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ASTROCHEMISTRY & ASTROBIOLOGY. Outline. 1. Astrochemistry & Meteoritic Organics. 2. Extraterrestrial Delivery. 3. Early Earth. Ehrenfreund et al. (2002) Astrophysical and Astrochemical Insights into the Origin of Life , Rep. Prog. Phys., 65, 1427-1487. Reading. - PowerPoint PPT Presentation
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ASTROCHEMISTRY & ASTROBIOLOGY
Outline
1. Astrochemistry & Meteoritic Organics
2. Extraterrestrial Delivery
3. Early Earth
ReadingEhrenfreund et al. (2002) Astrophysical and Astrochemical Insights into the Origin of Life,Rep. Prog. Phys., 65, 1427-1487
Cronin, J.R. & Chang, S. (1993) Organic Matter in Meteorites, in The Chemistry of Life’s Origins, J.M. Greenberg et al. (eds.), Kluwer, 209-258
Botta, O. & Bada, J.M. (2002) Extraterrestrial Organic Compounds in Meteorites, Surveys in Geophysics, 23, 411-467
Sephton, M.A. (2002) Organic Compounds in Carbonaceous Meteorites, Nat. Prod. Rep., 19, 292-311
Extraterrestrial Delivery of Biogenic Molecules
Extraterrestrial Delivery of Biogenic Molecules
Crovisier 2005
Evidence for chemicaldiversity Diversity among Oort cloudcomets
No systematic differencesbetween Oort cloud and
« Kuiper belt » comets
TYPES OF METEORITES
TYPE SUBTYPE FREQUENCY COMPOSITION FORMATION
Stones Carbonaceous 5 % Water, carbon Primitive Chondrites silicates, metals
Chondrites 81 % Silicates Heated underpressure
Achondrites 8 % Silicates Heated
Stony irons 1 % 50 % silicates, Differentiated 50 % free metal
Irons 5 % 90 % iron Differentiated 10 % nickel
Organics Found in Meteorites
Total Carbon Content: > 3% (by weight); Soluble Fraction: < 30% of total C
COMPONENTS:ACIDS:
Amino acidsCarboxylic acidsHydroxycarboxylic acidsDicarboxylic acidsHydroxydicarboxylic acidsSulfonic acidsPhosphonic acids
FULLERENES:
C60, C70
He@C60
Higher Fullerenes
HYDROCARBONS:
non-volatile: aliphaticaromatic (PAH)polar
volatile
OTHERS:
N-HeterocyclesAmidesAmines AlcoholsCarbonyl compounds
1 D-Aspartic Acid
2 L-Aspartic Acid
3 L-Glutamic Acid
4 D-Glutamic Acid
5 D,L-Serine
6 Glycine
7 -Alanine
8 -Amino-n-butyric Acid (g-ABA)
9 D,L-b-Aminoisobutyric Acid (b-AIB)
10 D-Alanine
11 L-Alanine
12 D,L--Amino-n-butyric Acid (b-ABA)
13 -Aminoisobutyric Acid (AIB)
14 D,L--Amino-n-butyric Acid (a-ABA)
15 D,L-Isovaline
16 L-Valine
17 D-Valine
X: unknown
Chromatograms of Meteorite Extracts
Ehrenfreund et al., 2001
Amino Acids in Carbonaceous Chondrites
Amino acids are readily synthesized under a variety of plausible prebiotic conditions (e.g. in the Miller-Urey Experiment).
Amino acids are the building blocks of proteins and enzymes in life on Earth.
Chirality (handedness) can be used to distinguish biotic vs. abiotic origins.
Most of the amino acids found in meteorites are very rare on Earth (AIB, isovaline).
•
•
•
•
R R'
OHCN+
+NH3
R CR'
OH
CN
R CR'
NH2
CN
R CR'
OH
C
O
NH2
R CR'
NH2
C
O
NH2 R CR'
NH2
C
O
OH
R CR'
OH
C
O
OH
R,R' = H or CnH2n+1
Cyanohydrin
Aminonitrile
-Hydroxy acid
-Amino acid
Strecker Amino Acid Synthesis in CM-type Chondrites
For a review: Botta and Bada, Surv. Geophys. 23, 411-467 (2002)
Strecker Amino Acid Synthesis
in CM-type Chondrites
HC C C N
NH3
CH CH C NH2N
CH2 CH2 C
O
H2NOH
-Alanine
Cyanoacetylene
HCN H2N CH2 C
O
OH
+ traces of other amino acids
Glycine
- 80ºC < T < + 80ºC
H2C C C N
NH3
CH CH C NH2N
Acrylonitrile
Levy et al., Icarus 145, 609-613 (2000).
Cronin & Chang,1993.
Amino Acid Synthesis in CI-type ChondritesAmino Acid Synthesis in CI-type Chondrites
Chirality
• Left- and right-handed mirror molecules are called enantiomers.
Enantiomers possess identical physical properties (melting point etc.).
They rotate the plane of planar-polarized light in opposite directions.
They cannot be chromatographically separated on a non-chiral column.
•
•
•
Separation on chiral column
or
Derivatization to form diastereoisomers, separation on non-chiral column
Enantiomeric Excesses in Meteoritic Amino Acids
Pizzarello and Cronin, Geochim. Cosmochim. Acta 64, 329-338 (2000)
-1
0
1
2
3
4
5
6
7
8
9
10
En
an
tio
me
ric
Ex
ce
ss
(%
)
Murchison
Murray
2-A
min
o-2
,3-d
imet
hyl
-p
enta
no
ic a
cid2S
,3S
/2R
,3R
2S,3
R/2
R,3
S
Iso
valin
e
-M
eth
yln
orv
alin
e
-M
eth
ylva
line
-M
eth
yln
orl
euci
ne
-M
eth
yl-n
-bu
tyri
c ac
id
No
rval
ine
Ala
nin
e
Val
ine
Mechanisms?Racemization?Amplification?
NATURE |VOL 416 | 28 MARCH 2002
ISOTOPIC RATIOS FOR “C” AND “H”
Irvine 1998
Terr.ocean= D= O Cosmic D/H ratio ~ 0.8-2x10-5
14N/15N~140IDPs
ISM DEPLETION CORES 14NH3/15NH3~140
NITROGEN ISOTOPE RATIOS
COMETS:
HC14N/HC15N~400
C14N/C15N~140
(TERRESTRIAL 14N/15N~270)
PROTOSOLAR 14N/15N~400
PROCESSING ISM TO ORGANIC POLYMERS ?
A piece of interplanetary
dust
DNA/RNA Components
Nucleobases in Carbonaceous Chondrites
are very important in the replicating system of all known
terrestrial organisms (in DNA and RNA)
have been detected in Murchison, Murray and Orgueil
meteorites at the 200-500 ppb level
(Schwartz and coworkers, 1979-1982)
various other (non-biogenic) N-heterocycles, including a
variety of alkylated pyridines, were found in meteorites
no isotopic measurements have been reported
N
NHN
NH
O
Hypoxanthine
N
NN
NH
NH2
Adenine Guanine Xanthine
N
NHN
NH
O
NH2 NH
NHN
NH
O
O
NH
NH
O
O
Uracil
Interstellar Dust: ice mantle evolutionInterstellar Dust: ice mantle evolutionInterstellar Dust: ice mantle evolutionInterstellar Dust: ice mantle evolution
Bernstein, Sandford, Allamandola , Sci. Am. 7,1999, p26Bernstein, Sandford, Allamandola , Sci. Am. 7,1999, p26
Mass Spectrum of the Room Temperature Residue of H2O:CH3OH:CO:NH3 (100:50:1:1) Ice Compared to the Mass Spectra
of Two Interplanetary Dust Particles (IPDs)
IDP Spectra - Clement et al., 1993Fig. - Jason Dworkin
Interstellar/Precometary Ice Photolysis: Abiotic Interstellar/Precometary Ice Photolysis: Abiotic
Synthesis of Important Prebiotic OrganicsSynthesis of Important Prebiotic Organics Interstellar/Precometary Ice Photolysis: Abiotic Interstellar/Precometary Ice Photolysis: Abiotic
Synthesis of Important Prebiotic OrganicsSynthesis of Important Prebiotic Organics
Bernstein et al. (2002) Nature, 416, 401.
CH C
O
OHC
NH2
O
HO
Amino malonic acid
O
C NH2H2N
Urea
HO CH2 CH2 NH2
Ethanolamine
NH
HN
O O
Hydantoin
O
NH
O
H2N
Cycloserine
NH CH2 C
O
OHC
O
H
N-Formyl glycine
Glycerol
CH CH2CH2HO
OH
OH
Glyceric Acid
CH C
O
OHCH2HO
OH
CH C
O
OHCH2HO
NH2
Serine
Photolysis of PAHs in Water Ice ProducesAlkanes, Ketones, Ethers, and Alcohols.
UV radiation
water ice at 10 K
Benzo[ghi]perylene
O
H
H
Ketone
OEther
OHAlcoholHH
HH
Aliphatic Bridge (added H atoms)
Both oxidation (alcohol, ether and ketone formation) and reduction (addition of hydrogen) reactions occuron photolysis of water ices containing PAHs. These are the same kinds of compounds observed in meteorites, fit spectra of emission objects and, in some cases, have biochemical significance.
Photolysis of PAHs in Water Ice ProducesAlkanes, Ketones, Ethers, and Alcohols.
UV radiation
water ice at 10 K
Benzo[ghi]perylene
O
H
H
Ketone
OEther
OHAlcoholHH
HH
Aliphatic Bridge (added H atoms)
Both oxidation (alcohol, ether and ketone formation) and reduction (addition of hydrogen) reactions occuron photolysis of water ices containing PAHs. These are the same kinds of compounds observed in meteorites, fit spectra of emission objects and, in some cases, have biochemical significance.
Bernstein et al.Science 283, 1135 (1999)
Photochemistry of PAHs in Ice: Abiotic Synthesis of Biogenic Compounds
UV radiation
anthracene/H2O 10 K
OH OH
O
O
R
Aloe-Emodin (extract of Aloe) Arch. Pharm. 247, 81 (1909)
Rhein (extract of chinese rhubarb) Ann. 50, 196 (1844)
O
O
UV radiation
naphthalene/H2O 10 K
O
O
O
O
OH
Juglone (in walnut & pecan shells) Bull. Soc. Chim. 1, 800 (1907)
These quinone type structures are very important in many living systems. For example, naphthaquinones (like juglone above) are essential for electron transport in simple organisms.Perhaps the earliest microbes absorbed extraterrestrial molecules provided by comets andmeteorites and as a result this class of compounds became incorporated into the biochemistry of terrestrial organisms. Juglone: Bernstein et al.Met. & Planet. Sci. 36, 351 (2001)
Anthroquinone: Ashbourne et al. in prep
Interstellar Ices
(H2O, CH3OH, NH3,CO, CH4, HCN, C2H2, PAHs, etc.)
N
N NH
N
NH2
Purines
N
HN
NH
N O
O
H3C
H3C
Flavins
HN
NH
O
O
Pyrimidines
H2N CH2 C
O
OH
Amino Acids
Abiotic Synthesis of Biogenically Useful Molecules in Cometary and Interstellar Ices
HO
OAlkaloids
OH O
OQuinones
O
OHOH
HO OH
Carbohydrates
Vitamins
OH
CH3
NH2
Courtesy Jason Dworkin
Organic Residue Remaining After the Low Temperature UV Irradiation of the Ice
H2O : CH3OH : CO : NH3 (100:50:1:1)
UV-Pumped LuminescenceNatural Light
Phase ContrastMicroscopy
FluorescenceMicroscopy
30 µmMurchison Meteorite
Deamer et al. 2003Proton Irradiated Ice
Dworkin &MooreWork in progress
UV photolyzed Ice Dworkin et al. 2001
Formation of Various Vesicular Structures from Meteorite and Ices
Major Sources (in kg/yr) of Prebiotic Organic Compounds in the Early Earth Terrestrial Sources kg/yr* UV Photolysis 3 x 108
Electric Discharge 3 x 107
Shocks from impacts 4 x 102
Hydrothermal Vents 1 x 108
Extraterrestrial Sources
IDP’s 2 x 108
Comets 1 x 1011
Total 1011
adapted from Chyba & Sagan (1992)
Habitable zone
Life on Earth
EARLY EARTH
• Strong bombardment through comets over 700 mill. years• Strong geological activity• First evidence for Life: ~ 3.6 billion years ago
• Black Smokers
Alternative abiotic synthesis routes
• Volcanic outflows
Could it be that our configuration of planets is extremely rare, perhaps even unique ?
The right distance from the star The right mass of the central star Stable planetary orbits A Jupiter-like neighbour The right planetary mass Plate tectonics An ocean ……
ASTRObiology