Design and Synthesis of New Sensitive Dienophiles, and Application to the Quantitative Analysis of Biologically Active Conjugated Dienes

1.高灵敏双烯亲和剂的合成设计合成了以共轭双烯为靶标的荧光或化学发光双烯亲和剂。以1，2，4-三唑啉-3，5-二酮为活性基团，与化学发光发色团连接，合成了一种高灵敏的化学发光双烯试剂。2.将荧光双烯试剂(DMEQ-TAD)应用于维生素D的荧光分析，(1)研究了血浆维生素D代谢物的荧光分析方法，成功地建立了人血浆中25-OHD_3、24，25-(OH)_2D_3和活性激素1，25-(OH)_2D_3的测定方法。除9Z-异构体外，DMEQ-TAD高选择性地生成单加合物，而9Z-异构体只生成双加合物，表明DMEQ-TAD可作为生物液中维甲酸的荧光标记。(3)DMEQ-TAD与微囊藻毒素(一种来自蓝藻的环七肽毒素)在共轭二烯部分反应生成环加合物。环境微囊藻毒素的荧光分析方法正在研究中。

1. Synthesis of highly sensitive dienophilesFluorescent or chemiluminescent dienophiles targeting conjugated diene were designed and synthesized. A highly sensitive chemiluminescent dienophile, in which a chemiluminescent chromophore (acridinium ester group) and a reactive 1,2,4-triazoline-3,5-dione group were connected, was newly synthesized.2.A fluorescent dienophile (DMEQ-TAD) was applied to the fluorometric analysis of vitamin D,vitamin A and microcystins.(1) Fluorometric analysis of plasma vitamin D metabolites was examined and new accurate methods for assaying 25-OHD_3,24,25-(OH)_2D_3 and an active hormone 1,25-(OH)_2D_3 in human plasma were successfully developed.(2) Reactions of DMEQ-TED with retinoic acid and its geometrical isomers having a pentaene system were examined. Except for the 9Z-isomer, reactions gave the mono-adducts in high selectivity while the 9Z-isomer gave only the bis-adducts indicating that DMEQ-TAD might be useful as a fluorescence labeling for retinoic acids in biological fluid.(3) DMEQ-TAD reacted with microcystins, a cyclic heptaptide toxin from blue-green algae, at the conjugated diene part to yield the cycloadducts. The fluorometric method for assaying enviromental microcystins is under investigation.