Probing the single pair rupture force of supramolecular quadruply hydrogen bonding modules by nano-adhesion measurement

Studying quadruply hydrogen bonding (QHB) module interactions in materials matrices presents a significant challenge because a wide variety of non-covalent interactions may be relevant. Here we introduce a method of surface modification with DeUG (7-deazaguanine urea), DAN (2,7-diamido-1,8-naphthyridine) and UPy (2-ureido-4[1H]-pyrimidone) modules to form self-assembled monolayers (SAMs) on a glass surface. The QHB interactions under mechanical stress were investigated by measuring adhesion force using PS-DAN (DAN modified polystyrene), PBMA-DeUG (DeUG modified poly butyl methacrylate) and PBA-UPy (UPy modified poly butyl acrylate) as adhesion promoters. A mechanical lap-shear test was used to evaluate the fracture resistance of QHB heterocomplexes. The maximum load at fail showed that QHB interaction contributed significantly (72%) to overall adhesion. For the QHB modified glass surface, using a polymer modified with its complementary QHB partner greatly facilitated their pairing efficiency, up to 40% for DAN-DeUG. A general method from which single pair ruptures force of QHB modules could be obtained using thermodynamic data obtained from solution chemistry was proposed. Using this method, the single pair rupture force for UPy–UPy was measured as 160 pN, and the single pair rupture force for DAN-DeUG was obtained as 193 pN.