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Homochirality: models and results Axel Brandenburg, Anja Andersen, Susanne Höfner, Martin Nilsson To appear in Orig. Life Evol. Biosph., q-bio.BM/0401036
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2 Photosynthesis Requires chlorophyll as catalyst What about chiralitry?
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3 Aminoacids in protein: left-handed Sugars in DNA and RNA: right-handed Louis Pasteur (1822-1895) animogroup carboxylgroup
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4 Racemic mixture (from lecture of Antoine Weiss) Racemization dating method
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5 Miller/Urey experiment 15 organic compounds 2% amino acids (11 different ones) racemic mixture Wait 1 week
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6 Chirality and origin of life Dead stuff not chiral, so is chirality –with racemic mixture: structure fragile Importance: –Prerequisite of life (provides curvature and twist) –Consequence of life (enzymatic reactions) Miller-Urey amino acids: both chiralities –in Murchison meteorite: mostly left-handed! –but contamination is debated… Reasons discussed: circularly polarized light, beta- decay (weak force), homochiral template
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7 Relevant experiments: nucleotides template-directed oligomerization poly (C D ) oligo (G D ) Mononucleotides with wrong Chirality terminate chain growth cytosine guanine ok poisoned Joyce, et al. (incl. Orgel) (1984) (using HPLC)
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8 Contergan: was sold as racemic mixture causes misformations Cures morning sickness during pregnancy (abundaned in December 1961)
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9 Relevant experiments: crystals Crystal growth with stirring: primary nucleation suppressed Crystal growth, many different nucleation sites: racemic mixture Autocatalytic self-amplification? Frank (1953), Goldanskii & Kuzmin (1989), …
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10 Auto-catalytic effect in dead matter Alkanol with 2% e.e. Treated with carboxylaldehyde
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11 Model by Saito & Hyuga (Jan 2004) Bimodal behavior
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12 Model by Sandars (Dec 2003, OLEB) Reaction for left-handed monomers Loss term for each constituent
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13 Combined equations Loss term for each constituent
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14 Including enantiomeric cross-inhibition Loss term for each constituent Racemic solution ~2 1-n
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15 Coupling to substrate S Q L comes from substrate acts as a sink of S S sustained by source Q Catalytic properties of substrate (depending on how much L and R one has) Q L = Q R (L n,R n ) Source of L 1 monomers Q L
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16 Self-catalytic effect Form of Q L = Q R (L n,R n ) Possible proposals for C L (similarly for C R )
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17 Birfurcation properties Mononucleotides with wrong Chirality terminate chain growth
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18 Stability Relative perturbation of racemic solution, 10 -4
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19 Conservation law Dependence on fidelity where
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20 Differences to Sandars Coupling to substrate: here proportional to E L –in Sandars: [L N ] Outer boundary condition: here open –in Sandars: prescribed damping term Future extensions: –Chain braking –add spatial 3D dynamics
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21 Reduced equations Quantitatively close to full model
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22 Initial bias Effect in reality very weak
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23 Spatially extended model Propagating front solutions Reaction-diffusion equation Proto type: Fisher’s equation wave speed with Tuomas Multamäki
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24 1D model (reaction-diffusion equation) Propagation into racemic environment
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25 2D model (reaction-diffusion equation) Short run
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26 2D model (reaction-diffusion equation) Time scale longer than for simple fronts
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27 P polymerization olymerization in 1D chain growth, Rn and Ln in different places
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28 The RNA world Central dogma of chemistry of life –DNA RNA protein enzyme all enzymes are themselves proteins? Walter Gilbert (1986)
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29 RNA itself as enzyme
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30 pre-RNA worlds Many problems: stability of sugars 2-amino ethyl glycin (AEG)
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31 pre-RNA worlds PE Nielsen (1993) better alternative: Nelson, Levi, Miller (2000)
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