硫杂杯[4]荧光探针的离子识别及分子逻辑门研究  

The Ion Identification and Molecular Logic Gate of a Thiacalix[4]arene Fluorescent Probe

作　　者：吴福勇 余梅[1] 牟兰[1] 曾晞[1] 王瑞晓 大和武彦 

机构地区：[1]贵州省大环化学及超分子化学重点实验室,贵州大学化学与化工学院,贵州贵阳550025 [2]Department of Applied Chemistry,Faculty of Science and Engineering,Saga University,Honjo-machi 1,Saga 840-8502,Japan

出　　处：《光谱学与光谱分析》2016年第1期157-162,共6页Spectroscopy and Spectral Analysis

基　　金：国家自然科学基金项目(21165006);教育部“春晖计划”项目(Z2012053);贵州省国际合作项目(20137002)资助

摘　　要：以硫杂杯[4]芳烃为母体,在其1,3-位连接羟乙基邻苯二甲酰亚胺,2,4-位以三氮唑为连接基,将苄基引入硫杂杯[4]芳烃的下沿,得到硫杂杯[4]-邻苯二甲酰亚胺衍生物荧光探针(s1)。探针s1发射强烈荧光,在CH_3CN介质中的相对荧光量子产率为0.43。在DMF/H_2O介质中,以310nm为激发波长,Fe^(3+)能选择性猝灭探针s1在390nm处的荧光;在CH_3CN介质中,以245nm为激发波长,I^-能选择性猝灭探针s1在310nm处的荧光,光谱滴定和等温滴定量热均测出探针s1与Fe^(3+)或与I^-形成1∶1配合物,结合常数均达105。结合自由能表明配合为自发过程。荧光猝灭检测Fe^(3+)和I^-的浓度线性范围分别为1.0×10^(-7)~1.6×10^(-4) mol·L^(-1)和1.0×10^(-7)~8.5×10^(-5) mol·L^(-1),检测限分别为2.30×10^(-8) mol·L^(-1)和1.17×10^(-8) mol·L^(-1)。同时,利用识别和竞争配合作用,控制Fe^(3+)和F^-的输入使探针s1发射荧光或荧光猝灭,构建了分子水平上的逻辑电路。红外光谱推测探针s1分子中三氮唑基的氮原子参与了识别Fe^(3+)的配位,而探针s1分子中三氮唑环上的芳氢与I^-形成氢键而实现识别。A disubstituted phthalimide-based thiacalix[4]arene derivative（probe s1）was synthesized from cone 1,3-thiacalix[4]arene and hydroxyethyl phthalimide,with benzyl appended the lower edge of thiacalix[4]-arene by triazole ring in the 2,4position.The relative fluorescence quantum yield of probe s1 is 0.43 in CH_3CN solvent.The strong fluorescence emission of probe s1 at 390nm wavelength can be selectively quenched by Fe^3＋in DMF/H_2 O solution.Similarly,the presence of I^-also induced a significant fluorescence quenching of probe s1 at 310nm wavelength in CH_3 CN solution.Spectral titration and isothermal titration calorimetry were showed that probe s1 with Fe^3＋or I^-both form 1∶1complexes,the binding constants up to 105 and coordinate process were spontaneous.The linear ranges of fluorescence detect Fe^3＋or I^-were 1.0×10^-7~1.6×10^-4 mol·L^-1 and1.0×10^-7~8.5×10^-5 mol·L^-1,detection limits were up to 2.30×10^-8 mol·L^-1 and 1.17×10^-8 mol·L^-1,respectively.Meanwhile,take advantage of identification and coordination action,a logic circuit constructed at the molecular level by controlling two input signals of Fe^3＋and F^-,which causing probe s1 cycling of fluorescence emission or quenching.IR spectrum speculated that the nitrogen atoms of triazole groups are involved in the complexation with Fe^3＋,while the hydrogen atoms of triazole groups were complexed with I^-by hydrogen bonding.

关 键 词：1 芳烃 荧光探针 分子逻辑门 FE^3+ I^- 

分 类 号：O657[理学—分析化学]