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

• Published in: Journal of the American Chemical Society Vol. 141; no. 35; pp. 13877 - 13886
• Main Authors: Hendrikse, Simone I. S, Su, Lu, Hogervorst, Tim P, Lafleur, René P. M, Lou, Xianwen, van der Marel, Gijsbert A, Codee, Jeroen D. C, Meijer, E. W
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 04.09.2019; Amer Chemical Soc
• Subjects: Chemistry; Chemistry, Multidisciplinary; Physical Sciences; Science & Technology; POLYMERS; COOPERATIVITY; CYLINDRICAL MICELLES
• ISSN: 0002-7863; 1520-5126; 1520-5126
• DOI: 10.1021/jacs.9b06607

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.