【作者】 张振宇；

【导师】 徐冬梅；

【作者基本信息】 苏州大学 ， 化学工程与技术， 2015， 硕士

【摘要】 本文以1,8-萘酰亚胺为荧光团,硫脲为识别基团合成了三种光谱探针ATBN、BTBN与ATUN。通过红外光谱、质谱、核磁共振、元素分析等手段表征了其结构。利用紫外-可见吸收光谱和荧光光谱研究了其对F-、Hg2+、Pb2+、Fe3+的传感性能、传感机理和应用。F-比色探针(ATBN):由N-正丁基-4-硝基-1,8-萘酰亚胺和氨基硫脲反应得到了一种F-比色探针ATBN。在ATBN的乙腈(含有微量水)溶液中加入F-,溶液在555 nm处的吸光度显著增强,颜色由浅黄色变为紫色。在F-浓度10~50μM范围内,吸光度与F-浓度之间有良好的线性关系。ATBN对F-的检测限为51.1μM,结合常数为1.45×105 M-1。ATBN与F-通过氢键形成1:1络合物。Fe3+、Pb2+和Hg2+多功能比色和荧光探针(BTBN):通过N-正丁基-4-肼基-1,8-萘酰亚胺与异硫氰酸苯酯反应合成了探针BTBN。BTBN可以在Me CN/H2O(99/1,v/v)体系中比色检测Fe3+与Pb2+,在Me CN/H2O(85/15,v/v)体系中荧光检测Hg2+。在Fe3+浓度0~150μM范围内,溶液吸光度与Fe3+浓度之间有良好的线性关系。BTBN对Fe3+的检测限为6.86μM,结合常数为1.85×103 M-1。在Pb2+浓度0~80μM范围内,溶液吸光度与Pb2+浓度之间有良好的线性关系。BTBN对Pb2+的检测限为5.09μM,结合常数为4.961×103 M-1。BTBN与Fe3+和Pb2+分别以1:1的形式可逆络合。BTBN可以在0~90μM的范围内荧光检测Hg2+,对Hg2+的检测限为82.1 n M,结合常数为6.334×103 M-1。BTBN与Hg2+之间先发生1:1络合,再发生不可逆脱硫成环反应。BTBN可以用于检测细胞以及环境水样中的Hg2+。可聚合的Fe3+、Pb2+和Hg2+多功能比色和荧光探针(ATUN):用烯丙基胺代替BTBN合成中的正丁胺得到一个可以发生聚合反应的多功能比色和荧光探ATUN。与BTBN相似,ATUN在Me CN/H2O(99/1,v/v)体系中能够可逆地比色检测Fe3+和Pb2+,在Me CN/H2O(50/50,v/v)体系中可以不可逆地荧光检测Hg2+。ATUN在比色检测Fe3+时,Fe3+浓度线性范围为0~150μM,检测限为8.34μM;比色检测Pb2+时,Pb2+浓度线性范围为0~70μM,检测限为11.22μM;荧光检测Hg2+时,Hg2+浓度线性范围为0~80μM,检测限为139.3 n M。ATUN与Fe3+、Pb2+、Hg2+都是形成1:1络合物,结合常数分别为1.254×103、3.561×103和6.353×103 M-1。更多还原

【Abstract】 In this paper, we synthesized three kinds of colorimetric and fluorescent probes(ATBN, BTBN, ATUN) based on 1,8-naphthalimide and thiourea. The structures of the probes were characterized by FT-IR, LC-MS, 1H NMR, 13 C NMR and elementary analysis. The sensing behaviors, sensing mechanism and application of the probes for F-, Fe3+, Pb2+ and Hg2+ were explored by UV-Vis absorption and fluorescence spectra.A colorimetric probe for F-(ATBN): The colorimetric probe(ATBN) for F- was synthesized by N-butyl-4-nitro-1,8-naphthalimide reacted with thiosemicarbazide. On addition of F-, a new absorption band centered at 555 nm was appeared accompanied by the color change of ATBN solution from pale yellow to purple in Me CN(containing a little water). In the scope of 10~50 μM of F- concentration, the absorbance of the solution kept good linear relationship with the F- concentration. The detection limit was 51.1 μM and the binding constant was 1.45×105 M-1. ATBN complexed with F- through hydrogen bonds to form a 1:1 complex.A multifunctional colorimetric and fluorescent probe for Fe3+, Pb2+ and Hg2+(BTBN): BTBN was synthesized by reacting N-butyl-4-hydrazine-1,8-naphthalimide with phenyl isothiocyanate. BTBN can colorimetrically detect Fe3+ and Pb2+ in Me CN/H2O(99/1, v/v) and fluorimetrically detect Hg2+ in Me CN/H2O(85/15, v/v). The linear concentration range for Fe3+ was 0~150 μM with the detection limit of 6.86 μM and the binding constant was 1.854×103 M-1. The linear concentration range for Pb2+ was 0~80 μM with the detection limit of 5.09 μM and the binding constant was 4.961×103 M-1. BTBN bound Fe3+(or Pb2+) reversibly according to 1:1 stoichiometry. In the Hg2+ concentration range of 0~90 μM, BTBN could irreversibly detect Hg2+ by fluorescence. The detection limit was 82.1 n M and the binding constant was 6.334×103 M-1. A 1:1 complex was formed between BTBN and Hg2+ first and then promoted the desulfurization cyclization. Moreover, BTBN was successfully employed to monitor Hg2+ in pond and tap water as well as in living cells.A polymerizable multifunctional colorimetric and fluorescent probe for Fe3+, Pb2+ and Hg2+(ATUN): Allyl amine replaced n-butylamine in BTBN synthesis to get a polymerizable multifunctional colorimetric and fluorescent probe ATUN. Similarly to BTBN, ATUN could colorimetrically detect Fe3+ and Pb2+ in Me CN/H2O(99/1, v/v) and fluorimetrically detect Hg2+ in Me CN/H2O(50/50, v/v). As a colorimetric probe for Fe3+, the linear concentration range was 0~150 μM with the detection limit of 8.34 μM. As a colorimetric probe for Pb2+, the linear concentration range was 0~70 μM with the detection limit of 11.22 μM. As a fluorescent probe for Hg2+, the linear concentration range was 0~80 μM with the detection limit of 139.3 n M. A 1:1 complex was formed between ATUN and Fe3+(or Pb2+, or Hg2+), and the binding constants were 1.254×103, 3.561×103, and 6.353×103 M-1, respectively.更多还原