Ting Richard, Lermer Leonard, Perrin David M
Department of Chemistry, The University of British Columbia, Vancouver, BC, V6T-1Z1, Canada.
J Am Chem Soc. 2004 Oct 13;126(40):12720-1. doi: 10.1021/ja046964y.
Herein we report evidence for a light-inducible DNAzyme. In so doing, we also disclose the synthesis and photochemical properties of a novel nucleoside: 8-(2-(4-imidazolyl)ethyl-1-thio)-2'-deoxyriboadenosine (d1). The light sensitivity of (d1) was evaluated via an examination of the photoinduced reactivation of DNAzyme 8-17E from an inactive form that contained a single nucleotide (d1) modification. Restoration of DNAzyme activity results from a photoinduced reversion of (d1) to unmodified deoxyadenosine. Deuterium studies indicate that water is the source of hydrogen in the C8-H product and not the alkylthio group, suggesting that reversion of (1) to adenosine is not a consequence of simple homolysis of the C8-S bond but of an unprecedented photochemical conversion. This adenosine, which affords significant control of catalytic reactivation of a DNAzyme, may find general use in photodecaging other biological systems.
在此我们报告了一种光诱导性脱氧核酶的证据。在此过程中，我们还披露了一种新型核苷的合成及光化学性质：8-(2-(4-咪唑基)乙基-1-硫代)-2'-脱氧核糖腺苷(d1)。通过检查含有单个核苷酸(d1)修饰的失活形式的脱氧核酶8-17E的光诱导再活化来评估(d1)的光敏感性。脱氧核酶活性的恢复是由于(d1)光诱导逆转回未修饰的脱氧腺苷。氘研究表明，水是C8-H产物中氢的来源，而非烷硫基，这表明(1)逆转回腺苷不是C8-S键简单均裂的结果，而是一种前所未有的光化学转化。这种对脱氧核酶催化再活化有显著控制作用的腺苷，可能在光解其他生物系统中得到广泛应用。
