Selection and Self-Assembly in Non-Equilibrium Environments - - PowerPoint PPT Presentation
Selection and Self-Assembly in Non-Equilibrium Environments - - PowerPoint PPT Presentation
Selection and Self-Assembly in Non-Equilibrium Environments Seminar: Physics of the Emergence of Life Mario Gaimann and Manuel Reinhardt Munich, 31 st of May 2019 Motivation Chemical Selection as a Corner Stone of Life Select a wanted product
Motivation
Chemical Selection as a Corner Stone of Life
Select a wanted product in a large and complex reaction network Attractive mechanism for the formation of protocells out of prebiotic molecules For living systems, a selection mechanism has to work outside of equilibrium
Simplified Chemical Reaction Network
Chemical Reaction Network
Components
C3 C4 C5 C6
Precursor Cn Product CnCn
C3C3 C4C4 C5C5 C6C6 C3C6 Nonsymmetric Products are also possible, e.g. C4C5 or C3C6.
- M. Tena-Solsona et al., Nat. Commun. 9, 2044 (2018)
Chemical Reaction Network R= –C2H5 –C3H7 –C4H9 –C5H11 Fuel Cn H2O Cn 2H+ Precursor Cn Product CnCn Intermediate Cn* Waste Products are very unstable, decay quickly by hydrolysis. There are more chemical processes involved than depicted here (e.g. back reactions). The experimental group developed a kinetic model in Matlab where most processes are included.
- M. Tena-Solsona et al., Nat. Commun. 9, 2044 (2018)
Experimental Setup
Precursor Cn
Fuel
- Mix 300 mM of one precursor and 10
mM of fuel (EDC)
- Measure product (anhydride)
concentration as a function of time Reasonable Expectations
- All precursors are chemically very
similar ⇒ should exhibit similar behavior
- Anhydride concentration grows rapidly
at first but also decays quickly
Experiment 1: Single Precursor
- M. Tena-Solsona et al., Nat. Commun. 9, 2044 (2018)
Experimental Results 5 4 3 2 1 60 min 40 80 120 Concentration (mM) Time (min) C6C6 C4C4 C3C3 C5C5 Anhydride concentrations
Observations
- Longer anhydrides hydrolyze
(decay) more slowly
- C5C5 and C6C6 concentrations
especially show a very pronounced long tail
- For C5C5 and C6C6: Solution
becomes turbid as soon as fuel is added Q: What could explain the special behavior of C5C5 and C6C6?
- M. Tena-Solsona et al., Nat. Commun. 9, 2044 (2018)
Phase Separation
Phase separation
No inhibition Inhibition Oil droplet Aqueous solution C3 C3C3 C5C5 C5
1 2 4 10 2 4 100 2 Persistency factor C3C3 C4C4 C5C5 C6C6 Anhydride persistency factors
<latexit sha1_base64="Bg1GdqtrhIg84B0Uj+tY6wV0f/U=">ABt3icbY7NSsNQEIUn9a/Gv6hLN8G6cGNJ6kJcCEVBFBQq2B8wJdzcTJpLk9yYe1MoMY/gA+hLuPA5XLpwo69iokXQelbfnDPDHCcOmJCG8aZUZmbn5heqi+rS8srqmra+0RE8TSi2KQ940nOIwIBF2JZMBtiLEyShE2DXGZ6UeXeEiWA8upbjGPshGUTMY5TIwrK185FthUT6wsv8sZvwYCyYyPUjfivb0kWotDFT0iMmYu5rZWM+rGl/RpMCdQa+483L83z2bK1ruZymIUaSBkSIG9OIZT8jiWQ0wFxVrVRgTOiQDBLI0a5i3vl21y1BMqSPB7J7JQlRL8sJv2CDXyZq0UT8+/faeg06uZ+vXFVDqGb1VhC7ZhF0w4gCacQvaQOEJXuEdPpRDxVY8xf9erSiTm034JeX2E+jefs0=</latexit>Solubility Reaction constant Reaction rate Const.
- M. Tena-Solsona et al., Nat. Commun. 9, 2044 (2018)
Competition Experiment: Setup
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Competition Experiment: Setup
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- M. Tena-Solsona et al., Nat. Commun. 9, 2044 (2018)
Competition Experiment: Setup
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Competition Experiment: Expectations?
Chemical Reaction Network:
Ø Two pathways for C3C5
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Higher abundance of C3C5?
Competition Experiment: Results
- M. Tena-Solsona et al., Nat. Commun. 9, 2044 (2018)
Competition Experiment: Results
Low fuel concentration:
v Higher abundance of C3C5 v No phase separation
- M. Tena-Solsona et al., Nat. Commun. 9, 2044 (2018)
Competition Experiment: Results
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Low fuel concentration:
v Higher abundance of C3C5 v No phase separation
Competition Experiment: Results
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High fuel concentration:
v Higher abundance of C5C5 v Phase separation slows decay of C5C5, cumulative advantage!
Low fuel concentration:
v Higher abundance of C3C5 v No phase separation
Competition Experiment: Discussion
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- Nat. Commun. 9, 2044 (2018)
Persistence and growth
- f existing droplets over
many cycles
Competition Experiment: Discussion
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- Nat. Commun. 9, 2044 (2018)
The longer hydrophobic anhydride C5C5 is self-selected in an non-equilibrium environment! Kinetic selection, not thermodynamic selection!
Persistence and growth
- f existing droplets over
many cycles
Towards the Origin of Life
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Extension of the model:
Incorporate more precursors (C3, C4, C5, C6) Ø Product with longest carbon chain C6C6 is self-selected
Towards the Origin of Life
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Non-equilibrium self- selection as a general principle
Extension of the model:
Incorporate more precursors (C3, C4, C5, C6) Ø Product with longest carbon chain C6C6 is self-selected
Potential Applications
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v Self-erasing inks with tuneable lifetimes
Precursor
1 cm
Anhydride
Potential Applications
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v Self-erasing inks with tuneable lifetimes v Kinetic trapping of carboxylate precursors into fibres
Precursor
1 cm
Anhydride +100 mM fuel Precursor
10 µm
after 10 min after 24 hr
Anhydride gel with carboxylate fibres
Recap
No inhibition Inhibition Oil droplet Aqueous solution C3 C3C3 C5C5 C5
Phase separation inhibits decay of some Products Slow decay can be used as a selection mechanism. For this to work we need fuel and starvation cycles. A simple reaction network as a model of reality
- M. Tena-Solsona et al., Nat. Commun. 9, 2044 (2018)
References
References
1.
- M. Tena-Solsona et al., Nat. Commun. 8, 15895 (2017)
2.
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