Many marine organisms have developed adhesives that are able to bond under water, overcoming the challenges associated with wet adhesion. A key element in the processing of several natural underwater glues is complex coacervation, a liquid–liquid phase separation driven by complexation of oppositely charged macromolecules. Inspired by these examples, the development of a fully synthetic complex coacervate‐based adhesive is reported with an in situ setting mechanism, which can be triggered by a change in temperature and/or a change in ionic strength. The adhesive consists of a matrix of oppositely charged polyelectrolytes that are modified with thermoresponsive poly(N‐isopropylacrylamide) (PNIPAM) grafts. The adhesive, which initially starts out as a fluid complex coacervate with limited adhesion at room temperature and high ionic strength, transitions into a viscoelastic solid upon an increase in temperature and/or a decrease in the salt concentration of the environment. Consequently, the thermoresponsive chains self‐associate into hydrophobic domains and/or the polyelectrolyte matrix contracts, without inducing any macroscopic shrinking. The presence of PNIPAM favors energy dissipation by softening the material and by allowing crack blunting. The high work of adhesion, the gelation kinetics, and the easy tunability of the system make it a potential candidate for soft tissue adhesion in physiological environments.

Most commercially available soft tissue glues offer poor performance in the human body. We have developed an injectable adhesive whose setting mechanism is activated by a change in environmental factors (i.e. temperature and/or ionic strength). The material is developed by mimicking a mechanism observed in many natural maritime glues: complex coacervation, a liquid-liquid phase separation between oppositely charged polyelectrolytes. Complex coacervates are characterized by a high-water content, which inevitably weakens the glue. Here, we aim to increase the adhesive performance by systematically tuning the water content, a key parameter affecting the material properties. Among the several strategies here explored, the most effective one is the mechanical removal of water using an extruder, resulting in a work of adhesion increase of one order of magnitude compared to the original formulation.

The development of visible-light 3D printing technology by using water-soluble initiating systems has attracted widespread attention due to their potential applications in the manufacture of hydrogels. Besides, at present, the preparation of water-soluble photoinitiators suitable for visible light irradiation (such as LEDs) still remains a challenge. Therefore, this work is devoted to developing water-soluble photoinitiators (PI)/photoinitiating systems (PIS) upon irradiation with a LED @ 405 nm. In detail, a new water-slightly-soluble chalcone derivative dye [(E)-3-(4-(dimethylamino) phenyl)-1-(4-(2-(2-(2-methoxyethoxy) ethoxy) ethoxy) phenyl) prop-2-en-1-one] was synthesized here and used as a PI with a water-soluble coinitiator, i.e., triethanolamine (TEA) which was also used as an electron donor. When combined together, a charge transfer complex (CTC) formed immediately which exhibited excellent initiating ability for the free radical photopolymerization of poly(ethyleneglycol)diacrylate (PEG-DA). In light of the powerful CTC effect, the [dye-TEA] CTC could not only exhibit enhanced water solubility and mechanical properties but could also be effectively applied for 3D printing. This CTC system is environmentally friendly and cost-saving which demonstrates a great potential to prepare hydrogels via photopolymerization.

In this work, we report the systematic investigation of a multiresponsive complex coacervate-based underwater adhesive, obtained by combining polyelectrolyte domains and thermoresponsive poly(N-isopropylacrylamide) (PNIPAM) units. This material exhibits a transition from liquid to solid but, differently from most reactive glues, is completely held together by non-covalent interactions, i.e., electrostatic and hydrophobic. Because the solidification results in a kinetically trapped morphology, the final mechanical properties strongly depend on the preparation conditions and on the surrounding environment. A systematic study is performed to assess the effect of ionic strength and of PNIPAM content on the thermal, rheological and adhesive properties. This study enables the optimization of polymer composition and environmental conditions for this underwater adhesive system. The best performance with a work of adhesion of 6.5 J/m² was found for the complex coacervates prepared at high ionic strength (0.75 M NaCl) and at an optimal PNIPAM content around 30% mol/mol. The high ionic strength enables injectability, while the hydrated PNIPAM domains provide additional dissipation, without softening the material so much that it becomes too weak to resist detaching stress.