Adaptation in constitutional dynamic libraries and networks, switching between orthogonal metalloselection and photoselection processes.
Fiche publication
Date publication
juillet 2014
Auteurs
Membres identifiés du Cancéropôle Est :
Pr LEHN Jean-Marie
Tous les auteurs :
Vantomme G, Jiang S, Lehn JM
Lien Pubmed
Résumé
Constitutional dynamic libraries of hydrazones (a)A(b)B and acylhydrazones (a)A(c)C undergo reorganization and adaptation in response to a chemical effector (metal cations) or a physical stimulus (light). The set of hydrazones [(1)A(1)B, (1)A(2)B, (2)A(1)B, (2)A(2)B] undergoes metalloselection on addition of zinc cations which drive the amplification of Zn((1)A(2)B)2 by selection of the fittest component (1)A(2)B. The set of acylhydrazones [E-(1)A(1)C, (1)A(2)C, (2)A(1)C, (2)A(2)C] undergoes photoselection by irradiation of the system, which causes photoisomerization of E-(1)A(1)C into Z-(1)A(1)C with amplification of the latter. The set of acyl hydrazones [E-(1)A(1)C, (1)A(3)C, (2)A(1)C, (2)A(3)C] undergoes a dual adaptation via component exchange and selection in response to two orthogonal external agents: a chemical effector, metal cations, and a physical stimulus, light irradiation. Metalloselection takes place on addition of zinc cations which drive the amplification of Zn((1)A(3)C)2 by selection of the fittest constituent (1)A(3)C. Photoselection is obtained on irradiation of the acylhydrazones that leads to photoisomerization from E-(1)A(1)C to Z-(1)A(1)C configuration with amplification of the latter. These changes may be represented by square constitutional dynamic networks that display up-regulation of the pairs of agonists ((1)A(2)B, (2)A(1)B), (Z-(1)A(1)C, (2)A(2)C), ((1)A(3)C, (2)A(1)C), (Z-(1)A(1)C, (2)A(3)C) and the simultaneous down-regulation of the pairs of antagonists ((1)A(1)B, (2)A(2)B), ((1)A(2)C, (2)A(1)C), (E-(1)A(1)C, (2)A(3)C), ((1)A(3)C, (2)A(1)C). The orthogonal dual adaptation undergone by the set of acylhydrazones amounts to a network switching process.
Référence
J Am Chem Soc. 2014 Jul 2;136(26):9509-18