A Reversible Proton Generator with On/Off Thermoswitch.

ABSTRACT

A reversible polymer photoacid with a thermal on/off switch at physiological temperature able to trigger a large pH modulation of its environment is prepared. Light is used to control the acidity of the solution. Additionally, the temperature could be used to modulate the photoacid efficiency, practically turning on and off the ability of the polymer to produce protons. The behavior of this thermoresponsive photoacid copolymer is the result of the combined action of the temperature-responsive N-isopropylacrylamide and of a reversible photoacid monomer based on a spiropyran derivative. The acidification of the aqueous medium is activated by irradiation at λ = 460 nm. The reverse reaction is achieved by removing the light stimuli or by exposing the solution to UV-light. Increasing the temperature above the lower critical solution temperature of the copolymer deactivates the photoacid and irradiation at λ = 460 nm does not lead to the generation of protons or to any detectable change in the pH value of the solution. Hence, the addition of N-isopropylacrylamide as a comonomer acts as a thermal on/off switch for the photoacid and the coupling of temperature-and light-responsiveness in the polyphotoacids yields a "thermophotoacid".