Constitutional Dynamic Chemistry
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Constitutional Dynamic Chemistry. Preface, Topics Curr. Chem., 2012,
Constitutional Dynamic Systems, Editorial, Israel J. Chem. 2013,53(1-2), 9-10.
Chem. Commun. 2010, 46, 7466-7476.
| Constitutional Dynamic Chemistry (CDC) provides an evolutional approach to the generation of chemical diversity on both the molecular and supramolecular levels through the implementation of reversible covalent reactions and non-covalent intermolecular interactions respectively. It confers to chemical systems a fifth dimension, that of constitution, in addition to the 4D spatial/temporal chemical space. The self-assembly of the components into well-defined architectures across size scale, controlled by mastering molecular/supramolecular constitutional affinities, embodies the flow of structural information from molecular level toward nanoscale dimensions. It is highly dependent on the nature of the network and has been shown to be influenced by factors such as shape, valency, orientation and flexibility of components. |
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Natural systems have build up complex evolutive functions over many centuries. The actual challenges are to implement Constitutional Dynamic Systems for confering to non-natural chemical systems the features of natural selection and functional evolution. They lie at the forefront of present cross-disciplinary research, extending over the vast field of scientific challenges related to the property (function)-driven generation of adjustable (adaptive) artificial systems and directed at understanding the fundamental aspects of the self-organization of matter, involving in particular controlled structure generation, adaptation and replication processes. They open up wide perspectives to imagining a fundamental transition from molecular/ supramolecular design toward constitutional self-selection approaches, which may also bear great potential in various applications.
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Constitutional Dynamic Libraries toward Dynamic Constitutional/Interactive Systems
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| Multistate and phase change selection in constitutional multivalent systems
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Topics Curr. Chem., 2012, 322, 33-54.
J. Mater Chem, 2010, 20, 9443–9448
Angew. Chem. Int. Ed. 2007, 46, 4268-4272.
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Molecular architectures and materials can be constitutionally self-sorted in the presence of different biomolecular targets or external physical stimuli or chemical effectors, thus responding to an external selection pressure. The high selectivity and specificity of different bioreceptors or self-correlated internal interactions may be used to describe the complex constitutional behaviors through multistate component selection from a dynamic library. The self-selection may results in the dynamic amplification of self-optimized architectures, during the phase change process. The sol-gel resolution of dynamic molecular/ supramolecular libraries leads to higher self-organized constitutional hybrid materials, in which organic (supramolecular)/inorganic domains are reversibily connected.
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Hierarchical dynamic resolution of Guanine, G supramolecular libraries of linear G-ribbons and G-quartet/G-quadruplex in the presence of templating K+ cation followed by sol-gel process. Scanning Electronic Microscopy- SEM images of the left- and right-hand twisted hexagonal nanorods resulted by sol-gel transcription of the chiral hexagonal G-quadruplex in the hybrid organic-inorganic material and of silica microsprings resulted by calcination of hybrid nanorods.
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Constitutional transcription of base-pairing codes by sol-gel resolution of dynamic supramolecular libraries resulting in the formation of (a) Hoogsteen packing of the Adenine MA hybrid material; (b) Watson-Crick packing of the Uracil MU hybrid material and (c) A2WCU2H packing of the Adenine-Uracil MA-U hybrid material; (d) Postulated model of self-organization of parallel H-bonded nucleobase aggregates and hydrophobic propyltriethoxysilane layers. (e) Guide to the eye interplanar dSi-Si distances calculated from the geometry of minimized structures versus experimental interplanar Bragg diffraction distances. The squares correspond to the unpolymerized powders of precursors A, U and their 1:1 mixture AUmix, while coloured circles correspond to hybrid materials MA, MU and MA-U. (f) TEM images of MA-U hybrid material.
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Cation-template resolution of a dynamic supramolecular guanine system in which G-quartet is reversibly exchanging with linear ribbons followed by a secondary irreversible sol-gel selection of G-quadruplex hybrid materials.
Constitutional hybrid materials based on G-quadruplex and ureidocrown-ether architectures applied by using a "dynamic reversible hydrophobic interface" between the organic and inorganic phases.
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