Selection and Self-Assembly in Non-Equilibrium Environments - - PowerPoint PPT Presentation

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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


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Seminar: Physics of the Emergence of Life Mario Gaimann and Manuel Reinhardt Munich, 31st of May 2019

Selection and Self-Assembly in Non-Equilibrium Environments

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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

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Simplified Chemical Reaction Network

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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)
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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)
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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)
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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)
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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

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Solubility Reaction constant Reaction rate Const.

  • M. Tena-Solsona et al., Nat. Commun. 9, 2044 (2018)
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Competition Experiment: Setup

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  • M. Tena-Solsona et al., Nat. Commun. 9, 2044 (2018)
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Competition Experiment: Setup

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  • M. Tena-Solsona et al., Nat. Commun. 9, 2044 (2018)
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Competition Experiment: Setup

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  • M. Tena-Solsona et al., Nat. Commun. 9, 2044 (2018)
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Competition Experiment: Expectations?

Chemical Reaction Network:

Ø Two pathways for C3C5

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  • M. Tena-Solsona et al., Nat. Commun. 9, 2044 (2018)

Higher abundance of C3C5?

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Competition Experiment: Results

  • M. Tena-Solsona et al., Nat. Commun. 9, 2044 (2018)
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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)
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Competition Experiment: Results

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  • M. Tena-Solsona et al., Nat. Commun. 9, 2044 (2018)

Low fuel concentration:

v Higher abundance of C3C5 v No phase separation

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Competition Experiment: Results

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  • M. Tena-Solsona et al., Nat. Commun. 9, 2044 (2018)

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

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Competition Experiment: Discussion

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  • M. Tena-Solsona et al.,
  • Nat. Commun. 9, 2044 (2018)

Persistence and growth

  • f existing droplets over

many cycles

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Competition Experiment: Discussion

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  • M. Tena-Solsona et al.,
  • 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

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Towards the Origin of Life

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  • M. Tena-Solsona et al., Nat. Commun. 9, 2044 (2018)

Extension of the model:

Incorporate more precursors (C3, C4, C5, C6) Ø Product with longest carbon chain C6C6 is self-selected

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Towards the Origin of Life

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  • M. Tena-Solsona et al., Nat. Commun. 9, 2044 (2018)

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

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Potential Applications

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  • M. Tena-Solsona et al., Nat. Commun. 8, 15895 (2017)

v Self-erasing inks with tuneable lifetimes

Precursor

1 cm

Anhydride

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Potential Applications

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  • M. Tena-Solsona et al., Nat. Commun. 8, 15895 (2017)

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

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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)
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References

References

1.

  • M. Tena-Solsona et al., Nat. Commun. 8, 15895 (2017)

2.

  • M. Tena-Solsona et al., Nat. Commun. 9, 2044 (2018)

3. "Carboxylic acid." Wikipedia, The Free Encyclopedia, 30 May 2019.