Solar System and possibly the early Earth.     

Reactions of thiols and selenols with the FeMoS cluster [Fe(MoS4)2]3−

The known complex [Et₄N]₃[Fe(MoS₄)₂] has been shown by EPR and visible spectral studies to react with both thiophenol and selenophenol. The reaction results in a change in the characteristic S=3/2 EPR spectrum of this species from a complex rhombic pattern to one of a very simple axial appearance. Although this effect is similar to that observed for reaction of these species with the iron- molybdenum cofactor of nitrogenase, a moiety known to consist of a FeMoS cluster species, the large excesses of reagents and the long reaction times required for complete formation of product indicate that these reactions are of questionable direct relevance to the biological system. The reaction corresponding to the EPR spectral change from rhombic to axial in the [Fe(MoS₄)₂]³⁻/PhSeH system has also been partially characterized by product isolation which indicates that attack by selenol of the two terminal MoS₂ moieties in the starting material has occurred.     

A conceptual design for cosmo-biology experiments in Earth's Orbit.

A conceptual design was developed for a cosmo-biology experiment. It is intended to expose simulated interstellar ice materials deposited on dust grains to the space environment. The experimental system consists of a cryogenic system to keep solidified gas sample, and an optical device to select and amplify the ultraviolet part of the solar light for irradiation. By this approach, the long lasting chemical evolution of icy species could be examined in a much shorter time of exposure by amplification of light intensity. The removal of light at longer wavelength, which is ineffective to induce photochemical reactions, reduces the heat load to the cryogenic system that holds solidified reactants including CO as a constituent species of interstellar materials. Other major hardware components were also defined in order to achieve the scientific objectives of this experiment. Those are a cold trap maintained at liquid nitrogen temperature to prevent the contamination of the sample during the exposure, a mechanism to exchange multiple samples, and a system to perform bake-out of the sample exposure chamber. This experiment system is proposed as a candidate payload implemented on the exposed facility of Japanese Experiment Module on International Space Station.