Abstract
A self-replicating system based on a cycloaddition of a fulvene derivative and a maleinimide is investigated using a two-pronged approach combining NMR spectroscopy with computer simulations. In the course of the reaction, two diastereomers are formed with identical rates in the absence of replication. When replication is enabled, a network emerges in which one diastereomer takes over the resources as a selfish autocatalyst while exploiting the competitor as a weak altruist. The structure and dynamics of the reaction network is studied using 1 D and 2 D NMR techniques supported by dynamically averaged ab initio chemical shifts and ab initio molecular dynamics simulations. It is shown that this combination is a powerful means to understand the observed experimental behaviour in great detail.
Highlights
A self-replicating system based on a cycloaddition of a fulvene derivative and a maleinimide is investigated using a two-pronged approach combining NMR spectroscopy with computer simulations
The field of self-replication chemistry [1-23] currently aims to understand and to control the energy landscape determining the type of autocatalytic growth, which distinguishes the chemistry of parabolic coexistence[24] from the biological physics building on the Darwinian principle [25]
Especially those which are the design offspring of the system introduced by Wang and Sutherland [16], offer particular advantages in the quest for a more detailed understanding of replicator dynamics: They are large enough to exhibit autocatalysis coupled to information transfer and they are small enough to be treatable from first principles
Summary
A self-replicating system based on a cycloaddition of a fulvene derivative and a maleinimide is investigated using a two-pronged approach combining NMR spectroscopy with computer simulations. We introduce a replicator which utilizes a fulvenebased Diels-Alder reaction (see Fig. 1) and show that the conjunction of ab initio molecular dynamics (AIMD) as developed by Car and Parrinello[26] with NMR kinetics supported by computed chemical shifts and 2D-NMR methods allows us to decipher the structural and energetic rationale behind the observed behaviour, while static computational methods currently used in the field did not reproduce the experimental data.
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