【作者】 扈靖；

【导师】 张明杰； 张文勤；

【作者基本信息】 天津大学 ， 有机化学， 2008， 博士

【摘要】 本论文以香豆素类化合物为母体,在其不同化学位点连接不同的识别基团,得到了一系列性质各异的金属离子探针,用荧光光谱和紫外光谱研究了这类探针对环境极性的敏感程度和对不同金属离子的识别能力。设计、合成了十二个含有N、O和S原子的不同识别基团单臂和双臂单香豆素荧光团分子探针。单臂荧光探针体系中,我们通过对香豆素不同位点的修饰,得到了基于ICT机理的有效专一识别Fe3+的荧光探针7-二乙氨基-N-(2-羟乙基)-3-香豆素甲酰胺(E1)。双臂香豆素类荧光分子探针体系中,我们研究了含有不同杂原子的识别基团对PET型荧光探针识别性能的影响,优化了探针的选择性,得到了可以选择性识别某种过渡金属和重金属离子的荧光增强型分子探针4-[双(N-乙酰氧乙基)氨甲基]-7-甲氧基香豆素(B3)和4-[双(N-二乙氨基硫代甲酰硫乙基)氨甲基]-7-甲氧基香豆素(B4);而在ICT型荧光探针的研究中,我们发现具有不同杂原子的识别基团可以对识别性能产生影响的同时,连接位置的改变也对识别能力有很大的影响。如相同的识别基团二乙醇胺从香豆素的6-位转移到7-位识别性能明显提高,得到了可以较好识别Cu2+和Fe3+的荧光探针。以一条具有识别功能的链将两个信号单元连接起来,设计、合成了十三个新的双香豆素荧光团分子探针。在PET型系列探针设计中发现将四甲基三丙撑四胺引入识别基团得到一种不仅可以作为灵敏的氢离子荧光分子开关的探针,荧光强度变化在100倍以上;还可以在水溶液中敏感地选择性络合促进荧光增强识别Hg2+和Fe3+的探针2,6,10,14-四甲基-1,15-双(7-甲氧基-4-香豆素基)-2,6,10,14-四氮杂十五烷(G4)。将比色识别探针( Colorimetric Sensor )应用于Fe3+的检测是非常罕见的。在比色识别探针设计中,得到两种Fe3+比色探针N,N’-双(7-二乙氨基-3-香豆素甲酰基)间苯二甲氨(H3), N,N’-双(7-二乙氨基-3-香豆素甲酰基)己二胺(H4)。同时在ICT型探针的设计中,将亚丙二硫基和亚乙二硫基引入识别基团,得到了两个Hg2+荧光探针1,9-双(4-甲基-7-香豆素氧基)-3,7-二硫杂壬烷(I1), 1,8-双(4-甲基-7-香豆素氧基)-3,6-二硫杂辛烷(I2)。利用C=N键异构( C=N isomerization )机理设计了九个以香豆素为母体的希夫碱、腙和酰腙类荧光探针。我们对这类化合物的阳离子识别研究得到两种选择性络合促进荧光增强识别Cu2+的探针3-(2-羟基苯亚胺)甲基-7-二乙氨基香豆素(J1),3-[4-二(2-羟乙基)氨基苯亚胺甲基]-7-二乙氨基香豆素(J2),它们适合于环境微量Cu2+的检测,同时得到一种专一性Fe3+比色探针7-二乙胺基-3-香豆素甲醛缩氨基硫脲(J9)。更多还原

【Abstract】 A series of probes with various receptors attached to coumarin fluorophores were designed for the detection of metal ions. Their sensitivity to solvent polarity and recognition ability to metal ions were studied through the UV and FL spectra.Twelve of single- and double-armed probes were designed by introducing various receptors containing N, O and S atoms to the comarins. The fluorescent probe with single-armed receptor, 3-N-（2-hydroxyethyl）carboxamido-7-（diethylamino） coumarin （E1） shows remarkably sensitivity and selectivity response to Fe3+, which was turned out as an ICT mechanism. In others with double-armed receptors, the probes 4-（N,N-bisacetoxyethylaminomethyl）-7-methoxycoumarin. （B3） and 4-[(N,N- bis（diethylaminodithiocarboxyethyl aminomethyl）-7-methoxycoumarin （B4） with pronounced fluorescence enhancement response to special heavy and transition metal ions were proposed as PET mechanism; for those with double-armed receptors following ICT mechanism, their performances are influenced by not only the structure of the receptors but also the attaching position of it.Thirteen fluorescent probes with twin coumarin fluorophores were designed. When 6,10-dimethyl-2,6,10,14-tetraazapentadecane was introduced as spacer and receptor. The probe 2,6,10,14-tetramethyl-1,15-bis（7-methoxy-4-coumarinyl）-2,6,10, 14-tetraazapentadecane （G4） based on PET mechanism was found to enhance the fluorescence intensity to 100 times, which can be used as fluorescent switches for protons. This probe can also recognize Hg²⁺ and Fe³⁺ sensitively in aqueous solution. The colorimetric sensors used to the detection of Fe³⁺ are very scarce. In this thesis, sensors N,N-bis（7-diethylamino-3-coumarinformyl）-m-phenylenebis（methylamine） （H3）, N,N-bis（7-diethylamino-3-coumarinformyl）hexanediamine （H4） were found to show excellent selectivity towards Fe³⁺. Two sensors 1,9-bis（4-methoxy-7- coumarinoxy）-3,7-dithianonane （I1）, 1,8-bis（4-methoxy-7-coumarinoxy）-3,6- dithia- octane （I2） for recognition of Hg²⁺ were also obtained by introducing 1,3-bis（methylthio）propandiyl and 1,2-bis（methylthio）ethandiyl respectively as the spacer.Nine probes based on the C=N isomerization were also synthesized and it was found that two probes 3-（2-hydroxyphenyliminomethyl）-7-diethylaminocoumarin （J1）, 3-[(4-bis（2-hydroxyethyl）aminophenyliminomethyl]-7-diethylaminocoumarin （J2） show fluorescence enhancement to Cu²⁺ significantly, which can be used for trace measurement of Cu²⁺ in the enviroment. Another probe 7-diethylamino -3-cumarinaldehyde thiosemicarbazone （J9） was found as colorimetric sensor to Fe³⁺.更多还原