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P6: Posters – Prebiotic Chemistry
Time: Tuesday, 05/Jul/2011: 10:00am - 11:00am
Location: Hall Antigone


The irradiation of methyl cyanide (CH3CN) ice at 15 K with 200 keV protons

Sohan Jheeta1, Daniele Fulvio2, Maria Elisabetta Palumbo2, Gianni Strazzulla2, Nigel J Mason1

1Dept. of Physics & Astronomy, The Open University, England, United Kingdom; 2Istituto Nazionale di AstroFisica, Osservatorio Astrofisico di Catania, Catania, Italy

The following species were found to be synthesized during the proton irradiation of methyl isocyanide: (CH3NC), hydrogen cyanide (HCN/CN-), methylenimine (H2C=NH), ketenimine (H2C=C=NH), cyanoacetylene (HCCCN), and methane (CH4). These results and details of the possible production routes will be presented at the conference.


Radiolytic products from carbonates: Implications for the prebiotic Earth.

Guadalupe Albarran1, Carol Collins2, Keneth Collins2

1Universidad Nacional Autonoma de Mexico, Mexico; 2Univerdidade Estadual de Campinas, Brazil

In this study we have used solid Ca14CO3 auto-irradiated as an approach to duplicate the radioactive environment of the Primitive Earth. 6 carboxylic acids, 1 aldehyde, 1 alcohol were obtained from reactions of the species formed during the auto-irradiation. The principal product at low doses (130 kGy) was formic acid (87.5 % ), formed by hydrolysis of the CO2 ion-radical. At a high dose (63 MGy); oxalic acid was produced (57 %), resulting from solid-state dimerization of the same radical.


Radiation action in biomolecular systems: direct and indirect processes in ion-biomolecule collisions

Marie-Christine Bacchus1, Emese Rozsályi2, Gabor Halász3, Ágnes Vibók2

1Laboratoire de Spectrometrie Ionique et Moleculaire, Université Lyon I et CNRS, France; 2Department of Theoretical Physics, University of Debrecen, Hungary; 3Department of Information Technology, University of Debrecen, Hungary

Action of high energy radiations, as cosmic rays may induce damage on biological medium. Important damage is due to secondary particles, low-energy electrons, radicals, ions, generated along the track. We have developed a theoretical approach of charge transfer in collisions of carbon ions with uracil and halouracil targets. A comparative study of reactions with the OH radical that may be formed in the aqueous solvent and CO molecule is presented. Anisotropy and vibration effect are analyzed.


Finding the clues for prebiotic acidic hydrothermal phosphorylations

Ge Tian, Maheen Gull

State Key Laboratory of Inorganic Synthesis and Preparative Chemistry,College of Chemistry, Jilin University,Peoples Republic of China

Prebiotic acidic hydrothermal conditions were mimicked and biological phosphate esters such as glycerol phosphates (glycerol-2-phosphate, sn-glycerol-3-phosphate and phosphoethanolamine) and glucose phosphates (glucose-1-phosphate, glucose-6-phosphate and glucose-diphosphate) were synthesized under hydrothermal conditions, in the presence of the mixture of minerals.


Chemical model for the prebiogenesis of tetrapyrrole macrocycles

Jonathan Lindsey, Vanampally Chandrashaker, Masahiko Taniguchi, Marcin Ptaszek

North Carolina State University, United States of America

A non-enzymic reaction pathway – differing slightly from the modern biosynthesis – converts two acyclic substrates (aminolevulinic acid and a levulinic acid derivative) to a pyrrole (resembling porphobilinogen) that undergoes self-condensation to give uroporphyrinogen, the universal precursor to all naturally occurring tetrapyrrole macrocycles. The reaction proceeds anaerobically in water (25-85 °C, pH 5-7, 10-240 mM) in 10% yield. Other tetrapyrroles are available with analogous substrates.


Nanopore Origin of Life

Richard Wilde

Department of Chemistry, Texas Tech University, United States of America

It is proposed that life originated in the nanopores of porous rock at deep-sea hydrothermal vents. The nature of the rock is not as important as its porosity. The rock could have been porous basalt, pyrite, or calcium carbonate at alkaline vents. The porous nature of the rock would have allowed a chemistry unique to confined spaces and protection of the early chemicals. A research plan to implement this study will be presented.


Liquid-crystalline self-assembly of nucleic acids: a new pathway for the prebiotic elongation of RNA?

Tommaso Bellini1, Giuliano Zanchetta1, Noel A. Clark2

1Dipartimento di Chimica, Biochimica e Biotecnologie, University of Milano, Italy; 2Department of Physics, University of Colorado, Boulder, Colorado, USA

New patterns of self-assembly of short oligonucleotides have recently been discovered. As DNA and RNA oligos hybridize, they tend to segregate from unpaired strands and to pile up in chains, thus favoring the ligation of their terminals. These mechanisms provide selectivity and act as a template for the elongation of the oligomers. The positive feedback between oligomer length and self-assembly appears as an important route for the formation of extended chains in prebiotic environments.


Anaerobic Corrosion of Iron Meteorites on the Early Earth. Routes to high energy intermediates.

David Bryant1, Terence Kee1, David Greenfield2, Caroline Smith3, Matthew Pasek4, Ian Scowen5, Tasnim Munshi5, Howell Edwards5

1Department of Chemistry, University of Leeds, UK; 2Centre of Corrosion Technology, MERI, Sheffield Hallam University, Sheffield UK; 3Department of Mineralogy, Natural History Museum, London, UK; 4NASA Astrobiology Institute, University of Arizona, Tucson, Arizona USA; 5School of Life Science, University of Bradford, Bradford, UK

Iron meteorites would have been subject to corrosion on the early Earth despite the low levels of O2 in the atmosphere. The presence within these meteorites of phosphorus rich inclusions provides the potential for galvanism. The corrosion potential of a sample of Sikhote-Alin meteorite has been studied using XPS and scanning Kelvin probe and the actual corrosion in acid vapour has been studied using Raman spectroscopy with supporting images obtained by infinite focus microscopy and SEM/EDX


From Simplicity to Complexity: Reduced Oxidation State Phosphorus in Prebiotic Chemistry.

Katie Marriott, David Bryant, Terence Kee

University of Leeds,, United Kingdom

Work on the photochemical hydrolysis and Galvanic corrosion of inclusions within iron meteorites suggests that H3PO2 and H3PO3 would have been readily accessible on prebiotic Earth. Two different yet related chemical systems are analysed. Firstly, H3PO2 selectively reacts with carbonyls leading to interesting molecular architectures. Secondly, a system based on H3PO3 and its potential to be converted to condensed P-oxyacids which may have had some functional value within prebiotic environments.


Formation and chiroptical properties of amino acids in simulated interstellar ices

Uwe Meierhenrich1, Cornelia Meinert1, Jean-Jacques Filippi1, Jan Hendrik Bredehöft2, Jun-ichi Takahashi3, Laurent Nahon4, Nykola Jones5, Soeren Hoffmann5, Pierre de Marcellus6, Louis d'Hendecourt6

1University of Nice-Sophia Antipolis, France; 2University of Bremen, Germany; 3NTT Microsystem Integration Laboratories, Atsugi, Japan; 4Synchrotron SOLEIL, Gif-sur-Yvette, France; 5Aarhus University, Denmark; 6Institute d'Astrophysique Spatiale, Orsay, France

Representative interstellar molecules such as H2O, CH3OH, CO, CO2, and NH3 were condensed on a helium-cooled solid surface at 12 K while being irradiated. New multidimensional GC-MS techniques allowed the identification of new chiral organic molecules including different amino acids and diamino acids. The differential absorption of cpl by individual amino acid enantiomers was recorded in the vacuum-UV spectral range, where new and intense circular dichroic transitions were observed.


A chemical reactor for peptide formation, elongation and accumulation on the Primitive Earth, and its implication for the emergence of homochirality.

Grégoire Danger1, Raphaël Plasson2, Laurent Boiteau3, Robert Pascal3

1Laboratoire de Physique des Interactions Ionique et Moléculaire, France; 2NORDITA, Stockholm, Sweden.; 3quot;Dynamique des Systèmes Biomoléculaire Complexe", "Institut des Biomolécules Max Mousseron", France

In this contribution, we will present a chemical reactor capable of promoting amino acid activation and condensation, allowing their elongation into oligopeptides that could accumulate in environments considered as favorable to the emergence of life. Furthermore, because our scenario is formed of a cyclic sequence of reactions with continuous flow of energy and matter, we will present our investigations on its possible implications in the prebiotic emergence of homochirality.


Role of Iron Oxides in the Formation of Nucleobases from Formamide: Implication in Chemical Evolution

Uma Shanker, Kamaluddin -, Gurudas Bhattarcharjee

Indian Institute of Technology Roorkee, Roorkee, Uttarakhand, India

Formamide, a hydrolysis product of HCN is known as the precursor of various biologically important compounds, e.g., nucleobases (purines & pyrimidines) and amino acids. We report our results on the synthesis of nucleobases, adenine, cytosine, purine, 9-(hydroxyacetyl) purine and 4(3H)-pyrimidinone from formamide using iron oxide (hematite) and oxide hydroxides (goethite and akaganeite) as catalyst. Goethite and hematite produced purine in higher yield as compared to akaganeite


Habitats of the first organisms

Armen Mulkidjanian

School of Physics, University of Osnabrueck, D-49069, Germany, Lomonosov Moscow State University, Moscow, 119991, Russia

The prevalence of Zn in the ubiquitous cellular systems indicates that the first organisms developed in Zn-rich environments. The Zn levels could be high at the sites of hydrothermal activity, where Zn ions precipitated as particles of zinc sulfide (ZnS). Under the high pressure of primordial atmosphere, the ZnS-enriched precipitates could form within reach of solar radiation. They may have catalysed abiogenic photosynthesis and protect the first RNA-like polymers from photodestruction.


Role of Iron Oxides in the Oligomerization of Glycine and Alanine: Implication in Chemical Evolution

Kamaluddin -, Uma Shanker, Gurudas Bhattacharjee

Indian Institute of Technology Roorkee, India

Catalytic activity of iron oxides namely, goethite, akaganeite and hematite in the intermolecular condensation of glycine and L-alanine. All the three forms of iron oxides worked as efficient catalysts for the peptide bond formation. Maximum yield of peptides was found after 28 days at 900 C. Reaction at 1200 C favored formation of diketopiperazine derivatives. High yield of oligomers with goethite is probably due to its high surface area and surface acidity.


Why are we failing to make RNA?

Anthony Mellersh, Paul Smith

University of Derby, United Kingdom

We propose that the first biomolecules were synthesized on mineral/organic surfaces and give examples of how this would be achieved. They would mimic protein enzymes in that they select, orientate, and activate reactants and then release the product. The processes are similar to modern enzymes allowing a smooth transition when protein synthesis emerges. These systems would offer a new approach to the question posed. We propose the term Geozymes. See http://www.geozyme.com .


Nucleic Acids in Non-Aqueous Environment

Irena Mamajanov, Aaron Engelhart, Heather Bean, Nicholas Hud

Georgia Institute of Technology, United States of America

The main polymers of life are products of dehydration reactions, implying that proto-biopolymers were formed under low water activity. We have searched for ionic liquids and deep eutectic solvents (DES) that support nucleic acid folding. Here, we report that nucleic acids form duplex, triplex and G-quadruplex structures in a water-free DES composed of urea and choline chloride. This discovery suggests new research directions, since it obviates the need for water in chemical evolution.


Adsorption of Ribose Nucleotides on Manganese Oxides with Varied Mn/O Ratio: Implication in Chemical Evolution

Kamaluddin -, Brij Bhushan

Indian Institute of Technology Roorkee, India

Manganese oxides, namely, Manganosite (MnO), Bixbyite (Mn2O3), Hausmannite (Mn3O4) and Pyrolusite (MnO2) were synthesized and their adsorption affinity towards ribose nucleotides has been studied at neutral pH. Results of our studies suggest that highest binding of ribonucleotides occured with Manganosite (MnO) as compred to the other manganese oxides and thus supports the concept that activity of chemical evolution was more pronounced under reducing atmosphere of the primitive earth.


Interaction of Metal Octacyanomolybdates with Ribose Nucleotides: Implications in Chemical Evolution

Anand Kumar, Kamaluddin -

Department of Chemistry, Indian Institute of Technology, Roorkee,India

The present report deals with the interaction of ribose nucleotides, namely; 5′-AMP, 5′-GMP, 5′-CMP and 5′-UMP with a series of metal octacyanomolybdate (MOCMo). Adsorption of nucleotides on Mn-, Fe-, Co-, Ni-, Cu-, Zn-, Cd- octacyanomolybdate followed Langmuir adsorption isotherm. Xm and KL values were calculated. Adsorption was found to be maximum on ZnOCMo while minimum in FeOCMo. The biomonomers so concentrated might have been protected from degradation.


Model of one-electron transport. Thermodynamic parameters calculation of electron attachment to bound proton of oxyacids A-OH

Anton Stanislavovich Zubkov1, Vasilii Igorevich Artyukhov1,2, Leonid Alexandrovich Chernozatonskii1, Olga Serafimovna Nedelina1

1Emanuel Institute of Biochemical Physics, Russian Academy of Sciences, Moscow, Russia; 2Department of Mechanical Engineering and Materials Science, Rice University, Houston, Texas, USA

We calculated thermodymamic parameters of dissociative photoelectron attachment to oxyacids in the context of model of low-energy electron transport by molecular anions. It was found that excess electron is dipole-bound to acidic protons on the opposite side from their respective oxygen atoms for oxyacids with large pKα. The metastable electron-adduct state can either serve as an electron relay intermediary (autodetachment), or dissociate releasing a hydrogen atom (fragmentation).


Self-propagation of amino acids: further step towards the chemical origin of Life

Syuzanna R. Harutyunyan, Francesca Caprioli

University of Groningen, The Netherlands

Replication and homochirality of biomolecules are quintessential features of living systems. Autocatalytic reactions are at the origin of self-replication and homochirality. While investigating the origin of these processes we have developed autocatalytic systems using biologically relevant small organic molecules. We have found, for the first time, that it is possible to utilize quaternary aminoacids as catalysts for their own formation in relation with their extraterrestrial role.


Abiogenic synthesis of oligopeptides in open space conditons

Michael Simakov, Eugenia Kuzicheva, Natalia Gontareva

Institute of Cytology, RAS, Russian Federation

The reactions of amino acids in solid mixtures were the primary objective of our investigation - the abiogenic synthesis of dipeptides from mixtures of simple amino acids with different sources of energy: (1) VUV; (2) protons (2-6 MeV); (3) g–radiation and (4) all spectra of the open space energy. We have shown the solid mixtures of amino acids produce more complex compounds under different energy sources which may destroy molecules as well as allow the synthesis of more complex ones.


The chemical evolution that was caused by adaptability of electronic structure on carbon atom

Shinji Karasawa

Miyagi National College of Technology (Professor emeritus), Japan

A carbon atom has many possible electronic structures. Organic molecule possesses adaptability to surroundings by the characteristics of carbon atom. Hydrogen bond of water gives liquidity. The thermal motion randomizes neighboring molecules. Acceptable reaction among randomized combination carries out a trial-and-error. But the result of reaction affects the next reaction. Chain of reactions for chemical evolution in the aqueous medium takes place along a course of the time.


Sugar-driven prebiotic synthetic processes supporting abiogenesis

Arthur Weber

SETI Institute, United States of America

We have investigated abiogenesis using sugar substrates because sugars (1) possess energized carbon groups capable of driving synthetic reactions without any other source of energy, and (2) are easily formed by formose-like condensations of formaldehyde and small two-carbon aldehydes (glycolaldehyde, glyoxal, and glyoxylate). Our studies show that spontaneous sugar transformation reactions yield products essential for abiogenesis, including alternative pyrazinone nucleobase monomers.


Formation of self-propagating amyloid-like fibrillar structures from EGGSVVAAD, a prebiotically plausible nonapeptide: Implications for the origins of life

C. Peter J. Maury, Mikko Liljeström, Fang Zhao

University of Helsinki, Finland

We show that a prebiotically plausible short peptide spontaneously forms amyloid-like fibrillar structures in aqueous solution.This gives experimental support for the amyloid world-hypothesis that posits that peptide-based beta-sheet molecular structures were the first self-replicating informational biomolecules that evolved on the primitive Earth.


The EvoGrid: in silico simulation grid for origin of life endeavours

Bruce Damer1, Peter Newman2, Ryan Norkus2, Graham John3

1University College Dublin, Ireland; 2DigitalSpace, United States of America; 3University of California at San Diego, United States of America

The EvoGrid is an open, distributed molecular dynamics simulation grid under development at several institutions worldwide. The EvoGrid is designed to bring industrial scale simulation to bear on problems in origin of life endeavors including the modeling of de novo emergence of structures and reactions in a prebiotic chemical milieu. The first results of EvoGrid prototype testing will be presented and a call for collaboration on defining future directions and experiments issued.


A Model for the Origin of Amino acid Homochirality

Haiyan Wang1, Daxiong Han2, Yufen Zhao3

1Third Institute of Oceanography, State Oceanic Administration of China, Xiamen, China; 2Department of Pharmacy, Medical College of Xiamen University, Xiamen, China; 3College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, China

The source of homochirality is one of the most important topics in the research on the origin of life. In the present study, we demonstrate that amino-acid homochirality, as a unique feature of life, might have originated synchronously with the Genetic Code. And the emergence of phosphoryl amino-acid 5’-nucleosides (aaNs) having a P-N bondis described as a model of the origin of amino-acid homochirality and Genetic Code.


Delivery of prebiotic material on the first generations of Milky Way planets: Was it possible ?

Giovanni Vladilo, Marco Fulle

INAF - Osservatorio Astronomico di Trieste, Italy

Organic material delivered from space on Earth around 4 Gyr ago may have played a crucial role in the origin of terrestrial life. Was prebiotic material available for space delivery in previous generations of planets? To address this issue we review the evidence for organic material in interstellar environments representative of the young Milky Way. The picture that emerges is unfavourable, but definitive statements must await a better understanding of pre-stellar and proto-planetary chemistry.


Nucleotide Formation under Prebiotic Conditions via Paterno-Buchi Reaction and Stepwise Nucleobase Formation

Gerhard Zieboll, Terence Kee

School of Chemistry, University of Leeds, United Kingdom

The formose reaction is generally accepted to be of prebiotic relevance regarding the formation of sugars. Malonaldehyde is a photolysis and radiolysis product of sugars in slightly alkaline medium. It is therefore reasonable to assume that malonaldehyde was present on the prebiotic earth. We investigate the formation of pentoses through the photochemical cycloaddition of various carbonyl compounds and malonaldehyde in aqueous and organic media.


Photoinduced catalytic synthesis of biologically important metabolites from formaldehyde and ammonia

Irina Delidovich1, Lyudmila Matvienko1, Oxana Taran1, Alexander Simonov1, Valentin Parmon1,2

1Boreskov Institute of Catalysis, Russian Federation; 2Novosibirsk State University, Russian Federation

UV-irradiation of formaldehyde aqueous solution yields acetaldehyde, glyoxal, glycolaldehyde and glyceraldehyde, which can serve as precursors of more complex biochemically relevant compounds. The possibility of formation of sugars (including ribose, ribulose and xylulose), amino acids, pyruvaldehyde and pyruvic acid from the simple aldehydes and NH3 under UV-irradiation or/and in the presence of mineral catalysts (homogeneous borates & phosphates, zeolite, montmorillonite, apatite) is revealed.


Formation of complex molecules on the Interstellar grain under various Interstellar conditions

Ankan Das1, Sandip Chakrabarti1,2

1Indian Centre for Space Physics, India; 2S. N. Bose National Centre for Basic Sciences, India

Interstellar grain provides the space for the chemical enrichment of the Interstellar molecules. Now a days it is believed that most of the observed Interstellar complex molecules are mainly formed on the grain surfaces(at least a part) and are synthesized to the gas phase. We have done a Monte Carlo simulation to study the chemical enrichment of the Interstellar grain mantle under the various Interstellar conditions. Simulation results are compared with the different observations made so far.


Formation of prebiotic molecules during the collapse of molecular cloud: A time dependent study

Liton Majumdar1, Ankan Das1, Sandip K. Chakrabarti2,1, Sonali Chakrabarti3,1

1Indian Centre for Space Physics, India; 2S.N.Bose National Centre for Basic Sciences, India; 3Manindra Chandra College, India

Pre-biotic molecules are observed along different line of sights. It is anticipated that the pre-biotic molecules are formed during the collapse of the molecular cloud, Here we use Total variation diminishing (TVD) scheme to study the physical properties of the collapsing cloud and a large chemical network is attached with this hydrodynamical model to extensively study the chemical evolution during this process.


Nitrile reactivity in Titan's atmosphere

Thomas Gautier1, Nathalie Carrasco1, Arnaud Buch2, Cyril Szopa1, Ella Sciamma-O'Brien1, Guy Cernogora1

1LATMOS, Université de Versailles St Quentin, France; 2LGPM, Ecole Centrale Paris, Châtenay Malabry, France

We present the analysis of the gas phase resulting from simulation of Titan's atmosphere using RF plasma. Study of the gas phase is performed using cryogenic trapping of products. Products are analyzed with Gas Chromatography coupled to Mass Spectrometry. Results show more than 40 organic products, mainly nitriles with some hydrocarbons. The nitrile reactivity possibly leading to the formation of Titan's aerosols is then studied.


Prebiotic solid material from a Titan's atmospheric simulation

Thomas Gautier1, Nathalie Carrasco1, David Touboul2, Arnaud Buch3, Cyril Szopa1, Isabelle Scmitz-Afonso2

1LATMOS, Université de Versailles St Quentin, France; 2ICSN, Centre de recherche CNRS, Gif-sur-Yvette, France; 3LGPM, Ecole Centrale Paris, Chatenay Malabry, France

We analyzed a solid residue coming from copolymerization of organic gases. These gases, mainly nitriles and hydrocarbons, are produced in a simulation of Titan's atmosphere. The residue was studied using several analytical chemistry methods. Residue appeared to be a mixture of several copolymers with a large inclusion of nitrogen. Numerous pre-biotic nitrogenous molecules such as urea had also been detected.


An Evaluation of the Inefficiency Objection in Origin of Life Theories: A Lesson from Simpson’s Paradox

Prasanta Bandyopadhyay, Trevor Beard, John Peters, Kristen Intemann, Sara Waller

Astro-biology Biogeocatalysis Research Center, United States of America

Proponents of the Metabolism First Theory and the RNA World Theory raise an objection called “the inefficiency objection” (IO) against each other. The IO states that the reactions proposed by competing theories are both too inefficient and not specific enough to explain the generation of early life. We use Simpson’s paradox as a tool for challenging this objection. We argue that reactions can be inefficient locally, yet concurrently they could be efficient globally, leading to life’s emergence


Raman Microscopy: a Technique for Monitoring Pre-Biotic Reactions on Mineral Surfaces

Patrick J. Gasda, Anupam Misra, Shiv K. Sharma, G. Jeff Taylor

University of Hawai'i, Manoa, United States of America

We have tested the feasibility of using Raman spectroscopy to study complex systems with various amino acid-mineral combinations. Raman experiments using tyrosine aqueously deposited on a natural rutile sample shows that a new peak at 1591.6 cm-1 for tyrosine can be detected, indicating that tyrosine is interacting with the mineral. Future work with an atmospheric/temperature-controlled chamber will determine the nature of this interaction in further detail.


A Search for Maillard Products in the Murchison Meteorite

Henderson Cleaves, George Cody

Carnegie Institution of Washington, United States of America

Organics in carbonaceous chondrites likely formed from precursors such as HCHO, NH3 and HCN, which explains the amino acids detected. Some also contain sugar-like molecules possibly derived from formose reactions. This is problematic as HCHO reacts with NH3 to give HMT, and with HCN to give HOCH2CN. Sugars also react with amines via the Maillard reaction producing heterocycles which could be proxies for the presence of sugars. The results of a search for these in Murchison are reported here.


Organic matter in Kamchatka hydrothermal systems and its application to the origin-of-life scenario

Vladimir Kompanichenko

Institute for Complex Analysis, Russian Federation

About 100 organic compounds were detected in liquid and gas phases of Kamchatka hydrothermal systems, including hydrocarbons, lipid precursors, amino acids. The data are incorporated into the author’s origin-of-life scenario: 1) spontaneous self-assembly of prebiotic microsystems composed of hydrocarbons, lipids, amino acids (300-100ºC); 2) their transformation into living units in the course of thermodynamic inversion, through non-spontaneous synthesis of sugars, ATP, nucleic acids (100-70º).


South-Kamchatka hydrothermal model for the origin of life

Vladimir Kompanichenko

Institute for Complex Analysis, Russian Federation

South-Kamchatka natural model characterizes: general thermodynamic and geochemical conditions in upper 1-kilometer part of the Mutnovsky and Pauzhetsky hydrothermal systems; spatial gradients and temporal fluctuations of the parameters of rising fluid; set of organic compounds that could be involved into self-assembly/synthesis of prebiotic microsystems. Basing on the model, laboratory experiments on prebiotic chemistry under changeable conditions can be carried out.


Prebiotic chemistry of nucleic acids - as seen from quantum chemical calculations

Judit Sponer1, Arnost Mladek1, Bobby G. Sumpter2, Jiri Sponer1, Miguel Fuentes-Cabrera2

1Institute of Biophysics, ASCR, Czech Republic; 2Center for Nanophase Materials Sciences, and Computer Science and Mathematics Division, Oak Ridge National Laboratory, USA

In this presentation we overview our recent quantum chemical studies on the prebiotic synthesis of nucleic acid (NA) components. In particular, we show the advantages of our technique as compared to classical prebiotic experiments. We address the stabilization of aldopentoses via complexation with borates, thermodynamics of the nucleoside/nucleotide formation via the classical reaction as well as via the Sutherland-synthesis, and the relevance of the arsenate/phosphate substitution in NA.


Prebiotic Significance of Extraterrestrial Ice Photochemistry: Detection of Hydantoin in Organic Residues

Pierre de Marcellus1, Marylène Bertrand2, Michel Nuevo3,4, Frances Westall2, Louis Le Sergeant d'Hendecourt1,5

1Univ Paris-Sud, “Astrochimie et Origines”, Institut d’Astrophysique Spatiale, UMR 8617, F-91405 Orsay, France; 2Centre de Biophysique Moléculaire, UPR 4301, Université d’Orléans, France; 3NASA Ames Research Center, Space Science Division, Moffett Field, CA 94035, USA; 4SETI Institute, Mountain View, CA 94043, USA; 5CNRS, F-91405 Orsay, France

Ultraviolet photo-irradiation of interstellar ice analogs leads to the production of several molecules of possible prebiotic interest that are recovered in organic residues at room temperature. Here, we detect small quantities of hydantoin, a species known to play an important role in the formation of poly- and oligopeptides and also detected in meteorites. This result shows the importance of the photochemistry of interstellar ices in the formation of organics in Solar System materials.


Cyanide complexes formation and their role in chemical evolution processes

Maria Colin-Garcia1,2,3, Alicia Negrón-Mendoza2, Fernando Ortega-Gutiérrez3, Sergio Ramos-Bernal2

1Centro de Astrobiología (CSIC/INTA), Spain.; 2Instituto de Ciencias Nucleares, Universidad Nacional Autónoma de México, Mexico; 3Instituto de Geología, Universidad Nacional Autónoma de México, Mexico

Hydrogen cyanide is a parent molecule of many biorganic compounds, i.e. amino acids. Still, it is very reactive and volatile, so stabilization mechanisms are required. When solutions of HCN are mixed with clay minerals blue compounds were formed. Analysis suggest the formation of blue Prussian, by the reaction between CN- and iron. This reaction could have accomplished in many environments of primitive Earth and could be important since ferrocyanides are less toxic and more stable than cyanides.


Influence of Mineral Surfaces in the Development and Stabilization of Organic Molecules in Prebiotic Conditions

Ellen Yvette Aguilar-Ovando, Alicia Negrón-Mendoza

Instituto de Ciencias Nucleares, UNAM, Mexico

The influence of Sodium Montmorillonite on the chemical transformations undergone by nucleosides (purinic and pirimidinic) when subjected to prebiotic conditions simulating the primitive Earth is been examined. By using X-ray diffraction, UV-vis spectrophotometry and HPLC, the experiments prove the concentration capacity and protective role against external sources of ionizing radiation (specifically γ-ray) that some solid surfaces (like clays) can provide to organic compounds adsorbed on them.


The role of minerals for the formation of oligopeptide using a newly developed mineral-mediated hydrothermal reactor system

Kunio Kawamura, Hitoshi Takeya, Takao Kushibe, Yuka Koizumi

Osaka Prefecture University, Japan

Although the experiments under hydrothermal conditions support the hydrothermal formation of oligopeptides, the length and yield are not sufficient to preserve biochemical functions. We developed a mineral-mediated hydrothermal flow reactor system, which enables monitoring reactions within 1 – 200 s at 300 °C with mineral particles. We found that carbonate minerals show notable enhancement of the spontaneous elongation of alanine 4-mer while sulfide minerals do not show notable influence.


Tanpopo: Astrobiology Exposure and Micrometeoroid Capture Experiments

Akihiko Yamagishi1, Shin-ichi Yokobori1, Kensei Kobayashi2, Makoto Tabata3, Sunao Hasegawa3, Hirofumi Hashimoto3, Hajime Yano3, Masamichi Yamashita3, Hideyuki Kawai4, Kyoko Okudaira5, Satoru Nakajima6, Hikaru Yabuta6, Hajime Mita7, Kazumichi Nakagawa8

1Tokyo Univ. Pharm. Life Scie, Japan; 2Yokohama National University; 3ISAS/JAXA; 4Chiba University; 5The University of Aizu; 6Osaka University; 7Fukuoka Institute of Technology; 8Kobe University

Microbes have been collected at high altitude up to several tens km using balloons and aircrafts. To test the possible interplanetary migration of terrestrial life, we propose the microbe sampling experiments on International Space Station (ISS) . Ultra low-density aerogel will be exposed to space to capture micro-particles. The samples will be distributed to scientists to examine mineralogical, organo-chemical and microbiological characteristic of the particles.


Effects of VUV photochemistry on prebiotic organic molecules in low Earth orbit and in laboratories

Marylène Bertrand1, Annie Chabin1, André Brack1, Hervé Cottin2, Didier Chaput3, Michel Viso3, Frances Westall1

1CNRS, France; 2LISA, University Paris Est-Créteil & Paris Diderot; 3CNES, Toulouse et Paris

In the context of the emergence of the life on Earth, our group studies the formation and fate molecules synthesized in space. We have carried out studies on organic molecules that were exposed to space conditions on board the International Space Station, as well as in experiments in laboratories. After exposure, the molecules were extracted, derivatized and analyzed by GC-MS. The resistance to irradiation is function of the chemical nature of the exposed molecules and depends on the VUV range.


Photochemical processes based on Titanium dioxide produce intermediates of the citric acid cycle

Raffaele Saladino1, John Robert Brucato2, Antonio De Sio3, Giorgia Botta1, Emanuele Pace3, Lisa Gambicorti4

1University of Tuscia, Italy; 2Astrophysical Observatory of Arcetri, Firenze, Italy; 3Department of Physics and Astronomy, University of Florence, Firenze, Italy; 4CNR – National Institute of Optics, Firenze, Italy

The emergence of the citric acid cycle is one of the most remarkable aspects to understand the origin and evolution of metabolic pathways. We report here that biogenic and non-biogenic carboxylic acids are synthesized by UV irradiation of formamide in the presence of titanium dioxide afforded six of the eleven components of the reductive version of the citric acid cycle.


Non-enzymatic information transfer in a prebiotic environment

Felix Olasagasti1,2, Hyunsung John Kim2, Nader Pourmand2, David W. Deamer2

1UPV/EHU-Euskal Herriko Unibertsitatea, Spain; 2University of California, Santa Cruz

We simulated a prebiotic environment containing lipid molecules where dry and wet periods were cycled under a CO2 atmosphere. Including a DNA template in the medium, we were able to detect the presence of its complementary product after five dry/wet cycles. The product of the reaction had a 0.5% yield with respect to the template and its sequence showed that the misincorporation rate was 9.9%, as expected from a primitive and imperfect replication process.


Adenine, a component of nucleotides, interacts with decanoic acid, a possible component of the first cellular membranes

Roy Black1, David Deamer2

1Amgen Inc., Seattle, United States of America; 2University of California, Santa Cruz, Dept of Biomolecular Engineering, United States of America

The process by which amphiphilic membranes first associated with RNA in the pre-biotic environment remains unclear. We have found that adenine, a component of nucleotides, associates with decanoic acid, a prototypic amphiphilic molecule. Such interactions could facilitate both the formation of membranes and the chemical reactions leading to nucleotides, and thereby explain why amphiphiles and RNA were co-localized in protocells.


Peptide Formation and Phosphate Transfer Mediated by N-phosphono-amino acids (NPAAs)

Yufen Zhao

Xiamen University, Peoples Republic of China

The prebioticly-available N-phosphono-amino acids (NPAAs) were shown to be active in both peptides formation and phosphate transfer. Phosphate transfer between two molecular NPAAs leads to N-pyrophospho-amino acids which spontaneously produce Cyclic Acylphosphoramidates for peptide formation. Mg2+ catalyzed phosphate transfer from NPAAs to nucleoside monophosphates produce nucleoside diphosphates. It is suggested that such non-enzymatic processes might have been existed in primitive earth.


A tholin with lactate dehydrogenase enzyme-mimic activity

Cesar Menor-Salvan, Marta Ruiz-Bermejo, Luis Rivas, Susana Osuna-Esteban, Sabino Veintemillas-Verdaguer

Centro de Astrobiologia, Spain

Tholins are complex organic materials generated by irradiation of CH4, CO or CO2 atmospheres. The nature and properties of their macromolecular structures received lesser attention. We show that some tholins generated by irradiation of CH4/N2 atmospheres could mimic the lactate deshydrogenase activity and share some properties with polipeptides suggesting that the role of tholins in the origin of metabolism could be relevant.


Eutectic phases in water-ice : an efficient medium for biopolymerization

Pierre-Alain Monnard, Mark Dörr, Philipp M.G. Löffler, Rafał Wieczorek

University of Southern Denmark, Denmark

Non-enzymatic biopolymerization by monomer condensation is necessary for the emergence of life. However, this reaction is not favored in an aqueous medium. We have investigated the transient quasi-comparmentalization of monomers and catalysts (metal-ions and peptides) into a self-assembled medium, the eutectic phase in water-ice, and have established that this medium can in principle support the formation of phosphodiester bonds, thus of RNA analogs.


Magnetically induced enantioselective crystallization of sodium chlorate with hydrophobic amino acid impurities at the water-air interface

Susana Osuna-Esteban, María Paz Zorzano, Cesar Menor-Salvan, Marta Ruiz-Bermejo, Sabino Veintemillas-Verdaguer

Centro de Astrobiologia, Spain

Using crystallization of sodium chlorate as a probe for plausible amino acid enantiomeric excesses (e.e.) at water-air interface we found that an upwards pointing magnetic field induces a detectable L e.e., whereas a downwards pointing field induces a D excess. This suggest that Earth geomagnetic field may have played a significant role on the prebiotic origin of homochirality inducing an e.e. on all hydrophobic chiral amino acids.


Ionizing Radiation Assisted, Abiotic Formation of Methane

Zbigniew Paweł Zagorski, Ewa Maria Kornacka

Institute of Nuclear Chemistry and Technology, Poland

Abiotic sources of CH4 on Mars are discussed. Supply of CO2 is abundant, but H is scarce and way from CO2 to H2O involves many steps. Simulated regolith with adsorbed water, hydrated carbonates, or solid CO2/H2O composite, were gamma or fast electrons irradiated, simulating conditions on the surface of Mars. Multi-ionization spurs simulate high LET. Results of irradiations were observed by ESR technique for intermediate reactive products and by GC for stable products of radiolysis.


Peptide catalysed prebiotic polymerization of RNA

Rafał Wieczorek1,2, Pier Luigi Luisi1, Pierre-Alain Monnard2

1Dipartimento di Biologia, Università degli Studi di Roma Tre; 2FLinT Center, Department of Physics and Chemistry, Universit, Denmark

Dipeptide SerHis is reported to catalyse oligomrization of RNA monomers. This reaction was achieved in prebiotically plausible environment of water/ice eutectic phase. Successful oligomerization of RNA monomers catalysed by the SerHis was observed in a broad range of pH, and with all four natural nucleobases. Since short peptides are plausible products of prebiotic chemistry the ability of such peptides to catalyse RNA synthesis could be a link between prebiotic chemistry and the RNA world.


Ionizing Radiation Assisted, Abiotic Formation of Methane

Zbigniew Paweł Zagorski, Ewa Maria Kornacka

Institute of Nuclear Chemistry and Technology, Poland

Abiotic sources of CH4 on Mars are discussed. Supply of CO2 is abundant, but H is scarce and way from CO2 to H2O involves many steps. Simulated regolith with adsorbed water, hydrated carbonates, or solid CO2/H2O composite, were gamma or fast electrons irradiated, simulating conditions on the surface of Mars. Multi-ionization spurs simulate high LET. Results of irradiations were observed by ESR technique for intermediate reactive products and by GC for stable products of radiolysis.


A novel C-C bond forming reaction of prebiotic interest: The reductive coupling of aldehydes by H2S in aqueous solutions

Mohammed Kajjout, Yanek Hebting, Pierre Albrecht, Pierre Adam

Laboratoire de Biogéochimie Moléculaire, Institut de Chimie de Strasbourg UMR7177 CNRS-Université de Strasbourg, France

A novel reductive coupling reaction of non or poorly enolisable aldehydes induced by H2S or sulfides in water and leading to disubstituted ethylenes has been discovered. This reaction leads from glyoxylic acid to various compounds of prebiotic interest comprising, notably, fumaric, succinic, malic, and citric acids which play a role in the reductive citric acid cycle. Such a reaction might, notably, have been operative at the sulfide-rich environments of hydrothermal vents.


Phase Transitions of Non-Racemic Mixtures of Enantiomers: A Path towards Homochirality

Arkadii Tarasevych1,2, Aurélien Bellec2, Jean-Claude Guillemin2

11Institute of Bioorganic Chemistry and Petrochemistry, National Academy of Sciences of the Ukraine, Kyiv, Ukraine; 2UMR CNRS 6226 'Sciences Chimiques de Rennes', France

Homochirality – is a prerequisite for the origin of life. However, how has evolved the probably racemic prebiotic world to the homochiral life? The two main hypotheses discussed by the scientific community are the asymmetric autocatalysis (Frank’s model) and the enrichment via phase transition of scalemic mixtures of enantiomers. Our results on enantioenrichment via “solid – gas” phase transition (sublimation) of non-racemic mixtures of natural amino acids could give a part of the answer.


Photophosphorylation of ADP to ATP on Supramolecular Organo-silicate Matrices

Taisiya A. Telegina, Michael P. Kolesnikov, Yulia L. Vechtomova, Mikhail S. Kritsky

A.N.Bach Institute of Biochemistry RAS, Russian Federation

A model for abiotic photophosphoryation of ADP to ATP was studied. Spatial organization of electron movement was obtained by association of abiotic pigments of flavin or pterin nature with silicate substrate. Irradiation of matrices with ultraviolet or blue lightin the presence of ADP, orthophosphate and peroxide resulted in ATP formation. We suppose that the main stages of energy transformation during photophosphorylation on organo-silicate matrices are similar to those of biological photophosphorylation.


Effects of the incorporation of polycyclic aromatic hydrocarbons into fatty acid membranes on vesicle size, stability and permeability

Joost Groen1, David W. Deamer2, Alexander Kros1, Pascale Ehrenfreund1

1Leiden University, the Netherlands; 2University of California Santa Cruz, USA

PAH molecules can potentially be integrated into a minimal life form as container elements. We show the incorporation of several oxidized PAHs in fatty acid membranes by epifluorescence microscopy and report on the critical vesicle concentration and permeability. We used conductimetric titration as a method of determining the critical vesicle concentration of fatty acid vesicles with good accuracy and reproducibility and UV-Vis spectrometry to determine permeability.


The Role of Montmorillonite in its Catalysis of RNA Synthesis

Michael F. Aldersley1, Prakash C Joshi1, Jonathan D. Price2, James P. Ferris1

1Rensselaer Polytechnic Institute, Troy, NY, United States of America; 2Midwestern State University, Wichita Falls TX, United States of america

We have shown that the catalytic process is dependant upon the cations present, the pH and the layer charge on the catalyst surface. However, the shape and size of the nucleotide species present seemed to have little effect on the oligomerisation. X-ray diffraction and the application of the Scherrer equation to diffraction peak widths showed that the nucleotides were occupying the interlayers.


Catalysis of an exclusive RNA Dimer Synthesis by Montmorillonite

Michael F. Aldersley, Prakash C Joshi, James P. Ferris

Rensselaer polytechnic Institute, United States of America

A synthetic method has been developed to specifically provide dimers comprising standard nucleotide residues. For example, a 5’-phosphorimidazolide of a ribonucleotide (an activated nucleotide) is added to a nucleoside in the presence of a montmorillonite catalyst at neutral pH with the absence of protecting groups. In general, approximately 30% of the imidazolide is converted into the 2’-5’ product, 30% into the 3’-5’ product with the rest hydrolyzed to the corresponding 5’-monophosphate.


Motif frequency and evolutionary search times in RNA populations

Michael Stich, Susanna C Manrubia

Centro de Astrobiología (CSIC/INTA), Spain

RNA molecules are an appropriate experimental and theoretical model to study the genotype-phenotype map and evolutionary processes taking place in simple replicator populations. We show through extensive simulations how the evolution of an RNA population is constrained by (a) the type of motif, (b) the abundance of the motifs in a random pool, (c) number of base pairs, and (d) nucleotide composition. We describe the implications of our work for the RNA world scenario of the origin of life.


Theoretical approach to the emergence of homochirality

Gaël Marloie, Julien Pilmé, Françoise Pauzat, Yves Ellinger

Université Pierre et Marie Curie, France

Life on Earth is inseparable from homochirality. However, not only is the origin of this enantiomeric excess unknown but not even a single chiral molecule has been identified so far in the interstellar medium. We chose to investigate the possibilities open by a selective adsorption at chiral surfaces. The results obtained for aminoethanol, alanine and lactic acid show that the selectivity is linked mainly to the difference in the geometries of the adsorbates induced by the chiral surface.


A ‘Systems Chemistry’ Perspective on the Origins of Life

Andres de la Escosura Navazo1, Carlos Briones Llorente2, Kepa Ruiz Mirazo3

1Universidad Autónoma de Madrid, Spain; 2Astrobiology Centre CSIC INTA, Spain; 3University of the Basque Country, Spain

In this communication, we will discuss the most important implications that employing a ‘systems view’ would have in the field of prebiotic chemistry. In this way, the limitations of traditional ‘synthetic chemistry’ approaches to the problem of the origin of life will become apparent, while the potential of new methodologies that are enabling to deal with complex mixtures of (bio)molecules will be revised in detail.


Surface science approach for molecular self-assembly in prebiotic chemistry

Eva Mateo-Marti

Centro de Astrobiologia (INTA/CSIC), Spain

Understanding chemical interaction of molecules on surfaces provides fundamental information in prebiotic chemistry field. We study the adsorption of single amino acids on surfaces, furthermore, the formation of self-assembled molecular nano-structures, diffusion process and their chemical reactivity, by means of complementary and powerful surface science techniques. This research is based on an innovative approach; studies under ultra high vacuum conditions and chemisorption from solution.


Progress towards Demonstrating Homochirality in Prebiotic RNA Synthesis

Prakash Joshi, Michael Aldersley, James Ferris

Rensselaer Polytechnic Institute, United States of America

Montmorillonite clay minerals are not only excellent catalysts for the prebiotic synthesis of RNA but they also facilitate homochiral selection.


Pyrophosphate Generation Via an Ambient Proton-Motive Force: Laboratory Tests of an Alkaline Hydrothermal Origin-of-Life Scenario

Laura M. Barge1, Lauren M. White1,2, Ivria Doloboff1,3, Isik Kanik1, Michael J. Russell1

1Caltech / Jet Propulsion Laboratory, United States of America; 2University of California, Santa Barbara, Department of Chemistry and Biochemistry; 3Santa Monica College

The alkaline hydrothermal origin of life hypothesis proposes that the ambient proton-motive force attendant to hydrothermal systems on the early Earth, combined with the precipitation of catalytic iron sulfide membranes, may have provided energy to drive important prebiotic reactions such as the formation of pyrophosphate (PPi). In this study we are examining the incorporation of phosphate into an iron sulfide precipitate formed at the interface between acidic and alkaline solutions and the formation of PPi.


Stability of amino acids and their oligomerization under high pressure conditions

Tsubasa Otake1, Takashi Taniguchi2, Yoshihiro Furukawa1, Hiromoto Nakazawa2, Takeshi Kakegawa1

1Tohoku University, Japan; 2National Institute for Materials Science, Japan

Our oligomerization experiments using amino acid powders (glycine or alanine) at high temperatures (180–400ºC) and pressures (1.0–5.5 GPa) demonstrated that amino acids were oligomerized up to pentamer, and that deamination is a key process when determining the stability of amino acids and peptides at high pressures. These results suggest that diagenetic/metamorphic environments of marine sediment need to be considered as playing an important role for the prebiotic peptide formation.


Template Directed Oligomer Ligation in Eutectic Phases in Water-Ice

Mark Doerr, Philipp M. G. Loeffler, Rafał Wieczorek, Pierre-Alain Monnard

FLinT/Dept. Chemistry and Physics (IFK)/SDU Denmark, Denmark

The latest results of our experiments of template directed, non-enzymatic and metal mediated ligation of activated oligoribonucleotides in eutectic water-ice phases are presented. Different activation strategies are compared and an outlook towards applications in molecular evolution and artificial cell systems (« protocells ») will be given.


Exploring the Fate of Nitrogen Heterocycles in Complex Prebiotic Mixtures

Karen E. Smith1,2, Michael P. Callahan2,3, Henderson J. Cleaves2,4, Jason P. Dworkin2,3, Christopher H. House1,2

1Department of Geosciences and Penn State Astrobiology Research Center, The Pennsylvania State University, 220 Deike Building, University Park, PA 16802, USA; 2NASA Astrobiology Institute; 3NASA Goddard Space Flight Center, Solar System Exploration Division, Greenbelt, MD 20771, USA; 4Geophysical Laboratory, The Carnegie Institution for Science, Washington, DC 20015, USA

We have taken a complex prebiotic mixture produced by a spark discharge acting on a gas mixture of N2, CO2, CH4, and H2 and reacted it with 4 nitrogen heterocycles. We found that guanine and uracil did not react with the spark mixture, isoxanthopterin formed mainly a cyanide adduct, and 5-hydroxymethyluracil formed several products. This suggests that there are alternative nucleobases that are more reactive under prebiotic conditions and may have been involved in producing precursor nucleotides.


The Earliest History of Ion Channels

Michael A. Wilson1,2, Milan Mijajlovic1, Andrew Pohorille1,2

1NASA Ames Research Center, United States of America; 2University of California, San Francisco

Computer simulations are reported on antiamoebin and trichotoxin ion channels. These simple helical peptide bundles provide models of protobiological ion channels, as they are much simpler than modern protein channels. A prebiotic model of channel regulation based on iron binding to an extracellular domain is also discussed. The simple channels are almost as efficient as modern channels. We therefore propose that channels evolved structural complexity in order to acquire precise regulation.


Formation of amino acid precursors and their aggregates in possible primitive Earth environments including submarine hydrothermal systems

Kensei Kobayashi1, Hironari Kurihara1, Hideharu Kuwahara1, Yumiko Obayashi1, Takeo Kaneko1, Hikaru Yabuta2, Hajime Mita3, Yoshinori Takano4

1Yokohama National University, Japan; 2Osaka University; 3Fukuoka Institute of Technology; 4Japan Agency for Marine-Earth Science and Technology

We examined possible formation of amino acids and their aggregates in possible primitive Earth environments. At first, we confirmed that precursors of amino acids could be formed from mildly reduced or neutral gas mixtures. When these precursors were treated in a flow reactor simulating submarine hydrothermal systems, organic aggregates were formed. The present results showed that bioorganic compounds and their aggregates could be formed in possible primitive Earth environments.


Prebiotic Peptide Formation

Guillermo Mosqueira1, Carlos Polanco2, Alicia Negron-Mendoza3, Sergio Ramos-Bernal3, Thomas Buhse2

1Dirección General de Divulgación de la Ciencia, Universidad Nacional Autónoma de México; 2Centro de Investigaciones Químicas, Universidad Autónoma del Estado de Morelos; 3Instituto de Ciencias Nucleares, Universidad Nacional Autónoma de México

We study a primitive oligomerization mechanism with the aid of a simple probabilistic model and computational tools. We compare the sequences produced with such theoretical means with those from more ancient organisms and find a fairly good match. A main premise of such studies is that the reactivity among monomers is different.


Analyses of thermal proteinoid from monoammonium malate and formation of proteinoid microsphere.

Hiroshi Kanamaru1, Yusuke Kuwahara1, Mami Tsuruyama1, Shinya Nomoto2, Hajime Mita1

1Fukuoka Institute of Technology, Japan; 2University of Tsukuba, Japan

Proteins are ones of the most important organic compounds in terrestrial living organisms. We focused on the thermal proteinoid which is a kind of polyamino acid was synthesized in molten stage of monoammonium malate and microsphere is formed In this study, we studied the physical and chemical properties of the proteinoid and its microsphere by LC-MS, GPC, IR, and SEM. And we found that microsphere is a self-organization product of small polyamino acids with hydrophobic interaction.


Organic compounds exposure and organic compounds analyses of captured particles in TANPOPO mission.

Hajime Mita1, Kensei Kobayashi2, Keisuke Ono2, Kumar S. Palash2, Kazumichi Nakagawa3, Hikaru Yabuta4, Yuichiro Ogata4, Satoru Nakashima4, Kenji Hamase5, Yurika Miyoshi5, Hiroshi Naraoka5, Eiichi Imai6, Kazuhiko Fukushima7, Kaori Saito7, Kyoko Okudaira8, Yuko Kawaguchi9, Shin-ichi Yokobori9, Makoto Tabata10, Hideyuki Kawai11, Hirofumi Hashimoto10, Hajime Yano10, Jun-ichi Takahashi12, Akihiko Yamagishi9

1Fukuoka Institute of Technology, Japan; 2Yokohama National University; 3Kobe University; 4Osaka University; 5Kyusyu University; 6Nagaoka University of Technology; 7Nagoya University; 8Aizu University; 9Tokyo University of Pharmacy and Life Sciences; 10Japan Aerospace Exploration Agency; 11Chiba University; 12NTT

TANPOPO is an astrobiological mission of analyses of interplanetary migration of microbes, organic compounds and micrometeoroids on Japanese Experiment Module (JEM) ‘KIBO’ of the International Space Station (ISS). In ‘Tanpopo’ mission, we will analyze organic compounds in micrometeoroids captured on the ISS-Kibo without terrestrial contaminants and damage. In addition, we will the alteration of bioorganic compounds and synthesis of dipeptide in the space environment.


Oligomerization of valine under high temperature and high pressure conditions

Yoshihiro Furukawa1, Tsubasa Otake1, Takato Ishiguro1, Hiromoto Nakazawa2, Takeshi Kakegawa1

1Tohoku University, Japan; 2National Institute for Materials Science, Japan

We performed heating experiments of compressed solid valine at several temperatures and pressures to investigate how they affect the reaction rates of peptide formation and the stabilities of valine and peptides under the conditions of diagenesis. We synthesized peptides up to hexamer. Increasing pressure inhibited the degassing decompositions of valine. This result suggests that the pressure increase the yields of peptides in diagenesis


Interaction of adenine with Na, Ca, Mg, Fe, Cu, Co-montmorillonite

Dimas Zaia1, Cláudio Souza1, João Baú1, Laura Zaia2, Cristine Carneiro1, Cássia Zaia3, Henrique de Santana1

1Laboratório de Química Prebiótica, Departamento de Química-CCE, Universidade Estadual de Londrina, Brazil; 2Departamento de Engenharia Química, Universidade Federal do Paraná, Brazil; 3Departamento de Ciências Fisiológicas-CCB, Universidade Estadual de Londrina, Brazil

Montmorillonites with metals (Na, Ca, Mg, Fe, Co, Cu) were prepared. FT-IR spectrum of adenine shows bands in 1603 and 1672 cm-1 which could be attributed to C=N stretching and NH2+ deformation. When adenine was dissolved in seawater and this sample was lyophilized the bands above shifted to 1610 cm-1 and 1700 cm-1. After adenine was adsorbed on Fe and Cu-montmorillonite the bands above were shifted to 1633 and 1700 cm-1. The spectra of the lyophilized solutions did not show any bands of the adenine.


A study of adsorption of cysteine on forsterite 91: Implications for prebiotic chemistry

Dimas Zaia, Cláudio Souza, João Baú, Cristine Carneiro, Henrique de Santana

Universidade Estadual de Londrina, Brazil

We studied the adsorption of cysteine on forsterite in two different initial pHs (2.00, 8.00). The adsorption of cysteine on forsterite did not depend on pH and it was about 100%. The FT-IR spectra of the adsorbed cysteine on forsterite and aqueous solutions showed bands of cysteine and cystine. The oxidation of cysteine to cystine can be associated to the reduction of Fe3+ to Fe2+.


Emergence of Population Structure and Functional Evolution in Simulations of Environmentally Driven Replication

Sara Imari Walker1,2,3, Martha A. Grover1,4, Nicholas V. Hud1,2

1NSF/NASA Center for Chemical Evolution, United States of America; 2School of Chemistry and Biochemistry, Georgia Institute of Technology; 3NASA Astrobiology Institute; 4School of Chemical and Biomolecular Engineering, Georgia Institute of Technology

A key question in the origin of life is how informational polymers self-organized into increasingly complex systems. We explore a model of prebiotic evolution with polymer replication/degradation driven by day-night cycles and present a mapping of system response to several model parameters to guide experimental searches for the simplest evolvable chemical systems. The dynamics observed provide new insights into system features needed to exhibit properties necessary for the emergence of life.


Self-assembly under dry conditions: the growth of PAH chains between two crystal solids

Thomas Markert1, Norbert Gast2, Frank Trixler2,3

1Institut für Theoretische Chemie, Universität Ulm, Ulm, Germany; 2Physik Department, Technische Universität München (TUM), Germany; 3Department Earth and Environmental Sciences, Ludwig-Maximilians-Universität München (LMU) & Center for NanoScience (CeNS), München, Germany

In numerous theories on prebiotic chemistry the mineral/water interface plays a major role. Here we present a process which allows even for insoluble molecules such as PAHs to form supramolecular structures on mineral surfaces. This process occurs at the interface between two different crystals and does not require any solvent: the organic molecules self-assemble into one- and twodimensional structures under ambient condition in an insoluble or even dry environment.


Effect of Dissociation of Water Molecule by Plasma on Chemical Evolutionary Formation of Carbon Compounds

Toratane Munegumi

Oyama National College of Technology, Japan

This research demonstrates the importance of hydrogen and hydroxyl radicals induced from water molecule by plasma including electric discharge, plasma jet blowing, and other energy sources in chemical evolutionary formation of many carbon compounds. Reduction of carbonate was carried by 4 hours’ nitrogen plasma jet blowing to give 70% formate after 240 min. The results show water molecule may hav mediated reductive reactions under the non-reduding atmosphere.


Interpretation by the DSNL-0 ribozyme and its implications to origins of life

Brian Larson1, Christopher Southgate2, Andrew Robinson2, Niles Lehman1

1Portland State University, United States of America; 2University of Exeter, United Kingdom

With the discovery of catalytic RNA molecules with a diverse catalytic inventory, a historical period has been suggested where RNA maintained both the phenotype and genotype of primitive life. Using a modified version of the DSL ribozyme, this in vitro evolution study investigates the potential role of interpretation as defined by Robison and Southgate as a selection pressure in early evolutionary steps in the emergence of life and foundation of such properties in an RNA world.


The abiotic fixation of nitrogen on mars and other terrestrial planets: conversion of nitrogen, through NO, into nitrate, nitrite, ammonia, and nitrous oxide.

David Summers1, Bishun Khare1, Ranor Basa2, David Rodoni2

1Carl Sagan Center - SETI Institute, United States of America; 2Foothill College, United States of America

One route for abiotic nitrogen fixation in a neutral atmosphere starts with formation of NO by shock heating. We present work on the subsequent chemistry of NO. One pathway is photochemical conversion to nitrate/nitrite through HNO. Another involves the photochemical formation of NO2, and its possible conversion to HNO3. Our most recent work show that NO can be directly reduced to ammonium by FeS. In such reduction, a catalytic disproportionation to N2O and NO2 also occurs.


Extraterrestrial and Terrestrial Minerals in "BION" Flight Experiment: Selection of the Best Matrix for Photochemical Processes

Natalia Gontareva1, Evgenia Kuzicheva1, Vyacheslav Ilyin2

1Institute of Cytology RAS, Russian Federation; 2Institute of medical and biological problems RAS, Russian Federation

Amino acids and nucleosides were irradiated (UVC 145 and 154 nm) in presence of lunar soil, Allende and Murchison meteorites, pyroxene and olivine in solvent-free conditions. Our purpose was to distinguish differences, if any, of minerals participating in chemical processes and to figure out the most efficient mineral matrix. The most “chemically active” mineral will be employed at flight experiment Bion-10M. Hardware and strategy of the whole experiment will be reported as well.


Prebiotic scenarii and surface science

Jean-François Lambert1, Mariona Sodupe2, Piero Ugliengo3

1Laboratoire de Reactivite de Surface (UMR7197 CNRS) UPMC, France; 2Departament de Química, Universitat Autònoma de Barcelona; 3University of Torino, Dip. Chimica IFM

In this contribution we assess the current state of "surface scenarii", i.e. prebiotic scenarii involving the participation of mineral surfaces. Progress has been slow in the field because surfaces have not been considered at the same level of molecular detail as the prebiotic molecules interacting with them. Drawing from our own and others' research, we show how recent progress in computational chemistry allows to better design experiments involving surfaces and understand their results.


Chiral nanotubes in the interstellar medium and the origen of biological chirality

Germinal Cocho, Hugo Ivan Cruz

Instituto de Fisica, Universidad Nacional Autonoma de Mexic, Mexico

There is quite strong evidence that chirality origen is prebiological and could take place in the interstellar medium. Experiments are proposed on amino acids in Cu or Au chiral surfaces on the action of electromagnetic radiation. The search of chiral nanotubes in meteorites arriving to earth is also consider. Evidence in support of these two proposal is also given.


Complexity, self-organization and catalytic activities of peculiar (life-like) metallorganic entities generated on Earth from or below mineral iron surfaces.

Rosanna del Gaudio1, Giuseppe Geraci2, Bruno D'Argenio3

1University of Naples Federico II Dept of Biological Sciences, Italy; 2Società Nazionale di Scienze Lettere ed Arti, Naples Italy; 3IAMC, CNR, Naples, Italy

We report evidence that both extraterrestrial and terrestrial minerals and rocks containing iron catalyze inorganic and organic reactions leading to production of metallorganic entities able to perform catalytic activities typical of modern life.While these properties indicate that they might be examples of prebiotic catalysts,complexity of their structures and chemical composition leave open the possibility that they might even represent a kind of non conventional form of pre-terrestrial life.


Citric acid, pyruvic acid, and homologs in carbonaceous meteorites: identifications and possible synthetic origins

George Cooper1, Chris Reed1, Dang Nguyen1, Malika Carter1, Yi Wang2

1NASA Ames Research Center, United States of America; 2DPRA/ZymaX Forensics Isotope

We report three new classes of meteoritic organic compounds: keto acids, hydroxy tricarboxylic acids and tricarboxylic acids. Some of the compounds such as pyruvic acid and citric acid are at the core of intermediary metabolism. Isotope values and molecular distributions point to extraterrestrial origins. Laboratory syntheses using 13C-labeled reactants indicate that pyruvate alone can produce several potentially important pre-biotic compounds including oxaloacetic acid and citric acid.


Impact Delivery of Prebiotic Molecules to Planetary Surfaces: Chemical Modeling

Jennifer Blank, Nicolas Winter

SETI Institute, USA

In this paper, we model the pressure dependence of amino acid polymerization during shock processing and discuss our results in the context of prebiotic chemical evolution during impact delivery of organic molecules to terrestrial planets.


Stationary reproduction in model protocells

Fabio Mavelli1, Kepa Ruiz-Mirazo2,3

1Dpt. Chemistry, University of Bari, Italy; 2Dpt. Logic and Philosophy of Science, UPV/EHU, Spain, Unidad de Biofísica (CSIC-UPV/EHU), Spain; 3Unidad de Biofísica (CSIC-UPV/EHU), Spain

Theoretical conditions were obtained for model protocells to spontaneously settle into a stationary self-reproducing regime, with a regular growth/division cycle and a standard size and chemical composition across generations. Following mostly geometric considerations, a general relationship between the different molecular and kinetic variables involved was analytically derived and then applied to specific cases, providing a direct link to a few measurable parameters of the system.


Iron-sulfur cluster biosynthesis - understanding the transition from the nonliving to the living Earth

Neelambari Joshi, Cedric Pienton, Eric Shepard, Ben Duffus, Joan Broderick, John Peters

Astrobiology Biogeocatalysis Research Center, United States of America

Iron-sulfur proteins are ubiquitous and catalyze a number of reactions important to metabolic energy transformations and carbon and nitrogen fixation. Our recent work on the biosynthesis of iron-sulfur clusters of hydrogenases and nitrogenases have provided insights into the evolutionary origin of these key enzymes. New insights into biological iron-sulfur cluster biosynthesis will be discussed in the context of prebiotic chemistry and ligand assisted catalysis.


Enantiomeric Excesses in Meteoritic Sugar Acids

George Cooper

NASA Ames Research Center, United States of America

Measurements of the enantiomer ratios of sugar acids from carbonaceous meteorites reveal anomalous excesses of the D enantiomers. The excesses are found in the four-, five-, and six-carbon members, apparently increase with carbon number, and are contained in both biological and rare compounds. If confirmed, the results suggest that meteoritic material could have played a role in the origin and/or evolution of life’s homochirality.


Photodegradation of Acetonitrile Under Simulated Prebiotic Anoxic Conditions

Daniele Merli, Daniele Dondi, Luca Pretali, Antonella Profumo, Elisa Fasani

Dipartimento di Chimica- Università degli Studi di Pavia, Italy

Acetonitrile photodegradation in simulated marine prebiotic anoxic conditions was investigated and the effects of various ions was studied.


Parity violation effects in heavy atom containing compounds.

Daniele Dondi, Daniele Merli, Antonella Profumo, Armando Buttafava, Antonio Faucitano

Dipartimento di Chimica- Università degli Studi di Pavia, Italy

The aim of this work is to put the basis for a theoretical PVED calculation of chiral compounds containing heavy elements that are already known in literature and thus their practical synthesis is feasible and the theoretically investigated properties could be experimentally verified. Our search has included models of molecules possessing atropisomerism and chiral crystals of achiral molecules containing heavy elements (i.e. cinnabar).


Peptides Synthesis under Thermal Synthesis Mode

Olga Victorovna Demina, Alexey Vladimirovich Laptev, Alexey Sergeevich Kononikhin, Eugene Nikolaevich Nikolaev, Andrey Alexandrovich Khodonov, Sergey Dmitrievich Varfolomeev

Emanuel Institute of Biochemical Physics of Russian Academy, Russian Federation

The problem of emergence of macromolecules such as proteins and nucleic acids is very important for understanding of life origin. We studied the possibilities of peptides syntheses from amino acids mixtures under both thermal synthesis mode and thermal cycling mode. Compositions of resulting mixtures and amino acid sequences of individual products have been identified by methods of ion cyclotron resonance mass spectrometry. Maximal diversity of products has been observed under thermal synthesis.


Asparagine in Chemical Evolutionary Process

Toratane Munegumi

Oyama National College of Technology, Japan

Although asparagine is a chemically reactive compound as well as a proteinous amino acid, there are not many reports to mention about the importance of asparagine. The research demonstrates the merits of asparagine in chemical evolutionary process as follows: (1) asparagine emerges from simple amino acids and formamide, (2) asparagine relates to the origin of homochirality of amino acids, (3) asparagine forms polypeptides .


Chemical Processing of Meteorites : Implications for Abiogenesis

Barry Herschy1, David Bryant1, David Greenfield2, Terence Kee1

1University of Leeds, United Kingdom; 2Sheffield Hallam University, United Kingdom

Meteorites have long been considered a source of prebiotic material which could have assisted in the origination of life on Earth. Phosphorus is critical to the biochemistry of all life on this planet. Investigations into the phosphorus species producible by anoxic meteoritic corrosion and attempts made to quantify the amounts of each species made have been conducted. This information can then be used to predict potential early Earth levels available for reaction in prebiotic chemistry.


Iron-sulfur cluster biosynthesis - understanding the transition from the nonliving to the living Earth

Cedric Pienton

Montana State University, United States of America

Iron-sulfur proteins are ubiquitous and catalyze a number of reactions important to metabolic energy transformations and carbon and nitrogen fixation. Our recent work on the biosynthesis of iron-sulfur clusters of hydrogenases and nitrogenases have provided insights into the evolutionary origin of these key enzymes. New insights into biological iron-sulfur cluster biosynthesis will be discussed in the context of prebiotic chemistry and ligand assisted catalysis.


Plasma spark discharge promoted prebiotic reaction of CO2 / sea water aerosol

Daniele Dondi, Daniele Merli, Luca Pretali, Elisa Fasani, Armando Buttafava

Università degli Studi di Pavia, Italy

An expressly designed apparatus was realized to allow us to perform reactions in the aerosol phase under plasma discharge. Experiments were conduced on water mixtures simulating the composition of the primordial oceans and different gaseous phases.


Comparison of the Roles of Nucleotide Synthesis, Polymerization, and Recombination in the Origin of Autocatalytic Sets of RNAs.

Paul Higgs

McMaster University, Canada

In order to investigate the origin of the RNA World, we study a mathematical model of RNA polymerization. We consider ribozymes that act as nucleotide synthases, polymerases, and recombinases. We show that autocatalytic states can arise with each of these kinds of ribozyme. If complexes formed by associations of shorter strands can act as catalysts without being covalently linked, this makes the emergence of an autocatalytic system from an abiotic polymerization system much more likely.


Effects of pH and temperature on dimerization rate of glycine: Evaluation of favorable environmental conditions for chemical evolution of life

Kasumi Sakata, Norio Kitadai, Tadashi Yokoyama

Osaka University, Japan

We studied the effects of pH and temperature on the dimerization rate of glycine (Gly). Gly solutions having pH from 3.1 to 10.9 were heated for 1–14 days at 120–140 °C, and changes in concentrations of products were evaluated. The dimerization rate of Gly reached a maximum at about pH 9.8 and the activation energy of 88 kJ/mol was obtained. Based on these results, we determined that Gly dimerizes most efficiently under alkaline pH (~9.8) at about 150 °C.


Towards a Prebiotic Model of Peptide Nucleic Acid (PNA) Directed Translation

Abhishek Singhal, Peter E. Nielsen

University of Copenhagen, Denmark, Denmark

The pseudopeptide nucleic acid mimic PNA (peptide nucleic acid) has been proposed as a possible prebiotic genetic material capable of performing sequence information transfer (“replication”). We now show that amino acid “charged” PNA oligomers can also perform sequence directed amino acyl transfer reactions, primitively mimicking tRNA/mRNA/ribosomal translation. The results relate to conditions for the translation process thereby contributing to the discussion of possible prebiotic emergence of translation.


The Formation and Chemistry of Reactive Species Produced in a Formamide Pulse Discharge: a Study of the Possible Precursors of Biomolecules

Petr Kubelík1,2, Svatopluk Civiš1, Martin Ferus1,2

1J. Heyrovský Institute of Physical Chemistry of the ASCR, Czech Republic; 2Institute of Physics, Czech Academy of Sciences, Czech Republic

A numerical kinetic model was constructed for the interpretation of the time resolved spectroscopic data acquired in formamide discharge experiment. Reactive radicals and atoms (e.g.: CN, NH, CH, H, C, N) as well as stable molecules (e.g.: HCN, N2O, CO, CO2, N2) chemistry was examined using this model and chemical dynamics of the prebiotic fragments formation was simulated.


The Dissociation of Formamide and Simple Molecular Fragments as the Origin of Life

Martin Ferus1,2, Svatopluk Civiš1, Petr Kubelík1,2

1J. Heyrovsky Institute of Physical Chemistry of the ASCR, Czech Republic; 2Institute of Physics, Czech Academy of Sciences, Czech Republic

High resolution FT-IR spectroscopy was used for the analysis of the gaseous decomposition products of the formamide molecule in three different systems: high energy LIDB plasma, glow discharge and UV photodissociation. A simulation of the reaction-dynamics was performed for the estimation of the main reaction pathways of formamide dissociation and simple molecular and radical fragment formation.


A Niche for Early Life in Early Archean Serpentine Mud Volcanoes at Isua, Greenland

Francis Albarède1, Marie-Laure Pons1, Ghylaine Quitté1, Toshiyuki Fujii2, Minik Rosing3, Bruno Reynard1, Frédéric Moynier4

1Ecole Normale Superieure, France; 2Research Reactor Institute, Kyoto University, Japan; 3Natural History Museum of Denmark, Copenhagen, Denmark; 4Department of Earth and Planetary Sciences, Washington University, St. Louis, MO, USA

Zn in Isua and Marianas serpentinites is conspicuously depleted in heavy isotopes. Zn isotope fractionation between aqueous Zn species was also investigated by ab initio methods. Under high PCO2 conditions, negative del66Zn is expected in sulfides precipitated at pH>9. Isua fluids (H2-rich, high-pH, 100-250°C) resemble the fluids sampled in the mud volcano serpentinites of the Mariana forearc. Archean serpentine mounds form a particularly favorable setting for the stabilization of amino acids.


Photochemistry of coronene and pyrene adsorbed on or trapped in water ices

Zhora Guennoun, Christian Aupetit, Joëlle Mascetti, Nicolas Daugey

Institut des Sciences Moléculaires - UMR5255, Université de Bordeaux, France

UV photochemistry of PAH models for astrochemistry has been investigated at cryogenic temperatures when they are in interaction with water in argon matrices, adsorbed on amorphous water films, and embedded in solid water. Quinone and diol photoproducts have been identified by FTIR spectroscopy with the support of DFT calculations. The photochemistry described here occurs at conditions relevant to dense molecular clouds, icy planetary surfaces and non ionizing regions.


Amino acids : new results in computation of Electronic Circular Dichroism Spectra

Martine Adrian-Scotto, Serge Antonczak, Uwe J. Meierhenrich

L.C.M.B.A.(UMR 6001), Université de Nice-Sophia Antipolis, France

Molecular Modeling can be a useful tool to access the knowledge of photon absorption by amino acids. Electronic transitions are here estimated using quantum mechanical calculations. The originality of this work is to propose average ECD spectra produced on the basis of a Boltzmann population analysis. We present our results obtained for the L-form of four amino acids, for wavelengths between 100 and 300 nm.


Mechanisms of Formamide Condensation to Purine Nucleobases

Greg Springsteen, Jeremy Hudson, Joseph Eberle, Raj Vachhani, Luke Rogers

Furman University, United States of America

The formation of nucleobases through formamide condensation is well-described. Reports of the mechanism of adenine synthesis typically include the condensation of multiple cyanides into a diaminomaleonitrile intermediate. The pathway to purine, the most abundant product, has been less-well studied, though progress through a pyrimidine intermediate has been reported. We will present data suggesting both of these mechanisms are incomplete descriptions, and will propose an alternative pathway.