Prebiotic Chemistry and the Origin of Life Prebiotic Chemistry and the Origin of Life. The possible role of UV radiation Claudia Crestini, Dipatimento di Scienze e Tecnologie Chimiche, Tor Vergata University, Rome, Italy Raffaele Saladino, Dipartimento di Agrobiologia ed Agrochimica, Università della Tuscia, Viterbo, Italy.  WUTA08
1st Italian Workshop on UltraViolet Techniques and Applications

The RNA World Hypothesis Time diagram for the origin of the first cell tra i vari processi un fenomeno rilevante sintesi biomolecole necessarie per la nascita del primo organismo chimica prebiotica Tra le biomolecole fondamentali per l’origine della vita gli acifdi nucleici hanno un ruolo rilevante in quanto conservano e trasferiscono l’informazione geneticaPrebiotic chemistry section of Origin of informational polymers Joyce, G.F. (2002) Nature 418, 214-221. Prebiotic chemistry: synthesis of biological molecules necessary for the birth of the first living cell Origin of informational polymers  Claudia Crestini - WUTA08

Heterotrophic theory A primordial soup of simple molecules arose first driven by non biological energy like radiation or heat assembled in complex molecules and led to primitive life forms Heterotrophic theory tra le teorie più studiate suggerita per la prima volta in the  Claudia Crestini - WUTA08

A heterotrophic origin of life? Reducing atmosphere Biomolecules synthesis Precursori chimici elementari si formano mediante reazioni nell’atmosfera prebiotica si concentrano nella prebiotic soup dove avvengono trasformazioni più complesse fino Prebiotic soup Complex molecules  Claudia Crestini - WUTA08

Formamide as prebiotic probe “Simulations based on Density Functional Theory show that formamide is the most stable species with molecular formula “CHON” Pauzat, F. et al. 6th EANA 2006 “This one-carbon molecule was detected in the gas phase of interstellar medium” Crovisier, J. Astrobiology: Future Perspectives, Kluwer Eds, 2004 Chapter 8, p. 179-203. “in the long period comet Hale-Bopp“ Bockelee-Morvan,D. et al. Astr. Astrophys. 2000 “and tentatively in the solid phase on grains around the young stellar object W33A “ W.A. Schutte et al. Astr. Astrophys. 1999  Claudia Crestini - WUTA08

Formamide. Phisical and Chemical properties “Formamide has a high boiling point, without azeotropic effects, and a wide range of uses as a solvent. It has an efficient solubilizing effect on nucleobases, nucleosides, nucleotides, amino acids, proteins, sugars, metalsand salts” Becker, B. J. Chem. Eng. 1970 Colloids and surfacesA: Physicochem Eng. Aspects 2003 219: 281-290. A comparison of micelle formation of ionic surfactants in formamide, in N-methylformamide and in N, N-dimethylformamide. M.Salim Akhter, Sadeq M. Alawi Langmuir. 2004 Jan 20;20(2):329-35. Solvation dynamics of formamide and N, N-dimethylformamide in aerosol OT reverse micelles. Shirota H, Segawa H.  Claudia Crestini - WUTA08

Elemental formamide chemistry Formata da ossidi per scarica elettrica o da hcn idrolisi che è uno dei precursori chimici (A) (B)  Claudia Crestini - WUTA08

The mineral Honeycomb Role of minerals metals and metal oxides in prebiotic chemistry La reattività della formammide può essere tunata da metalli e ossidi metallici  Claudia Crestini - WUTA08

The role of minerals and metal oxides on prebiotic processes The role of minerals and metal oxides on prebiotic processes. A general overview Minerals can accumulate the prebiotic precursors (concentration effect) Minerals can act as catalytic environments, reducing the activation energy for the formation of products Minerals can tune the selectivity of prebiotic syntheses Minerals may act as a template Minerals are benign environments to preserve newly formed biomolecules from degradation  Claudia Crestini - WUTA08

Claudia Crestini - WUTA08 Bioorganic Med. Chem. 9 (2001) 1249-1253 A Possible Prebiotic Synthesis of Purine, Adenine, Cytosine, and 4(3H)-Pyrimidinone From Formamide: Implications for the Origin of Life Raffaele Saladino, Claudia Crestini, Giovanna Costanzo, Rodolfo Negri and Ernesto Di Mauro Sintetizzate contemporaneamente  Claudia Crestini - WUTA08

Analyzing the reaction mechanism Analyzing the reaction mechanism. 13C/15N-NMR Experiments “route of the purine ring” Nella sintesi di alcune di queste molecole sono coinvolti anche hcn e ammonia che si formano…  Claudia Crestini - WUTA08

Analyzing the reaction mechanism. “route of the pyrimidine ring” Pyrimidine nucleobases require a redox stage for their synthesis  Claudia Crestini - WUTA08

Toward an extraterrestrial synthesis of nucleobases Extraterrestrial minerals, cda Draco constellation Anselm Kiefer High Museum of Art Atlanta, USA

Cosmic dust Claudia Crestini - WUTA08 Cdas are amorphous materials composed mainly by silica magnesium iron and other heavy metals  Claudia Crestini - WUTA08

Cosmic dust analogues preparation (Fayalite) 1) Fe2SiO4* 2) Mg0.5Fe1.5SiO4 * 3) MgFeSiO4 * (Olivine) SiO2, MgO, FeO2 4) Mg1.5Fe0.5 SiO4 * Laser Ablation 5) Mg2SiO4 * (Fosferite) Cosmic dust not available. Laser ablation for cdas in collaboration Cosmic dust analogue olivines (Mg,Fe)2SiO4 are synthesized by laser ablation technique (Nd-YAG 108 Wcm-2). Oxide pellets of MgO, FeO2, SiO2 are used as laser target vaporized in 10 mbar atmosphere of O2. Brucato, J. R. et al in The Astronomy and Astrophysics Review, Volume 11, Issue 2-3, pp. 97-152 (2003)  Claudia Crestini - WUTA08

Synthesis and Degradation of Nucleic Acid Components by ChemBioChem 6 (2005) 1368-1374 Synthesis and Degradation of Nucleic Acid Components by Formamide and Cosmic Dust Analogues Raffaele Saladino, Claudia Crestini, Veronica Neri, John R. Brucato, Luigi Colangeli, Fabiana Ciciriello, Giovanna Costanzo, and Ernesto Di Mauro Fe Si Mg fayalite forsterite olivine CDAs qualitative composition mAInly pyrimidines DHU:5,6-DiHydroUracil  Claudia Crestini - WUTA08

Synthesis and Degradation of Nucleic Acid Components by ChemBioChem 6 (2005) 1368-1374 Synthesis and Degradation of Nucleic Acid Components by Formamide and Cosmic Dust Analogues Raffaele Saladino, Claudia Crestini, Veronica Neri, John R. Brucato, Luigi Colangeli, Fabiana Ciciriello, Giovanna Costanzo, and Ernesto Di Mauro Yield defined as mg of product per gram of formamide. Fe Si Mg fayalite forsterite olivine mg/g Selectivity tuned by the elemental composition of the catalyst. Cdas * cytosin in higher amount thant terrestrian analogues. Cytosyne decrease decreasing iron in the catalyst compositon in accord with the hypothesized redox step in the general mechanism for pyrimidine nucleobases formation  Claudia Crestini - WUTA08

Moving towards nucleosides Photocatalysts for the synthesis of nucleosides. Nucleosides are the building …

From Formamide: Implications for the Origin of Life ChemBioChem 4 (2003) 514-521 One-pot TiO2-Catalyzed Synthesis of Nucleic Bases and Acyclonucleosides From Formamide: Implications for the Origin of Life Raffaele Saladino,a,* Claudia Crestini,b Umberto Ciambecchini,a Rodolfo Negri,c Giovanna Costanzo,c Ernesto Di Mauro c, With tio2 a large array of nucleobases adenine, cytosine and tymine and 3 acyclonucleosides in which a purine nucleotide is linked to a sugar in the side chain Adenine, cytosine and thymine 3 acyclonucleosides  Claudia Crestini - WUTA08

Thymine synthetic pathway R. H. Barker, 1975 In the synthesis of nucleobases and nucleosides formaldehyde generated in situ by hconh2 degradation plays a relevant role unica sintesi one pot della timina descritta in letteratura che è una delle basi più importanti Unic known one pot synthesis of thymine!  Claudia Crestini - WUTA08

Thymine from formamide Present day biosynthesis of thymidine La sintesi è simile alla via biosintetica alla timidina nella cellula  Claudia Crestini - WUTA08

Nucleosides from formamide Compd 9 Compd 10 In alta reasa  Claudia Crestini - WUTA08 Compd 11

Sugars synthetic pathway. The formose reaction. Butlerow, 1861. spiegare Single headed arrows represent aldol Condensations. Double-headed arrows represent enolizations. Aldotreose can undergo a reverse aldol condensation  Claudia Crestini - WUTA08

A novel formose reaction Unic known prebiotic syntesis of nucleosides! Activated formaldehydeunica sintesi nota di nucleosidi in condizioni prebiotiche  Claudia Crestini - WUTA08

Exploring the role of UV-radiation in prebiotic chemistry Up to now a volcanic scenario. A similarscenario could occur by uv irradiatiation

UV radiation in prebiotic chemistry. Pioneering studies Uv ray miller pionier dimer trimer diamminomalonitril hn cyclize key imidazole intermediate Diamminomalononitril cyclization to a key imidazole intermediate  Claudia Crestini - WUTA08

UV radiation in prebiotic chemistry. Pyrimidine From Cyanoacetaldehyde 30-50% yield hn Pyrimidine by hn from cianoacetaldehydehn double bond isomerization for cytosine ring closure Double bond isomerization for cytosine ring closure M. P. Robertson, S. L. Miller Nature 1995, 972.  Claudia Crestini - WUTA08

UV radiation in prebiotic chemistry. Glyoxal From formaldehyde H. Mordehai BioSystems 1979, 11(4), 227-32  Claudia Crestini - WUTA08

Exploring the role of UV-radiation on formamide prebiotic chemistry Formamide chemistry nearly no data for uv radiation

Senanayake, S. D. and Idriss, H. (2006) PNAS. USA 103 Photocatalysis and the origin of life: Synthesis of nucleoside bases from Formamide on TiO2(001) single surface. Senanayake, S. D. and Idriss, H. (2006) PNAS. USA 103 Confirmed our studies on uv radiation. All nucleobases synthesizaed our interest is to develop novel prebiotic chemistry of nucleic acids based on formamide under uv irradiation in the presence of ninerals or selected organic compounds that can act as photocatalysts we hope that the syncrotone facility can be used for this novel approach toesobiology. Uncorrected peak areas of desorbing products The surface structures of TiO2 (001) single crystal

Exploring the role of UV-radiation on formamide prebiotic chemistry our interest is to develop novel prebiotic chemistry of nucleic acids based on formamide under uv irradiation in the presence of minerals or selected organic compounds that can act as photocatalysts. we hope that the syncrotron facility can be used for this novel approach to esobiology  Claudia Crestini - WUTA08

Thank you for the kind attention!