Laboratoire de Chimie Supramoléculaire, Institut de Science et d'Ingénierie Supramoléculaires (ISIS), Université de Strasbourg , 8 Allée Gaspard Monge, 67000 Strasbourg, France.
J Am Chem Soc. 2014 Jul 2;136(26):9509-18. doi: 10.1021/ja504813r. Epub 2014 Jun 17.
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.
腙（a）A（b）B 和酰腙（a）A（c）C 的动态构象库会对化学效应物（金属阳离子）或物理刺激（光）做出重组和适应。当添加锌阳离子时，腙的集合[(1)A(1)B、(1)A(2)B、(2)A(1)B、(2)A(2)B]会发生金属选择，这会通过选择最合适的组分(1)A(2)B 来放大 Zn((1)A(2)B)2。酰腙的集合[E-(1)A(1)C、(1)A(2)C、(2)A(1)C、(2)A(2)C]通过系统的辐照进行光选择，这会导致 E-(1)A(1)C 光异构化为 Z-(1)A(1)C，从而放大后者。酰腙的集合[E-(1)A(1)C、(1)A(3)C、(2)A(1)C、(2)A(3)C]通过组分交换和选择对两种正交外源性试剂（化学效应物金属阳离子和物理刺激物光辐照）进行双重适应。当添加锌阳离子时，会发生金属选择，这会通过选择最合适的组分(1)A(3)C 来放大 Zn((1)A(3)C)2。酰腙的光选择是通过辐照导致 E-(1)A(1)C 光异构化为 Z-(1)A(1)C 构型，从而放大后者。这些变化可以用正方形的构态动态网络来表示，显示出对配体对((1)A(2)B、(2)A(1)B)、(Z-(1)A(1)C、(2)A(2)C)和拮抗剂对((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)的上调，同时对(E-(1)A(1)C、(2)A(3)C)、((1)A(3)C、(2)A(1)C)的下调。酰腙集合所经历的正交双重适应相当于网络切换过程。
