From structure to function via complex supramolecular dendrimer systems

Abstract

This tutorial review summarizes strategies elaborated for the discovery and prediction of programmed primary structures derived from quasi-equivalent constitutional isomeric libraries of self-assembling dendrons, dendrimers and dendronized polymers. These libraries demonstrate an 82% predictability, defined as the percentage of similar primary structures resulting in at least one conserved supramolecular shape with internal order. A combination of structural and retrostructural analysis that employs methodologies transplanted from structural biology, adapted to giant supramolecular assemblies was used for this process. A periodic table database of programmed primary structures was elaborated and used to facilitate the emergence of a diversity of functions in complex dendrimer systems via first principles. Assemblies generated by supramolecular and covalent polymer backbones were critically compared. Although by definition complex functional systems cannot be designed, this tutorial hints to a methodology based on database analysis principles to facilitate design principles that may help to mediate an accelerated emergence of chemical, physical and most probably also societal, political and economic complex systems on a shorter time scale and lower cost than by the current methods. This tutorial review is limited to the simplest, synthetically most accessible self-assembling minidendrons, minidendrimers and polymers dendronized with minidendrons that are best analyzed and elucidated at molecular, supramolecular and theoretical levels, and most used in other laboratories. These structures are all interrelated, and their principles expand in a simple way to their higher generations.

Novel stable dendrimersome formulation for safe bioimaging applications

“…[46][47][48][49][50] Despite the lack of a detailed description of the mechanisms driving this phenomenon, a number of hypotheses have been proposed, including lipoproteinmediated lipid transfer and direct interaction with albumin or lipoproteins. 41,42,49 Although detailed studies about the structural stability of dendrimersomes have already been reported, [16][17][18][19][20] these did not consider specifically and thoroughly the role of biological variables. For this reason, we considered it important to devote efforts to assess the ability of Gadoteridol-loaded dendrimersomes to retain their payload in a blood-like environment.…”

“…mechanical resistance, wall thickness, chemical groups exposed on the outer surface) has driven the search for new categories of amphiphiles other than phospholipids. [10][11][12] Two examples are represented by polymersomes [13][14][15] and dendrimersomes, [16][17][18][19][20][21][22] which are obtained through the self-assembly of amphiphilic block co-polymers or JDs, respectively. Whereas the potential of polymersomes in biomedical studies has been already demonstrated, 14,15 dendrimersomes have been proposed only very recently, and therefore their behaviour in biological environments is largely unexplored.…”

Synthesis of poly(2-hydroxyethyl methacrylate)-grafted poly(aminoamide) dendrimers as polymeric nanostructures

“…Recently, different polymeric nanostructures such as inorganic/polymeric hybrid nanoparticles [1,2], hollow nanostructures [3,4], and dendrimers [5,6] have got much attention due to their applications in drug delivery [7], gene delivery [8], etc. Among mentioned structures, dendrimers as three-dimensional (3D), highly branched, and monodispersed nanostructures are obtained by iterative sequence of reaction steps [9,10].…”

Self‐Assembly of Amphiphilic Janus Dendrimers into Mechanically Robust Supramolecular Hydrogels for Sustained Drug Release

“…[25] In addition to gels, dendrimers and dendrons readily mediate the formation of ordered hierarchical assemblies. [14,[26][27][28][29][30] In this work we utilize amphiphilic Janus dendrimers based on Percec-type constitutionally isomeric AB2 and AB3 O-alkylated benzyls (hydrophobic blocks) and hydroxyl terminated 2,2-bis(methylol)propionic acid (bis-MPA) polyester frame (hydrophilic blocks) to form supramolecular hydrogels with excellent mechanical properties at very low mass proportion (0.2 per cent by mass). We further confirm the fibrous structure morphology and study the release of active enzymes, peptides and small molecule drugs from the gels (Figure 1).…”

“…[4,5] Dendritic gels rely on well-defined, sequentially branched polymers (dendrimers) to form nanoscale networks. Dendrimers with various architectures and topologies offer a high number of functional surface groups which can be tailored to enhance binding affinity or material structure properties, [6][7][8][9][10][11][12] mediate the formation of hierarchically ordered assemblies and other complex systems, [13,14] transfer and amplify chirality, [15,16] facilitate the formation of crystalline complexes, [8] serve as powerful structuredirecting tectons [17] and as "supramolecular glue". [18,19] Dendritic gels rely on well-defined, sequentially branched polymers (dendrimers) to form nanoscale networks.…”