Cooperative Self-Assembly Transfer from Hierarchical Supramolecular Polymers to Gold Nanoparticles.
The transfer of information encoded by molecular subcomponents is a key phenomenon that regulates the biological inheritance in living organisms, yet there is a lack of understanding of related transfer mechanisms at the supramolecular level in artificial multicomponent systems. Our contribution to tackle this challenge has focused on the design of a thiolated π-conjugated linking unit, whose hierarchical, cooperative self-assembly in nonpolar media can be efficiently transferred from the molecular to the nanoscopic level, thereby enabling the reversible self-assembly of gold nanoparticle (AuNP) clusters. The transfer of supramolecular information by the linking π-system can only take place when a specific cooperative nucleation-elongation mechanism is operative, whereas low-ordered noncooperative assemblies formed below a critical concentration do not suffice to extend the order to the AuNP level. To the best of our knowledge, our approach has allowed for the first time a deep analysis of the hierarchy levels and thermodynamics involved in the self-assembly of AuNPs.
Departamento de Química Física I, Facultad de Ciencias Químicas, Universidad Complutense de Madrid , Avda. Complutense s/n, 28040, Madrid, Spain.
João Paulo
JP
Coelho
Departamento de Química Física I, Facultad de Ciencias Químicas, Universidad Complutense de Madrid , Avda. Complutense s/n, 28040, Madrid, Spain.
Gloria
G
Tardajos
Institut für Organische Chemie and Center for Nanosystems Chemistry, Universität Würzburg , Am Hubland, 97074 Würzburg, Germany.
Vladimir
V
Stepanenko
Institut für Organische Chemie and Center for Nanosystems Chemistry, Universität Würzburg , Am Hubland, 97074 Würzburg, Germany.
Alexander
A
Rödle
Institut für Organische Chemie and Center for Nanosystems Chemistry, Universität Würzburg , Am Hubland, 97074 Würzburg, Germany.
Gustavo
G
Fernández
Departamento de Química Física I, Facultad de Ciencias Químicas, Universidad Complutense de Madrid , Avda. Complutense s/n, 28040, Madrid, Spain.
Andrés
A
Guerrero-Martínez
D006046:Gold / Q000737:chemistry*; D053768:Metal Nanoparticles / Q000737:chemistry*; D018625:Microscopy, Atomic Force; D011108:Polymers / Q000737:chemistry*; D013056:Spectrophotometry, Ultraviolet; D013438:Sulfhydryl Compounds / Q000737:chemistry; D013696:Temperature
D011108:Polymers; D013438:Sulfhydryl Compounds; D006046:Gold
cooperativity; gold nanoparticle; self-assembly; supramolecular polymerization; π-conjugated systems