第四章荧光的猝灭.pptVIP

发生电子转移反应的猝灭剂并不限于金属离子，I-，Br-，CNS-，S2O32-等易于给出电子的阴离子对奎宁，罗丹明及荧光素钠等有机荧光物质也会发生猝灭作用。 例 1. 例 2. (1) 测定F-离子的比率型荧光探针 Scheme 1. Design concept of ratiometric fluorescent probe 1 for fluoride. Fig. 1. Absorption(left) and fluorescence (right)spectra of HPBI, PBI and 1. Fig. Absorption and fluorescence spectra of 1 after incubation with increasing concentrations of fluoride ion. Fig.3. Fluorescent emission changes (λex = 310 nm) of 1 upon addition of various anions (4.0 μM) (2) 测定ALP的比率型荧光探针 Exicted－State Intramolecular Proton Transfer 当荧光物质的浓度超过1g/L时，常发生荧光的自猝灭现象。包括如下几种： （1）荧光辐射的自吸收 假如荧光物质的吸收光谱和发射光谱有较大的重叠，由荧光物质发射的荧光，有一部分可能被自身的基态分子所吸收。随荧光物质浓度的增加，自吸收的现象会加剧。这种现象，实际上也是辐射能量转移过程，只不过能量的给体与供体为统一分子。 §4.7 自猝灭 (2) 形成激发态二聚体（Excimer） 荧光物质的激发态分子1M*与基态分子M形成激发态二聚体1（M*M） 有的激发态二聚体并不发荧光，有的虽发荧光，但其发光特性（如光谱范围、荧光峰位置、荧光量子产率和荧光寿命等）与单体的发射特性不同，这就引起原来荧光物质的荧光猝灭。 Excimers are dimers in the excited state (the term excimer results from the contraction of ‘excited dimer’). They are formed by collision between an excited molecule and an identical unexcited molecule: 1M* + 1M ----- 1(MM)* Many aromatic hydrocarbons such as naphthalene or pyrene can form excimers. The fluorescence band corresponding to an excimer is located at wavelengths higher than that of the monomer and does not show vibronic bands: Fig. Excimer formation with the corresponding momomer and excimer bands. Fig. Fluorescence spectra of pyrene at various concentrations in cyclohexane. A: 10-2; B: 7.75×10-3; C: 5.5×10-3; D: 3.25×10-3; E: 10-3; G: 10-4 mol L-1 10 7.75 5.5 3.25 1 0.1 芘浓度（mmol L-1） A sensitive and selective “turn on” fluorescent chemosensor for Hg(II) ion based on a new pyrene–thymine dyad Anal. Chim. Acta 2005, 549 , 10–13. Hg2+ Fig. Fluorescence spectra of a solution of dyad 1 in H2O/CH3CN (20:1, v/v) at pH 7 with the addition of Hg(ClO4) E（D/D+), E（A/A-)可通过电化学测量或理论计算LUMO和HOMO轨道能量的方法得到。 该公式是一个经验公式，它是在大量基础实验上建立起来的。有关从理论上对电子转移过程的研究是由Marcus所完成的。Marcus提出的电子转移模