RESUMEN
In this report, we describe the circularly polarized luminescence (CPL) of the RNA duplexes having one to four 2'-O-pyrene modified uridines (Upy) and the DNA duplexes having two, four, and six pyrene modified non-nucleosidic linkers (Py). Both the pyrene π-stack arrays formed on the RNA and DNA double helical structures exhibited pyrene excimer fluorescence. In the pyrene-modified RNA systems, the RNA duplex having four Upys gives CPL emission with glum value of <0.01 at 480 nm. The structure of pyrene stacks on the RNA duplex may be rigidly regulated with increase in the Upy domains, which resulted in the CPL emission. In the DNA systems, the pyrene-modified duplexes containing two and four Pys exhibited CPL emission with glum values of <0.001 at 505 nm. The pyrene π-stack arrays presented here show CPL emission. However, the glum values are relatively small when compared with our previous system consisting of the pyrene-zipper arrays on RNA.
Asunto(s)
Ácidos Nucleicos Heterodúplex/química , Pirenos/química , ARN/química , Dicroismo Circular , ADN/química , Luminiscencia , Compuestos Organofosforados/química , Uridina/químicaRESUMEN
Circularly polarized luminescence (CPL) was observed in pyrene zipper arrays helically arranged on an RNA duplex. Hybridization of complementary RNA strands having multiple (two to five) 2'-O-pyrenylmethyl modified nucleosides affords an RNA duplex with normal thermal stability. The pyrene fluorophores are assembled like a zipper in a well-defined helical manner along the axis of RNA duplex, which, upon 350â nm UV illumination, resulted in CPL emission with pyrene excimer formation. CPL (glum ) levels observed for the pyrene arrays in dilute aqueous solution were +2×10(-2) -+3.5×10(-2) , which are comparable with |glum | for chiral organic molecules and related systems. The positive CPL signals are consistent with a right-handed helical structure. Temperature dependence on CPL emission indicates that the stable rigid RNA structure is responsible for the strong CPL signals. The single pyrene-modified RNA duplex did not show any CPL signal.