Ioka Shuji, Saitoh Tsuyoshi, Iwano Satoshi, Suzuki Koji, Maki Shojiro A, Miyawaki Atsushi, Imoto Masaya, Nishiyama Shigeru
Department of Chemistry, Faculty of Science and Technology, Keio University, Hiyoshi 3-14-1, Kohoku-ku, 223-8522, Yokohama, Japan.
Department of Biosciences and Informatics, Faculty of Science and Technology, Keio University, Hiyoshi 3-14-1, Kohoku-ku, 223-8522, Yokohama, Japan.
Chemistry. 2016 Jun 27;22(27):9330-7. doi: 10.1002/chem.201600278. Epub 2016 May 24.
Five new firefly luciferin (1) analogues were synthesized and their light emission properties were examined. Modifications of the thiazoline moiety in 1 were employed to produce analogues containing acyclic amino acid side chains (2-4) and heterocyclic rings derived from amino acids (5 and 6) linked to the benzothiazole moiety. Although methyl esters of all of the synthetic derivatives exhibited chemiluminescence activity, only carboluciferin (6), possessing a pyrroline-substituted benzothiazole structure, had bioluminescence (BL) activity (λmax =547 nm). Results of bioluminescence studies with AMP-carboluciferin (AMP=adenosine monophosphate) and AMP-firefly luciferin showed that the nature of the thiazoline mimicking moiety affected the adenylation step of the luciferin-luciferase reaction required for production of potent BL. In addition, BL of 6 in living mice differed from that of 1 in that its luminescence decay rate was slower.
合成了五种新型萤火虫荧光素（1）类似物，并对其发光特性进行了研究。通过修饰1中的噻唑啉部分，制备了含有无环氨基酸侧链（2 - 4）以及与苯并噻唑部分相连的源自氨基酸的杂环（5和6）的类似物。尽管所有合成衍生物的甲酯均表现出化学发光活性，但只有具有吡咯啉取代苯并噻唑结构的咔唑荧光素（6）具有生物发光（BL）活性（λmax = 547 nm）。用AMP - 咔唑荧光素（AMP = 单磷酸腺苷）和AMP - 萤火虫荧光素进行生物发光研究的结果表明，模拟噻唑啉部分的性质影响了产生强效BL所需的荧光素 - 荧光素酶反应的腺苷化步骤。此外，6在活体小鼠中的BL与1不同，其发光衰减速率较慢。
