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This lecture explores the self-assembly of heterobimetallic systems, focusing on the formation of robust bis(guanidinium)/dicarboxylate heteroduplexes in water. The presentation covers the importance of synthetic H-bond systems for materials fabrication, such as supramolecular polymers and hydrogels. Strategies for developing H-bond-mediated duplex systems with high binding affinities in water are discussed, emphasizing the role of H-bond-assisted ionic pairs. The lecture delves into the analysis methods, including ITC and UV-VIS titration, to assess the binding interactions between the monomers. The goal is to create a high Kass duplex system in water, showcasing the potential for applications in materials science.