Thiourea as a "Polar Hydrophobic" Hydrogen-Bonding Motif: Application to Highly Durable All-Underwater Adhesion.

Here, we report that, in contrast to urea, thiourea functions as a "polar hydrophobic" hydrogen-bonding motif. Although thiourea is more acidic than urea, thiourea exchanges its N-H protons with water at a rate that is 160 times slower than that for urea at 70 °C. This suggests that thiourea is much less hydrated than urea in an aqueous environment. What led us to this interesting principle was the serendipitous finding that self-healable poly(ether thiourea) adhered strongly to wet glass surfaces. This discovery enabled us to develop an exceptionally durable all-underwater adhesive that can maintain large adhesive strength for over a year even in seawater, simply by mechanically mixing three water-insoluble liquid components on target surfaces. Because thiourea is hydrophobic, its hydrogen-bonding networks within the adhesive structure and at the adhesive-target interface are presumed to be dehydrated. For comparison, a reference adhesive using urea as a representative "polar hydrophilic" hydrogen-bonding motif was durable for less than 4 days in water. Highly durable all-underwater adhesives are needed in various fields of marine engineering and biomedical sciences, but their development has been a major challenge because a hydration layer that spontaneously forms in water always inhibits adhesion.

Supramolecular copolymerization of hydrophobic and hydrophilic monomers in liquid crystalline media.

In the case of covalent polymers, immiscible polymers can be integrated by covalently linking them together, but such a strategy is not possible in supramolecular polymers. Here we report the supramolecular copolymerization of two porphyrin-based monomers, C10P2H and TEGPCu with side chains bearing cyanobiphenyl (CB) groups at the ends of hydrophobic alkyl or hydrophilic tetraethylene glycol chains, respectively. These monomers undergo self-sorting supramolecular polymerization in highly diluted solutions ([monomer] = 3.4 × 10-9 mol% (2.0 × 10-8 mol L-1)) in nonpolar media due to the incompatibility of the side chains. Surprisingly, these monomers undergo supramolecular copolymerization under high concentration conditions ([monomer] = 7.7 mol%) in the medium of 4-cyano-4'-pentyloxybiphenyl (5OCB) to form a columnar liquid crystalline phase under thermodynamic conditions, where the individual columns are composed of supramolecular block copolymers. The combination of CB ends of both monomers and the 5OCB medium is essential for the two monomers to form an integrated structure in a condensed system without phase separation.