Addressing the still open question of the prebiotic origin of sequential macromolecules (peptides, nucleic acids) on the primitive Earth, we describe a molecular engine (the primary pump), which works at ambient temperature and continuously generates, elongates and complexifies sequential peptides. This new scenario is based on a cyclic reaction sequence, whose keystep is the activation of amino acids into their N‐carboxyanhydrides (NCA) through nitrosation by NOx. This process could have taken place on tidal beaches; it requires a buffered ocean, emerged land and a nitrosating atmosphere. With the help of geochemical studies and computer simulations of atmosphere photochemistry, we show that the primitive Earth during the Hadean may have satisfied all these requirements. © 2001 Society of Chemical Industry.

Recent developments in peptide synthesis have underlined the importance of optimising, on a preparative scale, the N-carbamoylation of amino acids by aqueous cyanate. To this purpose, a theoretical model of aqueous cyanate reactivity was designed. The parameters of the model were evaluated, for various pH and temperatures, from a critical survey of the literature, together with additional experimental data. Computer-simulated kinetics based on this model showed the reaction efficiency to be significantly dependent on pH, and suggested optimum conditions to be moderate temperatures and pH 8.5-9. Discussion of the practical convenience of these theoretical results led us to prefer 40-50 ЊC and a pH range of 7-8 as reaction conditions, thus maintaining reaction times within a few hours. Various N-carbamoyl amino acids (ureido derivatives of glycine, -valine, -alanine, -leucine, -methionine, N ε -trifluoroacetyl--lysine, β-alanine) were thus successfully synthesised on the gram to kilogram scales.

We propose a scenario for the dynamic co-evolution of peptides and energy on the primitive Earth. From a multi component system consisting of hydrogen cyanide, several carbonyl compounds, ammonia, alkyl amine, carbonic anhydride, borate and isocyanic acid, we show that the reversibility of this system leads to several intermediate nitriles, that irreversibly evolve to alpha-amino acids and N-carbamoyl amino acids via selective catalytic processes. On the primitive Earth these N-carbamoyl amino acids combined with energetic molecules (NOx) may have been the core of a molecular engine producing peptides permanently and assuring their recycling and evolution. We present this molecular engine, a production example, and its various selectivities. The perspectives for such a dynamic approach to the emergence of peptides are evoked in the conclusion.

This work describes the synthesis of new hydrophobic acyclic nitroxides [derived from 2,2,5‐trimethyl‐4‐phenyl‐3‐azahexane‐3‐nitroxide (TIPNO)] designed to be employed in radical miniemulsion polymerization. We present the synthetic strategies employed to obtain these different nitroxides and the determination of certain important parameters, such as the dissociation rate constant, the combination rate constant, and the decomposition rate constant, of the corresponding alkoxyamines. All these new nitroxides give good control of the bulk radical polymerization of styrene in comparison with the parent TIPNO. The molecular structure of some nitroxides presented herein has been elucidated by single‐crystal X‐ray diffraction, and their structural determination helps us to understand better the influence of the nitroxide structure on the activation energy. A molecular modeling study has also been conducted on these new nitroxides, and a good linear correlation between the activation energy and the CNC bond angle for a series of nitroxides with the same type of leaving radical has been found. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1926–1940, 2006