Self-assembled multivalent

Targeting Galectin-1 with Self-Assembled Multivalent Pseudopolyrotaxanes... 

Barnard, A., Posocco, R, Fermeglia, M., Tschiche, A., Calderon, M., Pricl, S., et al., 2014. Double-degradable responsive self-assembled multivalent arrays—temporary nanoseale recognition between dendrons and DNA. Org. Biomol. Chem. 12 (3), 446-455. 

Self-assembly of aromatic dendron subunits has been tried by the design of coordination to multivalent metal cations (i.e., metal-cored dendrimer complexes). Several metal-cored dendrimer complexes have successfully exhibited luminescence by antenna effects. 

Historically, the first multivalent glycoconjugate obtained by metal-assisted self-assembly was described in 1994 by Sakai and Sasaki (Fig. 35).267 The methodology was based on the trimerization of unsymmetrical Bipy-GalNAc (307) induced by the presence of Fe(II) salts, to give the tridentate Fen(bipy-GalNAc)3 cluster 308 as a mixture of four diastereomeric isomers (A-fac, A-fac, A-mer, and A-mer). 

Self-assembly of such dendrimers is a dynamic equilibrium process (Fig. 8.9). Conceivably, the non-covalent polyvalent ligands can be optimised with regard to their size and shape in the presence of natural multivalent receptors, as a kind of template for their own multivalent inhibitor, and thus open up a range of physiologically relevant polyvalent interactions [40 a]. 

The stepwise construction of self-assembled organic/inorganic multilayers based on multivalent supramolecular interactions between guest-functionalized dendrimers and nanoparticles and host-modified gold nanoparticles has been developed, yielding supramolecular LbL assembly (Fig. 13.8).12 Multilayer thin films composed of... 

Fig. 5 Generation of multifunctionality/multivalency by self-assembly. Octa-valency from either hydrazide and dialdehyde components/subunits (left), or preformed ligands (top right) in the case of the formation of [2x2] grid-type metallosupramolecular architectures. Insert. Schematic representation of the generation of hexadeca-valency from tetrasubstituted ligand molecules...

Mahalingam, V. Onclin, S. Peter, M. Ravoo, B. J. Huskens, J. Reinhoudt, D. N. Directed Self-Assembly of Functionalized Silica Nanoparticles on Molecular Printboards Through Multivalent Supramolecular Interactions. Langmuir 2004, 20, 11756-11762... 

While multivalency, self-assembly, and template effects provide strategies aiming at generating more and more complex architectures, supramolecular chemistry can also be utilized for controlling reactivity and even catalyzing reactions. Closely related to organocatalysis, supramolecular catalysts [39] accelerate reactions by... 

---