Spiropyran Photoswitches in the Context of DNA: Synthesis and Photochromic Properties

A new design is presented for the incorporation of spiropyran photoswitches into nucleic acids by oligonucleotide solid phase synthesis. This design enables interaction of the 6-nitrospirobenzopyran (NitroBIPS) photoswitch with the adjacent nucleobases and leaves the photochemical properties of NitroBIPS intact. UV/Vis spectroscopy and HPLC revealed that NitroBIPS incorporated into DNA consists of up to 40% merocyanine in its thermal equilibrium and undergoes reversible switching between the photoisomeric spiropyran (SP) and merocyanin (MC) state by alternating excitation using visible light or heat for at least fifteen switching cycles. Exchanging the chromene part of NitroBIPS on the DNA level gives access to differently substituted spiropyran derivatives allowing the screening for spiropyrans with suitable properties in a straightforward manner. Thus, by incorporating the highly hydrolysis-stable pyrido-spiropyran derivative PyBIPS pure light-triggered reversible switching of a spiropyran in DNA has been realized for the first time. Therefore, this design represents a new useful platform for investigating the photochromic behavior of different spiropyran photoswitches in a nucleic acid environment and for using spiropyrans to induce light- or heat-triggered changes in conformations or in fluorescence quenching properties of oligonucleotides.