Enhancing the Mechanical Properties of Guanosine-Based Supramolecular Hydrogels with Guanosine-Containing Polymers

• Published in: Macromolecules 2014-03, Vol.47 (5), p.1810-1818
• Main Authors: Way, Amanda E, Korpusik, Angie B, Dorsey, Taylor B, Buerkle, Lauren E, von Recum, Horst A, Rowan, Stuart J
• Format: Article
• Language: English
• Subjects: Applied sciences; Exact sciences and technology; Organic polymers; Physicochemistry of polymers; Polymers with particular properties; Preparation, kinetics, thermodynamics, mechanism and catalysts; Properties and characterization; Solution and gel properties
• ISSN: 0024-9297; 1520-5835
• DOI: 10.1021/ma402618z

We demonstrate that multivalent, polymeric 8-methoxyguanosine derivatives based on poly(dimethylacrylamide) can enhance the mechanical properties of the low molecular weight hydrogelator 8-methoxy-2′,3′,5′-tri-O-acetylguanosine at biologically relevant salt concentrations. It is proposed that these nongelling polymeric derivatives, under the conditions studied, can result in a significant enhancement of these supramolecular gels (e.g., for gels containing 1 wt % gelator G′ can be increased from ca. 2000 Pa with no additive to 80 000 Pa) by acting as supramolecular cross-linking units. Two competing mechanisms appear to play a role in these cogels. At low polymer concentrations the guanosine-containing polymers tend to act more as solubilizing agents for the gelator, thus weakening the gels, while at high guanosine-containing polymer concentrations the gels show a marked enhancement in mechanical properties consistent with them acting as supramolecular cross-linking agents. As such, the thermomechanical properties of these cogels depend on both the polymer:low molecular weight gelator ratio and the number of 8-methoxyguanosine repeat units present in the polymer additive. Thus, these polymeric guanosine-based additives impart the ability to tailor both the modulus and shear sensitivity of the gels. For example, cogels with a modulus ranging between ca. 95 and 80 000 Pa can be obtained through judicious selection of the type and amount of polymer additive.