Publication

Self-assembly of peptide-based diblock oligomers

Harm-Anton Klok
2000
Article
Résumé

The synthesis and supramolecular organization of a novel class of rod-coil type diblock oligomers will be discussed. The diblock oligomers consist of a rodlike α-helical oligopeptide segment that is conjugated to an oligo(styrene) coil. In comparison with most of the rod-coil type oligomers that have been investigated so far, these peptide-based diblock oligomers possess some unique features: (i) the conformation of the oligopeptide rod segment can be reversibly manipulated under the action of appropriate external stimuli, and (ii) the self-assembly of these molecules is (also) driven by directed hydrogen-bonding interactions. The diblock oligomers are prepared by ring-opening polymerization of γ-benzyl-L-glutamate N-carboxyanhydride using a primary amine-terminated oligo(styrene) as the initiator. The diblock oligomers form thermotropic liquid-crystalline phases, whose supramolecular organization depends both on the relative block-lengths and on the conformation of the peptide segment.

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droite|400px|thumb|Un exemple de molécules se liant par liaisons d'hydrogène. L'auto-assemblage moléculaire est le processus par lequel des molécules soi-montant adoptent un agencement sans la direction d'une source extérieure. En général, le terme fait référence à l'auto-assemblage intermoléculaire alors que l'auto-assemblage intramoléculaire prend plus communément le nom de pliage ou de repliement dans le cas de protéines.
Auto-assemblage
L’auto-assemblage, parfois rapproché de l'auto-organisation, désigne les procédés par lesquels un système désorganisé de composants élémentaires s'assemble et s'organise de façon spontanée et autonome, à la suite d'interactions spécifiques et locales entre ces composants. On parle d'auto-assemblage moléculaire lorsque les composants en question sont des molécules, mais l'auto-assemblage s'observe à différentes échelles, des molécules à la formation du système solaire et des galaxies en passant par l'échelle nanométrique.
Crystal engineering
Crystal engineering studies the design and synthesis of solid-state structures with desired properties through deliberate control of intermolecular interactions. It is an interdisciplinary academic field, bridging solid-state and supramolecular chemistry. The main engineering strategies currently in use are hydrogen- and halogen bonding and coordination bonding. These may be understood with key concepts such as the supramolecular synthon and the secondary building unit. The term 'crystal engineering' was first used in 1955 by R.
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