Nonlinear Transient Permeability in pH-Responsive Bicontinuous Nanospheres.

We demonstrate the construction of pH-responsive bicontinuous nanospheres (BCNs) with nonlinear transient permeability and catalytic activity. The BCNs were assembled from amphiphilic block copolymers comprising pH-responsive groups and were loaded with the enzymes urease and horseradish peroxidase (HRP). A transient membrane permeability switch was introduced by employing the well-known pH-increasing effect of urease upon conversion of urea to ammonia. As expected, the coencapsulated HRP displayed a transiently regulated catalytic output profile upon addition of urea, with no significant product formation after the pH increase. This transient process displayed a nonlinear "dampening" behavior, induced by a decrease in membrane permeability as a result of significant local ammonia production. Furthermore, the catalytic output of HRP could be modulated by addition of different amounts of urea or by altering the buffer capacity of the system. Finally, this nonlinear dampening effect was not observed in spherical polymersomes, even though the membrane permeability could also be inhibited by addition of urea. The specific BCN morphology therefore allows to optimally control catalytic processes by pH changes in the nanoreactor microenvironment compared to bulk conditions due to its unique permeability profile.

Dampened Transient Actuation of Hydrogels Autonomously Controlled by pH-Responsive Bicontinuous Nanospheres.

The fabrication of a soft actuator with a dampened actuation response is presented. This was achieved via the incorporation into an actuating hydrogel of urease-loaded pH-responsive bicontinuous nanospheres (BCNs), whose membrane was able to regulate the permeability and thus conversion of fuel urea into ammonia. The dampened response of these nanoreactors to the enzymatically induced pH change was translated to a pH-responsive soft actuator. In hydrogels composed of a pH-responsive and nonresponsive layer, the transient pH gradient yielded an asymmetric swelling behavior, which induced a bending response. The transient actuation profile could be controlled by varying the external fuel concentrations. Furthermore, we showed that the spatial organization of the BCNs within the actuator had a great influence on the actuation response. Embedding the urease-loaded nanoreactors within the active, pH-responsive layer resulted in a reduced response due to local substrate conversion in comparison to embedding them within the passive layer of the bilayer hydrogel. Finally, we were able to induce transient actuation in a hydrogel comprising two identical active layers by the immobilization of the BCNs within one specific layer. Upon addition of urea, a local pH gradient was generated, which caused accelerated swelling in the BCN layer and transient bending of the device before the pH gradient was attenuated over time.