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• Life from the Soup• Proteins versus RNA• Prebiotic syntheses of amino acids &
nucleobases• Prebiotic synthesis of sugars• Sugar in space• Conclusion
Life on Earth
← 4.6×109 yrs ago – Formation of Earth
← 3.5×109 yrs ago – Prokaryotic organisms
Now →
← 1.2×109 yrs ago – Eukaryotic organisms← 0.7×109 yrs ago – Multicellular organisms
Prebiotic
What started life?
What compounds were present in the beginning?
What compounds/reactions are required now?
The primordial ”soup”
N2CH2O CCH3CN H4
HCCCNCO2 CH2CHCNNH3CONCCN
H2O HCNSO2
Note: no photosynthesis - no O2!
Aminoacids
Natural products
Steroids
TerpenesLipids
Purines Polyketides
CarbohydratesAlkaloidsPyrimidines
Aminoacids
Some are more important!
Steroids
TerpenesLipids
Purines Polyketides
CarbohydratesAlkaloidsPyrimidines
The essentials of (modern) life
Proteinscomposed of amino acidscatalyse reactions
RNAcomposed of nucleobases,ribose and phosphatecarry genetic information
Which was first, RNA or proteins?
Proteins– superior catalysts, simple building blocks, stable
RNA– can be catalysts, complex building blocks, unstable
but can replicate themselves
Prebiotic amino acid syntheses
glycine 2,1%
alanine 1,7%
S.L. MillerScience 117 (1952) 528-529J. Am. Chem. Soc. 77 (1955) 2351-2361
Common monosaccharidesaldohexoses ketohexosealdopentoses
H
CHO
OH
OHH
OHH
CH2OH
ribose
HO
CHO
H
OHH
OHH
CH2OH
arabinose
H
CHO
OH
HHO
OHH
OHH
CH2OH
glucose
HO
CHO
H
HHO
OHH
OHH
CH2OH
mannose
CH2OH
O
HHO
OHH
OHH
CH2OH
fructose
Prebiotic carbohydrate synthesis:
The Formose reaction
CH2O (CH2O)nOH
A. Butlerow, Liebigs Ann. Chem. 53 (1861) 295-298O. Leow, J. prakt. Chem. 33 (1886) 321-351
de Bruyn-van Ekensteinrearrangement
OHO
HO
OH
HOO
HOHO
HO OH
O
OHHO
OH
OH
OH
OH
OH
D-Glucose 66% D-Mannose 3%
D-Fructose 31%
de Bruyn, Rec. Trav. Chim. 14 (1895) 150-Evans, Chem. Rev. 31 (1942) 537-559
de Bruyn-van Ekenstein mechanismGlucose Mannose Fructose
1,2-Enediol
CHO
OHH
HHO
H OH
OHH
CH2OH
CHO
HHO
HHO
H OH
OHH
CH2OH
CH2OH
O
HHO
H OH
OHH
CH2OH
OH
HHO
H OH
OHH
CH2OH
H OH
The first step...
H H
HO O
H H
O
H O
O
H OH
H H
+
H
HOOH
H H
O
H
HO OH
O
H
HOH
H
O
H H
formate methanol
glycolaldehyde
Sugars in formose(55% total yield of sugars)
Aldopentoses 7%(1.4% ribose)
Ketopentoses 8%
Aldohexoses 18%
Ketohexoses 18%
Tautomers of D-riboseCyclic forms (99,9%)
OHO
OH OHOH
OHO
OHOH
OH
OHHO OH
O
OH
HO OH
O
OHOH
α-furanose β-furanose
β-pyranoseα-pyranose
Acyclic forms (0,1%)
H OH
OHH
OHH
CH2OH
O H
H OH
OHH
OHH
CH2OH
HO OH
hydrate aldehyde
dihydroxyacetone
OH
CH2OH
O
CH2OH
O
OH
CH2OH
CH2OH
O
OH
HO
OH
CH2OH
CH2OH
O
OH
CH2OH
HO
OH+
D-sorbose26%
D-fructose34%D-glyceraldehyde
H.O.L. Fischer & E. Baer, Helv. Chim. Acta 19 (1936) 519-532
Glycolaldehyde phosphate 1CHO
CH2OPO3
CHO
CHOPO3
CHOH
CHOPO3
CH2OPO3
CHOH
CHO
CH2OPO3
CHO
CH2OPO3
Müller et al., Helv. Chim. Acta 73 (1990) 1410
Conclusion
The basic building blocks of proteins and RNA can be prepared from compounds expected to be present on early Earth.
The conditions to make them are incompatible, i.e. they can not be formed under the same reaction conditions and in the same place.
The strongest proof that they could have been formed prebiotically is their presence in extraterrestrial matter.