Dual Crosslinking Photo‐Switches for Orthogonal Photo‐Control of Hybridization Between Serinol Nucleic Acid and RNA

Abstract

Wavelength‐selective photo‐regulation by multiple chromophores responding to different wavelengths can expand the variation of photo‐manipulating systems. Herein, we report the orthogonal photo‐regulation of duplex formation between serinol nucleic acid (SNA) and RNA using light‐induced crosslinking reactions mediated by a new photo‐reactive nucleobase 8‐naphthylvinyladenine (NVA) and previously described 8‐pyrenylvinyladenine (PVA). An intrastrand crosslink was induced in an SNA strand containing two adjacent NVA residues by irradiation with 340–405 nm light; the crosslink was reversed by irradiation with ≤300 nm light. In an SNA strand with adjacent NVA and PVA residues, an intrastrand crosslink resulted from irradiation with 405–465 nm light that was reversed by irradiation with ≤340 nm light. Intrastrand photo‐crosslinking caused severe destabilization of an SNA/RNA duplex, resulting in dissociation to single strands. Cycloreversion resulted in duplex formation. With these NVA/NVA and NVA/PVA photo‐switches, four hybridization states of two SNA/RNA duplexes could be orthogonally photo‐controlled by irradiation with a suitable wavelength of light.

Acyclic Nucleic Acids with Phosphodiester Linkages—Synthesis, Properties and Potential Applications

“…Similar functionality was achieved with 8-naphthylvinyl-adenine (A N , 38, Chart 12), although in this case crosslinking to form the A N =A N adduct was performed with light of 340-405 nm (455 nm for A*=A*) and the restoration of A N occurred upon irradiation with ≤300 nm light (340 nm for A*) [73]. For a system A*, A N crosslinking to A*=A N was performed with light from 405 to 465 nm and recovery occurred upon irradiation with ≤340 nm.…”

Photochemical modifications for DNA/RNA oligonucleotides

“…122 The crosslinking and uncrosslinking reactions were rendered complete aer 1 h (irradiation at 455 nm) and 15 min (340 nm), respectively. 122 In the case of NV A, irradiation with 405 nm light for 60 s led to the disappearance of the absorption band around 360 nm, and irradiation with 300 nm light of this photo-adduct led to the cycloreversion: 61% of the initial absorption band was recovered within 120 s. 123 Four hybridization states of two SNA/RNA duplexes containing either the NV A/ NV A pair or NV A/ PV A could be orthogonally controlled using different wavelengths of light. 123 Thermodynamic or structural characteristics.…”

“…123 In all these cases, the intrastrand photo-crosslinking destabilize SNA/RNA duplexes, resulting in duplex dissociation while its cycloreversion led to duplex formation. 123 With these NV A/ NV A and NV A/ PV A photo-switches, the hybridization states of SNA/RNA duplexes could be independently controlled by using light of varying wavelengths. 123 Reaction characteristics.…”

“…123 With these NV A/ NV A and NV A/ PV A photo-switches, the hybridization states of SNA/RNA duplexes could be independently controlled by using light of varying wavelengths. 123 Reaction characteristics. Strylpyrene pairs (Spa and Spb) introduced as a part of D-threoninol linker in the opposite strands of DNA duplex could also undergo [2 + 2] photocycloaddition using visible light (l z 455 nm), but gave two diastereomers as a result of the rotation of the styrylpyrene residues.…”

“…The reverse reaction, cycloreversion, led to the restoration of the duplexes. 123 Biological applications. NV A and PV A were studied as a part of SNA/RNA as mentioned above as reversible crosslinkers that stabilize the SNA/RNA duplexes.…”