WUTA081st Italian Workshop on UltraViolet Techniques and Applications

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.

Joyce, G.F. (2002) Nature 418, 214-221.

 Claudia Crestini - WUTA08

The RNA World Hypothesis

•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

Reducing atmosphere

Biomolecules synthesis

Prebiotic soup Complex molecules

A heterotrophic origin of life?

 Claudia Crestini - WUTA08

Formamide as prebiotic probe

H NH2

O “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

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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.

“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

Formamide. Phisical and Chemical

properties

 Claudia Crestini - WUTA08

HCN + H2OH2N H

O

Formamide

+ H2O-O H

O

Ammonium formate

NH4+t1/2= ca. 40 yr

at 60°C and pH 6.0

t1/2 ca. 10 yrat 30°C and pH 6.0

radicalconditions

H H

O

Formaldehyde

Sugars

Thermaldegradation> 210 °C

HCN H2O

NH3 CO

Thermaldegradation

(Hofmann, Ber. 1882)

HNCO H2

(Lin, Langmuir 1994)

Hydrogencyanide

(A) (B)

(C)

(D)

Elemental formamide chemistry

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 Claudia Crestini - WUTA08

The mineral Honeycomb

Role of minerals metals and metal oxides in prebiotic chemistry

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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

N

N

N

NH

PurineNH

N

NH2

O

Cytosine

H

O

NH2 Catalyst

160°C o 100°C

N

N

N

NH

NH2

Adenine

N

HN

O

4(3H)-pyrimidinone

Catalyst CaCO3, Kaolin, Zeolite, Alumina, Silica

 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

* NH2COHHeat

HCN + H2OHCO2NH4* NH2COH + H2O

H NH2

O2

H2N N

OH

H

O

H

+ 2 HCN N

N

OH

HNH

NHH

N

N

OH

NH2H

NH2NH2H

NH2

H NH2

O

N

N N

N

H

N

N

NH2

NH2H

NH2NH2H

NH2

NH2

HO

H

formamide dimer

NH3

(Bredereck Ang. Chemie 1959)

- H2O

Analyzing the reaction mechanism. 13C/15N-NMR Experiments “route of the

purine ring”

 Claudia Crestini - WUTA08

Analyzing the reaction mechanism. “route of the pyrimidine ring”

H NH2

O2

H2N N

OH

H

O

H

+ 2 HCN N

N

OH

HNH

NHH

N

N

OH

NH2H

NH2H

HO

H

RedoxO N

N

HO

NH2

Cytosine

formamide dimer

H N

N

NH2

NH2H

NH2H

O

H

NH3

 Claudia Crestini - WUTA08

Draco constellationAnselm KieferHigh Museum of ArtAtlanta, USA

Toward an extraterrestrial synthesis of nucleobases

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Cosmic dust

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)

Fe2SiO4* (Fayalite)

Mg0.5Fe1.5SiO4 *

MgFeSiO4 *

(Olivine)

Mg1.5Fe0.5 SiO4 *

Mg2SiO4 * (Fosferite)

SiO2, MgO, FeO2

Laser Ablation

1)

2)

3)

4)

5)

Cosmic dust analogues preparation

 Claudia Crestini - WUTA08

NH

NH

O

O

H NH2

O

160°C, 48h N

N NH

N

N

NH

NH2

O

CDAs or olivines

NH

N

O

NH

NH

O

OH2N NH2

O

pyrimidinone cytosine uracil

DHU purine urea

CDAs qualitative composition

DHU:5,6-DiHydroUracil

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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

N

NH

NH2

O

mg/g

Yield defined as mg of product per gram of formamide.

 Claudia Crestini - WUTA08

Fe Si Mg

fayaliteforsterite

olivine

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

N

N N

N

NH2

O

R

O

O

glycosidicbond

Moving towards nucleosides

ChemBioChem 4 (2003) 514-521

One-pot TiO2-Catalyzed Synthesis of Nucleic Bases and Acyclonucleosides

From Formamide: Implications for the Origin of LifeRaffaele Saladino,a,* Claudia Crestini,b Umberto Ciambecchini,a Rodolfo Negri,c Giovanna

Costanzo,c Ernesto Di Mauro c,

H NH2

O

N

N NH

N

NH2

160 °C

N

N NH

N N

NH

NH2

O

HN

NH

O

TiO2

N

N N

N

HO

N

N N

N

NH

HO

O

H

O

MeHN

NH

O

O

CH2OH N

N N

N

O

OH

N

N N

N

O

N

N N

N

NH

O

O

H

OH

OH

OH

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Adenine, cytosine and thymine3 acyclonucleosides

HN

NH

O

O

CH2OH

H OH

O

HN

NH

O

O

H2C

O

H O

HN

NH

O

O

CH2

H

- CO2

H3O+ HN

NH

O

O

CH3

H

+HN

N

O

O

CH3

H

H

H+

HN

NH

O

O

CH3

HN

NH

O

O

H

H H

O

HCO2NH4* NH2COH + H2O

* NH2COHTiO2

HCOH R. H. Barker, 1975

Thymine synthetic pathway

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Unic known one pot synthesis of thymine!

HN

NH

O

O

CH3 HN

NH

O

OHCOH

HN

NO

O

OOP

OH

N

HN

NH

H

Methylentetrahydrofolate

NH

HN

HN

HN

NO

O

OOP

OH

CH3

Tetrahydrofolate

N

HN

NH

H

+ H2ONH

HN

HN

+ HCOH

NH

HN

HN

N

N

H2N

OHO

NH

COO

COO

_

_

Tetrahydrofolate

Present day biosynthesis of thymidinePresent day biosynthesis of thymidine

Formamide

Thymine from formamide

 Claudia Crestini - WUTA08

N

N N

N

O

OH

Compd 9

N

N N

N

O

OH

OH

Compd 10

N

N N

N

NH

O

O

H

OH

Compd 11

Nucleosides from formamide

 Claudia Crestini - WUTA08

Single headed arrows represent aldolCondensations. Double-headed arrowsrepresent enolizations. Aldotreose can undergo a reverse aldol condensation

H H

O H

HO H

OH

HO H

OH-H+

BasicconditionsH2O

H H

O HO H

OH-H+

HC OH2C OH

glyceraldehyde

HO H

OH-H+

HC OHC OH

H2C OH

aldotreose

H2C OH

C O

H2C OH

H2C OH

C O

HC OH

H2C OH

HC OHC OH

HC OH

H2C OH

aldotetrose

HO H

OH-H+

HC OH2C OH ribulose

xylulosearabinoseribosexyloselyxose

HC OHC OH

H2C OH

tagolosepsicosefructosesorbose

allosealtroseglucosemannose

x 2

H H

OSugars

HO-

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Sugars synthetic pathway. The formose Sugars synthetic pathway. The formose reaction. reaction.

Butlerow, 1861Butlerow, 1861..

N

N N

N

HN

N

N N

N

OH

N

N N

N

O

OH

N

N N

N

O

OH

OH

H

O

OH

N

N N

N

O

OH

HN H

O

N

N N

N

OH

HN

OOH

or

HO H

OH-H+

HO H

OH-H+

HO H

OH-H+

TiO2

TiO2

N9-formylpurine

N

N NH

N N

N N

N

OH

NH2CHO

A novel formose reaction

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Unic known prebiotic syntesis of nucleosides!

Exploring the role of UV-radiation in prebiotic chemistry

HCN + CN-

H CN

NH HCN

NC CN

HNH2

AMN

HCNH2N CN

H2N CN

DAMN

H2N H

NH

NH

NNC

H2N

h

AICN

NH

NH2NOC

H2N

AICA

H2O

HCN

N

N NH

N

NH2

C2N2

N

N NH

N

NH2

H2N

N

NH

NH

N

NH2

NCO-

O

HCN

HN

N NH

N

O

C2N2

HN

N NH

N

O

H2N

HN

NH

NH

N

O

NCO-

O

1 23 45 6

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UV radiation in prebiotic chemistry. Pioneering studies

Diamminomalononitril cyclization to a key imidazole intermediate

UV radiation in prebiotic chemistry. Pyrimidine From

Cyanoacetaldehyde

M. P. Robertson, S. L. Miller Nature 1995, 972.

H

O

C N

Cyanoacetaldehyde H

OH

C N

H2N NH2

O

NH2

NH

H C N

O

NH2

NH

NC H

O

N

NH

NH2

O

H2OHN

NH

O

O

30-50% yield

h

 Claudia Crestini - WUTA08

Double bond isomerization for cytosine ring closure

UV radiation in prebiotic chemistry. Glyoxal From

formaldehyde

H

Ohv

H H

O

H

O

OHH

O precursor of sugars

H. Mordehai BioSystems 1979, 11(4), 227-32

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Exploring the role of UV-radiation onformamide prebiotic chemistry

Uncorrected peak areas of desorbing products

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

The surface structures of TiO2 (001) single crystal

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

Exploring the role of UV-radiation on formamide prebiotic chemistry

Thank you for the kind attention!