电致化学发光体苝酰亚胺类分子的设计合成及生物传感器构筑

The two major problems in cathodic electrochemiluminescence(ECL) field are the focused high ECL potential of luminophore which results in large background interference, long detection time and limited mutiplex detection for biosensors. To develop luminophores with low and different ECL potential is an effective way to solve these problems. On the basis of obtained new data, we find perylene bisimide derivatives produce ECL at low potential and electron withdrawing groups will decrease the ECL potential. In this project, perylene bisimide derivatives will be used as ECL luminophores to functionalize carbon-based nanomaterial for constructing biosensors. We will develop our project from the following three aspects: (1) synthesis of perylene tetracarboxylic acid amide and perylene bisimide derivartives with different electron withdrawing group by changing the reaction temperature of perylenetetracarboxylic dianhydride and amine-group compounds, to investigate the influence of different electron withdrawing group such as carboxy-, sulfonic group, methylimidazole and trimethyl amine on the ECL potential and interpret the ECL mechanism; (2) construction of single biosensor based on water soluble perylene bisimide derivatives ECL luminophore with low ECL potential; (3) construction of potential-resovled mutiplexed biosensor based on perylene bisimide derivatives modified by trimethyl amine and perylene tetracarboxylic acid amide luminophores with ECL potential about -0.18 V and -0.75 V vs. Ag/AgCl, respectively.

目前阴极电致化学发光领域主要存在两个问题：大多数发光体的发光电位集中在高电位，导致传感器存在较大背景干扰，检测时间长以及电位分辨的多组分传感器发展缓慢。开发不同低电位下发光的阴极电致化学发光材料能有效解决这些问题。基于最新的实验数据，我们发现苝酰亚胺类分子在低电位下有强光辐射且分子中吸电子基团能降低发光电位。我们拟以此类分子为发光体，碳基材料为载体构筑传感器。本项目从以下三个方面开展：（1）通过调节苝四羧酸二酐与氨基化合物的反应温度生成苝四羧酸酰胺与不同吸电子基团修饰的苝酰亚胺两类分子，研究不同吸电子基团如羧基，磺酸基，甲基咪唑，三甲氨基对分子发光电位的影响，并阐释电致化学发光机理。（2）利用水溶性的苝酰亚胺衍生物分子构筑单组分传感器；（3）利用三甲氨基修饰的苝酰亚胺分子与苝四羧酸酰胺（以Ag/AgCl参比，发光电位分别为约-0.18 V，-0.75 V）构筑电位分辨的多组分传感器。

阴极电化学发光领域存在发光体发光电位普遍较高（>-1.8 V），氧气发射背景大，电位分辨的发光体严重缺乏等问题。这极大降低了电化学发光传感器检测灵敏度以及阻碍了电位分辨的比率传感器检测单组分及多组分同时检测的发展。项目运行以来，总体进展顺利，达到了预期目标，取得如下进展：(1)我们拓展了苝衍生物分子-苝四甲酸二酐，1,6,7,12-四氯苝四酸酐，N, N'-二甲基-3, 4, 9, 10-苝酰亚胺，N, N'-(3-二甲基氨丙基)-3, 4, 9, 10-苝酰亚胺，N, N'-二己酸盐-3, 4, 9, 10-苝酰亚胺在水相体系中的电化学发光性质的研究。我们发现1,6,7,12-四氯苝四酸酐，N, N'-二甲基-3, 4, 9, 10-苝酰亚胺, N, N'-二己酸盐-3, 4, 9, 10-苝酰亚胺与N, N'-(3-二甲基氨丙基)-3, 4, 9, 10-苝酰亚胺发光电位分别为-1.2 V，-0.42 V，-0.26 V，-0.26 V。在如此低的电位下，氧气发射背景被大幅消除。另外，这些发光体的波长长移到近红外区。1,6,7,12-四氯苝四酸酐的电化学发光波长为630 nm，N, N'-二甲基-3, 4, 9, 10-苝酰亚胺的电化学发光波长为689 nm。N, N'-2-(3-二甲基氨丙基)-3，4，9，10-苝四羧酸二酰亚胺的电化学发光波长为717 nm，N, N'-二己酸盐-3, 4, 9, 10-苝酰亚胺的电化学发光波长为700 nm。我们根据其电化学性质，荧光光谱，电化学发光光谱推测其电化学发光是由激发态二聚体产生的;（2）我们利用苝四甲酸二酐与苯胺形成多色电化学发光的超分子材料，该多色电化学发光是由激发态的苝四甲酸二酐单体，二聚体产生的，这为设计新颖多色发光材料奠定基础;（3）拓展了苝衍生物对肿瘤标志物的电化学发光传感应用：构建了低激发电位下单信号检测单组分的传感器；构筑了源于双波长信号汇集的单信号检测单组分的传感器；构筑了双电位比率检测传感器实现单组分精准检测；构筑了电位分辨的多组分同时检测传感器。