Reversible Photocontrol of Deoxyribozyme‐Catalyzed RNA Cleavage under Multiple‐Turnover Conditions

Abstract

Light is a highly effective and well-established bioorthogonal trigger by which the chemical or biochemical reactivities of nucleic acids can be localized in time and space.[1] Typically, photoactivation results from the irreversible removal of a masking group from strategic functionalities and has been utilized for the construction of DNA arrays, the study of RNA

Synthesis of Photo-Responsive Acridine-Modified DNA and Its Application to Site-Selective RNA Scission

“…Intrinsic activity of the cis-isomer is at least twice as high as that of the trans-isomer. Except for previous reports on photo-responsive ribozymes or deoxyribozymes, [16][17][18][19] this is the first photoresponsive site-selective RNA scission system. In order to accomplish more clear-cut switching, still more efficient isomerization of the azobenzene is necessary.…”

Deoxyribozymes: useful DNA catalysts in vitro and in vivo

“…This has been accomplished irreversibly by photocleavage of a light-sensitive nucleobase protecting group [104,105]. Alternatively, reversible photochemical control of RNA cleavage activity has been achieved by photoisomerization of an azobenzene group appended either to a deoxyribose [106] or to a non-nucleotidic backbone spacer [107,108]. In principle, such photochemical modulation would allow spatial control of DNA-catalyzed RNA cleavage, e.g., within a living organism, if light can be delivered appropriately.…”

The concept of photochemical enzyme models – State of the art

“…Photochromic switches have been successfully employed for influencing the rate of RNA or DNA single strand damage with modified nucleases or synthetic metal complexes [204][205][206][207]. In early attempts to create artificial endonuclease-like enzyme counterparts (photonucleases) the possibility of UV-light induced DNA-damage has also been explored [208].…”