Elucidating the Ordering in Self-Assembled Glycocalyx Mimicking Supramolecular Copolymers in Water

Abstract

Polysaccharides present in the glycocalyx and extracellular matrix are highly important for a multitude of functions. Oligo- and polysaccharides-based biomaterials are being developed to mimic the glycocalyx, but the spatial functionalization of these polysaccharides represents a major challenge. In this paper, a series of benzene-1,3,5-tricarboxamide (BTA) based supramolecular monomers is designed and synthesized with mono- (BTA-β-d-glucose; BTA-Glc and BTA-α-d-mannose; BTA-Man) or disaccharides (BTA-β-d-cellobiose; BTA-Cel) at their periphery or a monosaccharide (BTA-OEG4-α-d-mannose; BTA-OEG4-Man) at the end of a tetraethylene glycol linker. These glycosylated BTAs have been used to generate supramolecular assemblies and it is shown that the nature of the carbohydrate appendage is crucial for the supramolecular (co)polymerization behavior. BTA-Glc and BTA-Man are shown to assemble into micrometers long 1D (bundled) fibers with opposite helicities, whereas BTA-Cel and BTA-OEG4-Man formed small spherical micelles. The latter two monomers are used in a copolymerization approach with BTA-Glc, BTA-Man, or ethylene glycol BTA (BTA-OEG4) to give 1D fibers with BTA-Cel or BTA-OEG4-Man incorporated. Consequently, the carbohydrate appendage influences both the assembly behavior and the internal order. Using this approach it is possible to create 1D-fibers with adjustable saccharide densities exhibiting tailored dynamic exchange profiles. Furthermore, hydrogels with tunable mechanical properties can be achieved, opening up possibilities for the development of multicomponent functional biomaterials.

Particle engineering enabled by polyphenol-mediated supramolecular networks

“…However, this bottom-up approach for particle engineering requires a fine balance between the intrinsic supramolecular forces of assembly and the subsequent interfacial and stabilizing interactions, which has been an ongoing challenge 14 – 16 . To balance these supramolecular forces, synthetic approaches generally require the multi-step, rigorous synthesis of the supramolecular building blocks prior to assembly under exacting conditions 10 , 14 , 17 , 18 . Therefore, identifying readily available building blocks that are capable of assembling under ambient conditions with a high-degree of structural control and that exhibit an inherently high-binding affinity for a diverse range of materials will provide new opportunities for engineering complex nanostructured materials for various applications.…”

Supramolecular Double Helices from Small C3-Symmetrical Molecules Aggregated in Water

“… 39 Similar results have been recently obtained with BTAs that have carbohydrate groups at the periphery. 40 In the past, we were never able to elucidate the detailed structure of such fibers. For that, advanced cryo-TEM and analyses are required to characterize these polymers at a length scale that is close to the resolution and noise limit.…”

Exploring the Potential of Benzene-1,3,5-tricarboxamide Supramolecular Polymers as Biomaterials

“… 23 , 31 − 35 Furthermore, hydrogels were recently obtained by increasing the concentration of fibers. 34 , 36 The dynamic and self-healing characters of these hydrogels make them extremely powerful tools to mimic the extracellular matrix. Nevertheless, their application as biomaterials in, for example, tissue engineering is still limited, also due to the lack of detailed knowledge on how these supramolecular materials behave in physiological environments and, especially, on how they interact with biologically relevant species, that is, proteins and cells.…”