ABSTRACT A rotaxane consisting of a macrocycle ring with two azobenzene units mechanically interlocked onto a bolaamphiphilic axle was incorporated into droplet interface bilayers (DIBs). The azobenzene groups on the ring underwent quasi‐reversible, photoisomerization‐induced cycling between 1‐ E and 1 ‐ Z configurations when irradiated with 370 and 467 nm light, respectively, enabling programmable access to different history‐dependent electrical behaviors from the same membrane. In the 1 ‐E configuration, bilayers exhibited type‐IIactive memristance that coincided with increasingly elevated ionic conduction, associated with progressively enhanced bilayer permeability during voltage cycling. In the 1 ‐Z configuration, bilayers displayed type‐I, passive memcapacitive behavior, reflecting tighter lipid packing and reduced ionic permeability. Photoswitching also yielded a nonvolatile, photoresponsive memcapacitor that could be modulated repetitively with negligible loss, likely via reversible changes in membrane thickness. Concurrent ohmic leakage currents across the membrane were less than 0.3%. These results agree with previous studies with increasing membrane permeability using photoswitchable rotaxanes and provide new insights into the coupling between volatile and nonvolatile memcapacitance during photoisomerization. More broadly, they demonstrate a new strategy for the manipulation of neuromorphic behaviors in soft materials using light, with implications for brain‐inspired computation and sensing.
Podar et al. (Mon,) studied this question.