%0 Journal Article
%T Unravelling a fulvene based Replicator: Experiment and Theory in Interplay
%A Arne Dieckmann
%A Sabrina Beniken
%A Christian Lorenz
%A Nikos L Doltsinis
%A G¨šnter von Kiedrowski
%J Journal of Systems Chemistry
%D 2010
%I BioMed Central
%R 10.1186/1759-2208-1-10
%X 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]. Small organic replicators, 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. Here we introduce a replicator which utilizes a fulvene-based 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.We selected fulvene chemistry for replicator construction for two reasons: First, fulvene chemistry allows facile variation of the diene part. Second, with respect to an earlier described system [17], we aimed to arrive at a nonchiral reaction product in order to simplify the kinetic analysis. In principle, there are four possible products -- two endo and two exo diastereomers -- from the reaction of A and B, three of them being observed by NMR (Fig. 2). Only endo-products (NN, NX) are able to replicate via a termolecular complex. The kinetics of the reaction of A with B were studied by time-resolved 1H-NMR (600 MHz) in CDCl3 at 293 K (Fig. 2a). One main product is apparent whose curve exhibits a sigmoidal shape caused by an induction period, which is typical of autocatalytic reactions. To prove the specificity of the catalysis 2 eq benzoic acid was a
%U http://www.jsystchem.com/content/1/1/10