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
Claudia Crestini - WUTA08
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
Claudia Crestini - WUTA08
Claudia Crestini - WUTA08
The mineral Honeycomb
Role of minerals metals and metal oxides in prebiotic chemistry
Claudia Crestini - WUTA08
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
Claudia Crestini - WUTA08
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
Claudia Crestini - WUTA08
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
Claudia Crestini - WUTA08
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
Claudia Crestini - WUTA08
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-
Claudia Crestini - WUTA08
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
Claudia Crestini - WUTA08
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
Claudia Crestini - WUTA08
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
Claudia Crestini - WUTA08
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!
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