Water-Soluble Arylazoisoxazole Photoswitches.

Azoheteroarenes are emerging as powerful alternatives to azobenzene molecular photoswitches. In this study, water-soluble arylazoisoxazole photoswitches are introduced. UV/vis and NMR spectroscopy revealed moderate to very good photostationary states and reversible photoisomerization between the E- and Z-isomers over multiple cycles with minimal photobleaching. Several arylazoisoxazoles form host-guest complexes with ß- and γ-cyclodextrin with significant differences in binding constants for each photoisomer as shown by isothermal titration calorimetry and NMR experiments, indicating their potential for photoresponsive host-guest chemistry in water. One carboxylic acid functionalized arylazoisoxazole can act as a hydrogelator, allowing gel properties to be manipulated reversibly with light. The hydrogel was characterized by rheological experiments, atom force microscopy and transmission electron microscopy. These results demonstrate that arylazoisoxazoles can find applications as molecular photoswitches in aqueous media.

Rapid and reversible optical switching of cell membrane area by an amphiphilic azobenzene.

Cellular membrane area is a key parameter for any living cell that is tightly regulated to avoid membrane damage. Changes in area-to-volume ratio are known to be critical for cell shape, but are mostly investigated by changing the cell volume via osmotic shocks. In turn, many important questions relating to cellular shape, membrane tension homeostasis and local membrane area cannot be easily addressed because experimental tools for controlled modulation of cell membrane area are lacking. Here we show that photoswitching an amphiphilic azobenzene can trigger its intercalation into the plasma membrane of various mammalian cells ranging from erythrocytes to myoblasts and cancer cells. The photoisomerization leads to a rapid (250-500 ms) and highly reversible membrane area change (ca 2 % for erythrocytes) that triggers a dramatic shape modulation of living cells.

Reversible Photoresponsive Modulation of Osmotic Pressure via Macromolecular Host-Guest Interaction.

The high spatiotemporal resolution of light as an external stimulus allows the control of shape, mechanical properties, and even forces generated by photoresponsive soft materials. For this purpose, supramolecular systems that respond readily and reversibly to photoirradiation and convert microscopic changes into macroscopic effects are needed. This work demonstrates the reversible light-responsive modulation of the osmotic pressure of an aqueous solution of an azobenzene-containing polymer (azopolymer) and α-cyclodextrin. Osmometry shows that this multivalent and photoresponsive host-guest complex can be used to modulate the concentration of solutes in the solution. Upon alternating irradiation with UV and blue light, the osmolality is reversibly switched by 28 mOsm kg-1. The switching amplitude increases linearly with the concentration of azopolymer and cyclodextrin. This drastic change in osmotic pressure is achieved by carefully designing an azopolymer that provides multivalent interactions as well as high water solubility. In this way, our study demonstrates a tunable control of colligative properties by photoinduced modulation of supramolecular interactions.