双亲性噻吩羧酸衍生物的制备及潜指纹检测应用  

Preparation of amphiphilic thienyl carboxylic acid derivatives and application for latent fingerprint detection

作　　者：蒋钊 孔兆宇 乔瑞洁 刘子川 宋林洲 朱森强 朱红军 刘睿 JIANG Zhao;KONG Zhaoyu;QIAO Ruijie;LIU Zichuan;SONG Linzhou;ZHU Senqiang;ZHU Hongjun;LIU Rui(School of Chemistry and Molecular Engineering,Nanjing Tech University,Nanjing 211816,Jiangsu,China)

机构地区：[1]南京工业大学化学与分子工程学院,江苏南京211816

出　　处：《精细化工》2024年第9期1925-1932,共8页Fine Chemicals

基　　金：江苏省自然科学基金项目(BK20220351);江苏省高等学校基础科学研究项目(22KJB150027);大学生创新创业训练计划项目(2023DC0829)。

摘　　要：以5-溴噻吩-2-羧酸和4-(二苯基胺基)苯硼酸为原料,通过Suzuki偶联反应,合成了双亲性噻吩羧酸衍生物5-[4-(二苯基氨基)苯基]噻吩-2-羧酸(TTC-H)及其钾盐(TTC-K)。采用1HNMR和13CNMR对两个化合物进行了结构表征;利用UV-Vis吸收光谱、荧光发射光谱讨论了TTC-H和TTC-K及其聚集态的光物理性质,对其进行密度泛函理论计算和溶剂化显色测试;并对其晶体结构进行解析及Hirshfeld表面分析;将TTC-K水溶液通过化学浸渍法和雾化法应用于潜指纹成像。结果表明,TTC-H分子间存在C…H、H…H和O…H相互作用力,占比分别为31.6%、44.6%和14.6%(占总作用力的百分数,下同)。TTC-H与TTC-K均具有聚集诱导发光性质。将TTC-K水溶液通过化学浸渍法和雾化法应用于潜指纹成像,两种方法均可精确、高效地得到指纹的三级结构。浸渍法能在低浓度(5×10^(–5)mol/L)下实现对潜指纹的快速(≤5 s)识别,陈化稳定性好;而雾化法更容易操作,对于陈旧指纹(≤14 d)、水中浸泡指纹(≤7 d)均具有良好的成像效果。Amphiphilic carboxylic acid derivatives,5-[4-(diphenylamino)phenyl]-thiophen-2-carboxylic acid(TTC-H)and its potassium salt(TTC-K),were synthesized from Suzuki coupling reaction of 5-bromothiophen-2-carboxylic acid and 4-(diphenylamino)benzeneboronic acid,and characterized by 1HNMR and 13CNMR.The TTC-H and TTC-K were further evaluated by UV-Vis absorption spectroscopy and fluorescence emission spectroscopy for analyses on their photophysical properties as well as aggregated states,with density-functional theory calculations and solvation colorimetric effects carried out and their crystal structures analyzed by Hirshfeld surface analysis.TTC-K aqueous solution was then applied to latent fingerprint imaging by chemical impregnation and atomization methods.The results showed that there were weak interaction forces between TTC-H molecules,such as C…H(31.6%,accounting for the percentage of the total interaction force,the same below),H…H(44.6%)and O…H(14.6%).Both TTC-H and TTC-K possessed the property of aggregation-induced emission.TTC-K aqueous solution was then applied to latent fingerprint imaging by chemical impregnation and atomization methods.Both methods could accurately and efficiently obtain the tertiary structure of latent fingerprints.And even at low concentration(5×10^(–5)mol/L),the TTC-K aqueous solution reagent was able to rapidly identify latent fingerprints(≤5 s)by chemical impregnation method with good aging stability,while the atomization method is easier to be implemented,while exhibited good imaging capacity for both old fingerprints(≤14 d)and fingerprints soaked in water(≤7 d).

关 键 词：双亲性 羧酸盐 潜指纹 雾化法 聚集诱导发光 功能材料 

分 类 号：O69[理学—化学] TQ251.2[化学工程—有机化工]