摘要
从Lippert发现一些特殊结构的化合物具有发射双重荧光的现象以来,人们对双重荧光的研究不断深入,并设计合成了多种高效发光机理不同的双重荧光体,实验证明,双重荧光对荧光体所处环境具有依赖性,因此不同的双重荧光体被应用到各个领域,如分子认别、传感器、溶剂极性、紫外线吸收等,水杨酸-2′-乙基己基酯(EHS)是一种具有分子内质子转移(ESIPT)荧光的双重荧光体,被广泛应用于防晒化妆品中。
本论文研究了水杨酸-2′-乙基己基酯的分子内质子转移双重荧光对有机溶剂和表面活性剂环境的依赖性,对水杨酸-2′-乙基己基酯分子内氢键、分子间氢键荧光性质进行了实验证明,论证了水杨酸-2′-乙基己基酯增溶于不同胶束中的增溶位点和荧光的变化特性,证明难溶于水的水杨酸-2′-乙基己基酯可以增溶于表面活性剂胶束中,EHS分子插入到胶束的栅栏层中,柔性和疏水的2′-乙基己基碳链朝向胶束内核,而刚性水杨酸基则位于或靠近由极性头基团构成的胶束外壳层中。增溶有利于提高EHS分子对紫外光的吸收能力,结合位点周围微环境有利于分子内氢键的形成,表现出ESIPT荧光的大大增强,有效地将吸收的紫外光转化为可见光,为水杨酸-2′-乙基己基酯做为紫外吸收防晒剂的应用提供了一定的数据参考。
第一章:简述了具有双重荧光体物质的化学结构和发光机理以及表面活性剂的结构特征、分类及增溶原理,对化学防晒类化妆品的防晒原理、研究和发展水平及应用前景作了综述。
第二章:考察了水杨酸-2′-乙基己基酯(EHS)在不同有机溶剂中的荧光光谱和紫外吸收光谱,结果表明,EHS可生成分子问氢键和分子内氢键两种型体,对应发出分子间氢键和激发态分子内质子转移(ESIPT)双重荧光,EHS的双重荧光对溶剂有依赖性。
第三章:考察了水杨酸-2′-乙基己基酯(EHS)在非离子表面活性剂Triton X-100R中的吸收光谱和荧光光谱。结果表明,EHS可增溶于Triton X-100R胶束中,柔性的疏水的2′-乙基己基碳链朝向胶束内核,插入栅栏层中,而刚性的水杨酸基伸向胶束-水界面,在不同的介质中EHS荧光性质发生变化,增溶在Triton X-100R胶束中的EHS易生成分子内氢键,生成激发态分子内质子转移(ESIPT)荧光。激发态分子以发射可见光和非辐射的方式去活化,发射出的ESIPT荧光显著增强。
第四章:考察了阳离子、非离子和阴离子表面活性剂存在下水杨酸-2′-乙基己基酯(EHS)的吸收光谱和激发态分子内质子转移(ESIPT)荧光光谱,结果表明,EHS可增溶在胶束中,2′-乙基己基碳链朝向胶束内核,而水杨酸基朝向胶束-水界面;胶束环境有利于EHS分子对紫外光的吸收和分子内氢键的形成,从而使ESIPT荧光大大增强,激发态分子以发射可见光和非辐射去活化方式衰减;并根据EHS和表面活性剂分子的结构和大小,解释了EHS分子在胶束中的结合位点,荧光猝灭和酯水解的光谱测量进一步为此结合位点提供了佐证。
Since the first observation by Lippert of the dual fluorescence of some compounds with special structure,the designing of the new dual fluorescence body with vary mechanism has been a subject of intensive interest.It was found that dual fluorescence was related to the place environment polarity,so the different dual fluorescence body be applied to each realm,spread feeling machine,melting agent pole,ultraviolet ray absorption etc.Salicylic 2'-ethylhexyl salicylate(EHS) is a kind of dual fluorescence body based on excited state intramolecular proton transfer(ESIPT) mechanism. Currently it has been used as sunscreens in sun-care products widely.
This thesis mainly studied the dependence of dual fluorescence of the 2'-ethylhexyl salicylate on the environment of organic solvent and micelles.Intramolecular hydrogen bonding and intermolecular hydrogen bonding was examined by experiments,The spectral properties and binding sites of EHS in micelles has been discussed.Linear EHS molecule was solubilized in micelles with its flexible hydrophobic 2'-ethylhexyl chain toward the micellar core and with its dimethylamino moiety toward the micelle-water interface.When EHS was solubilized in micelles,the UV absorption of EHS was enhanced.The suitable microenvironment around binding sites was favoed formation of intramolecular hydrogen bonding resulting in greatly enhanced ESIPT fluorescence. Evidence of EHS using as sunscreen in sun-care products was proved in our study too.
Chapter 1:Chemistry structures and mechanism of dual fluorescence body was introduced briefly.Structure properties,classification and solubilization theory of surfactant were described briefly.Mechanism and prospect of sunscreens had been reviewed
Chapter 2:Absorption and fluorescence properties of EHS was examined in organic solvents.The experimental results shows that dual fluorescenceresults was from intermolecular hydrogen bonding and ESIPT.This dual fluorescence is depending on soluents.
Chapter 3:Absorption and fluorescence of EHS were examined in the non-ionic Triton X-100(R) micelles.It was found that linear EHS molecule was solubilized in micecles with its flexible hydrophobic 2'-ethylhexyl chain toward the micellar core and with its salicylate moiety toward the micelle-water inteface,Flurescence property of EHS was improved in different medium and intermolecular hydrogen bonding formation of EHS was favored,ESIPT flurescence was emitted.The excited EHS molecules decay via visible luminescence and non-radiativation increased,resulting in greatly enhanced ESIPT flurescence.
Chapter 4:Absorption and ESIPT fluorescence of EHS were examined in the presence of cationic,non-ionic and anionic surfactants.It was found that linear EHS molecule was solubilized in micelles with its flexible hydrophobic 2'-ethylhexyl chain toward the micellar core and with its salicylate moiety toward the micelle-water interface.UV absorbance of EHS was improved and intramolecular hydrogen bonding formation of EHS was favored,resulting in greatly enhanced ESIPT fluorescence.The excited EHS molecules decay via visible luminescence and non-radiative deactivation.The binding sites of EHS in micelles were explained at molecular level in terms of molecular structures and sizes of surfactants and EHS.Dynamic fluorescence quenching and spectral measurements of ester hydrolysis of EHS provide further evidences for the binding sites of EHS in different micelles.
引文
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