Nakamura Mitsunobu, Suzuki Junpei, Ota Fuyuki, Takada Tadao, Akagi Kazuo, Yamana Kazushige
Department of Applied Chemistry, Graduate School of Engineering, University of Hyogo, 2167 Shosha, Himeji, Hyogo, 671-2280, Japan.
Department of Polymer Chemistry, Kyoto University, Katsura, Kyoto, 615-8510, Japan.
Chemistry. 2016 Jun 27;22(27):9121-4. doi: 10.1002/chem.201602043. Epub 2016 Jun 6.
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 350 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.
在螺旋排列于RNA双链体上的芘拉链阵列中观察到圆偏振发光（CPL）。具有多个（两个至五个）2'-O-芘甲基修饰核苷的互补RNA链杂交可形成具有正常热稳定性的RNA双链体。芘荧光团沿着RNA双链体的轴以明确的螺旋方式像拉链一样组装，在350 nm紫外线照射下，会产生带有芘准分子形成的CPL发射。在稀水溶液中观察到的芘阵列的CPL（glum）水平为+2×10(-2) - +3.5×10(-2)，这与手性有机分子及相关体系的|glum|相当。正CPL信号与右手螺旋结构一致。CPL发射的温度依赖性表明，稳定的刚性RNA结构是强CPL信号的原因。单个芘修饰的RNA双链体未显示任何CPL信号。
