Prebiotic Chemistry of Formamidelrb.jinr.ru/astrobiology2011/program/18_Saladino.pdf · Prebiotic...
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Prebiotic Chemistry of
Formamide
University of Tuscia, Viterbo, Italy
Raffaele Saladino
Dipartimento di Scienze Biologiche ed Ecologiche, Università della Tuscia,
Via S. Camillo de Lellis s.n.c., 01100 Viterbo, Italy.
Dubna,Russia, December 2011
The RNA World Hypothesis
Joyce, G.F. (2002) Nature 418, 214-221.
University of Tuscia, Viterbo, Italy
GENETIC METABOLISM
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
University of Tuscia, Viterbo, Italy
And in Jupiter's satellite Europa
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 . Physical and chemical properties
University of Tuscia, Viterbo, Italy
“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 prebiotic chemistry:
Pioneering studies.
Koyama, T. et al Chem.Pharm. Bull. 1977, 1923.
Yamada, H. et al.Tetrahedron Lett. 1978, 4039
H
O
NH2
170°C-190°C N
N28 hrs NH
N
H
O
NH2
170°C-190°C N
N28 hrs N
H
NN
N NH
N
NH2
+
HCN
Purine
Purine Adenine
A)
B)
University of Tuscia, Viterbo, Italy
The role of minerals on prebiotic processes.
A general overview
•Minerals can accumulate the prebiotic precursors
(concentration effect)
•Minerals can act 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 benignin environments to preserve newly
formed biomolecules from degradation
University of Tuscia, Viterbo, Italy
First results
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,a,* Claudia Crestini, b Giovanna Costanzo,c Rodolfo Negrid and Ernesto Di Mauro c, d
University of Tuscia, Viterbo, Italy
Analyzing the reaction mechanism. 13C-/15N-NMR
Experiments“route of the pyrimidine ring”
* NH2COHHeat
HCN + H2O
HCO2NH4* NH2COH + H2O
University of Tuscia, Viterbo, Italy
University of Tuscia, Viterbo, Italy
Analyzing the reaction mechanism. 13C-/15N-NMR
Experiments“route of the pyrimidine ring”
Si
Al
Si
O
NC
H
H H
O
H H H
Al
oo o
o o o
o o o
Mn+
xH2O
oSi
4+, occasionally Al
3+
Al3+
, Mg2+
ChemBioChem 5 (2004) 1-9
Synthesis and Degradation of of Nucleobases and Nucleic Acids by
Formamide in the Presence of Montmorillonites Raffaele Saladino,a,* Claudia Crestini, b Umberto Ciambecchini,a Fabiana Ciciriello,c Giovanna Costanzo,c and Ernesto Di
Mauro c, d
Bu, Y.; Lin, M.C. Langmuir 1994
University of Tuscia, Viterbo, Italy
AICA: Amino Imidazole CarboxyAmide
fAICA: formyl Amino Imidazole
CarboxyAmide
fpurine: N(9)-formyl purine
University of Tuscia, Viterbo, Italy
Analyzing the reaction pathway. The“route of the
pyrimidine ring”
University of Tuscia, Viterbo, Italy
H NH2
O HN
N NH
N
O
NH
N
H2N
O
H2N
NH
N
HOCHN
O
H2N - H2O
HCN
Clays
In exant cell !
The first example of Chemiomimetic pathway
University of Tuscia, Viterbo, Italy
“certain biosynthetic pathways can be considered as
chemiomimetic of early prebiotic chemistry”
Eschenmoser, A.; Loewenthal, E. Chem. Soc. Rev. 1992, 1.
The origin of sugars and nucleosides
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,
University of Tuscia, Viterbo, Italy
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
Thymine synthetic pathway
HCO2NH4* NH2COH + H2O
* NH2COH
TiO2
HCOH R. H. Barker, 1975
University of Tuscia, Viterbo, Italy
Sugars synthetic pathway. The formose reaction.
Butlerow, 1861.
Single headed arrows represent aldol
Condensations. Double-headed arrows
represent enolizations. Aldotreose can
undergo a reverse aldol condensation
H H
O
Sugars
HO-
University of Tuscia, Viterbo, Italy
A novel formose reaction
University of Tuscia, Viterbo, Italy
Complex nucleoside derivatives
University of Tuscia, Viterbo, Italy
Philosophical Magazine 90 (2010) 2329-2337
Role of clays in the prebiotic synthesis of sugar from Formamide Raffaele Saladino,a,* Neri Veronica, Claudia Crestini,b
University of Tuscia, Viterbo, Italy
oo o
o o o
o o o
Mn+
xH2O
oSi
4+, occasionally Al
3+
Al3+
, Mg2+
KSF
N.W. Gabel,
C. Ponnamperuna
Nature 1967
Formamide prebiotic chemistry
with extraterrestrial materials
ChemBioChem 6 (2005) 1368-1374
Synthesis and Degradation of Nucleic Acid Components by
Formamide and Cosmic Dust Analogues Raffaele Saladino,a,* Claudia Crestini, b Veronica Neri,a John R. Brucato,d Luigi Colangeli,d Fabiana Ciciriello,c Giovanna
Costanzo,c and Ernesto Di Mauro c, d
University of Tuscia, Viterbo, Italy
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
Preparation of cosmic dust analogues
1)
2)
3)
4)
5)
University of Tuscia, Viterbo, Italy
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
DHUpurine urea
Fe Si Mg
olivine
fayalite
forsterite
CDAs qualitative composition
DHU:5,6-DiHydroUracil
University of Tuscia, Viterbo, Italy
Moving towards the metabolism
University of Tuscia, Viterbo, Italy
ATP
GTP
AM
INO
AC
IDS
NU
CL
EIC
AC
ID B
AS
ES
SU
GA
RS
AN
D L
IPID
S
CITRIC ACID CYCLE
O2
University of Tuscia, Viterbo, Italy
ATP
GTP
AM
INO
AC
IDS
NU
CL
EIC
AC
ID B
AS
ES
SU
GA
RS
AN
D L
IPID
S
REDUCTIVE CITRIC ACID CYCLE In eubacteria and archea
CO2
Metabolism part 1. Thermal conditions
Borate and Prebiotic Chemistry: A possible relationship with formamide
University of Tuscia, Viterbo, Italy
Origin Life Evolution Biosphere 41 (2011) 317-330
The effect of borate minerals on the synthesis of nucleic acid bases, amino acids and
biogenic carboxylic acids from formamide Raffaele Saladino,a,* Maurizio Barontini, Cristina Cossetti, Ernesto Di Mauro, Claudia Crestini
University of Tuscia, Viterbo, Italy
Baddeleyte ZrO2
Zircon ZrSiO4
Lithium zirconate Li2ZrO3
Lead zirconate PbZrO3
Barium zirconate BaZrO3
Zirconium oxinitrate ZrO(NO3)2
J. Molecular Evolution 71 (2010) 100-110
The role of the formamide/zirconia system in the synthesis of nucleobases and
Biogenic carboxylic acids Raffaele Saladino,a,* Neri Veronica, Claudia Crestini, Costanzo Giovanna, Michele Graciotti, Ernesto Di Mauro
University of Tuscia, Viterbo, Italy
Origin Life Evolution Biosphere 41 (2011) 437-451
Catalytic effects of Murchison material: prebiotic synthesis and degradation
of RNA precursors Raffaele Saladino,a,* Claudia Crestini, Cristina Cossetti, Ernesto Di Mauro, David Deamer
University of Tuscia, Viterbo, Italy
ATP
GTP
AM
INO
AC
IDS
NU
CL
EIC
AC
ID B
AS
ES
SU
GA
RS
AN
D L
IPID
S
FIST-REDUCTIVE CITRIC ACID CYCLE
CO2
Metabolism part 2. Photochemical conditions
University of Tuscia, Viterbo, Italy
Anatase commercial
Anatase ground
Monochromatic Irradiation 3.2 eV
Astrobiology 11 (2011) 815-824
Photochemical synthesis of citric acid cycle intermediates based on titanium dioxide Raffaele Saladino,a,* John Robert Brucato, Antonio de Sio,b
Giorgia Botta, Emanuele Pace, Lisa Gambicorti
150 200 250 300 350 400 450 500 550 600
108
109
1010
1011
1012
Flu
x (
Ph
/ s
)
Wavelength (nm)
400 600 800 1000 1200 1400 16001.50x10
11
3.00x1011
4.50x1011
6.00x1011
7.50x1011
9.00x1011
1.05x1012
Flu
x (
photo
ns /
s c
m2)
e- (mA)
Flux
Linear Fit of Flux
Equation y = a + b*x
Adj. R-Square 0.998
Value Standard Error
Flux Intercept -3.36692E9 4.32197E8
Flux Slope 5.66953E8 457797.44953
Tab 2.1: Integral of the photons and energy dose of the different irradiation runs at 387.5 nm.
Mineral Powder Photon Dose Energy dose
(mW*s=J)
Exp. : Anatase BG 5.32 15 Photons 2.7
Exp. : Anatase FG 5.32 15 Photons 2.7
Exp. : Rutile 3.56 15 Photons 1.8
Exp. : Mix Rutile + Anatase 2.90 15 Photons 1.5
Exp. : Formamide 2.94 15 Photons 1.5
BG= Big grains >500 nm
FG= Fine grains<100 nm
Monochromatic Irradiation 3.2 eV , 387.5 ± 2.14 nm
University of Tuscia, Viterbo, Italy
University of Tuscia, Viterbo, Italy
R. Saladino, J.R. Brucato, A. de Sio, E. Pace
University of Tuscia, Viterbo, Italy
University of Tuscia, Viterbo, Italy
University of Tuscia, Viterbo, Italy
ATP
GTP
AM
INO
AC
IDS
NU
CL
EIC
AC
ID B
AS
ES
SU
GA
RS
AN
D L
IPID
S
FIST-REDUCTIVE CITRIC ACID CYCLE
CO2
events
high
low
formamide
bases
nucleosides
phosphorylation
(polymerization)
thermodynamic
niches
stabilization
helpers
micelles
Minerals catalysed prebiotic synthesis of nucleic
acid components from formamide. Degree of
confidence
University of Tuscia, Viterbo, Italy
Claudia Crestini (U.Tor Vergata) Fabiana Ciciriello (U. La Sapienza)
Raffaele Saladino (U. Tuscia) Giovanna Costanzo (IBPM)
Ernesto Di Mauro (U. La Sapienza)