高灵敏性氟离子荧光探针

发布时间：2018-08-02 21:27

【摘要】：香豆素类化合物因其多种优良的特性,作为荧光探针已成为了研究热点。氟离子是人体所必需的微量元素,适量的氟离子摄入有益于牙齿和骨骼的健康,过多或过少摄入氟离子都会对人体产生不良影响。因此,氟离子的检测具有重大意义。本文选择性的合成了以香豆素为母体的氟离子荧光探针。论文的主要内容:(1)利用香豆素为母体,以叔丁基二甲基氯硅烷做为引入硅醚的试剂,合成了四个含有Si-O键的氟离子荧光探针化合物L1、L2、L3、L4,其检测机理是利用F和Si之间的强亲和力,对Si-O键进行破坏,从而产生识别作用。产率分别为40%、45%、52%、48%。(2)利用香豆素为母体,综合考虑了溶剂、催化剂、试剂、温度、时间等条件,并选用对甲苯异氰酸酯为反应试剂,合成了2个新型的以香豆素为母体的铈离子荧光探针化合物L5、L6。产率分别为90%、79%。(3)选择化合物L1作为探针分子,对其进行相关荧光性能的测试研究。研究发现,探针L1分子在乙腈和水的比例为1:9的溶液中,探针L1分子对氟离子的检测性能最佳,且其具有高灵敏性,其最低检测限可以达到0.1μM 通过对比探针L1分子在不同pH条件紫外吸收和荧光发射光谱,发现其可适用在pH为2-10的范围内,在此范围内较为稳定适合用于检测;在乙腈和水的比例为1:9的溶液中,通过加入Cl-,Br-,I-,CH_3COO-,HSO4-,H_2PO4-这6种阴离子作为干扰离子进行选择性和抗干扰性检测,发现探针L1分子对氟离子的检测具有很高选择性和抗干扰性,在这6种离子存在的情况下,对其检测氟离子没有任何有效性影响。(4)选择化合物L5作为探针分子,对其进行相关荧光性能的测试研究。研究发现,探针L5分子在乙腈和水的比例为1:9的溶液中,探针L5分子对铈离子的检测性能最佳,且在其最低检测限为0.1μM时仍具有较高灵敏性;通过对比探针L5分子在不同pH条件紫外吸收和荧光发射光谱,发现其可适用在pH为4-7的范围内,在此范围内较为稳定适合用于检测;在乙腈和水的比例为1:9的溶液中,通过加入 Li+,Zn~(2+),Sr~(2+),Ni~(2+),Co~(2+),Ca~(2+),Fe~(2+),Hg~(2+),Ag+,Al~(3+),Cr~(3+),Fe~(3+),F-,Cl-,Br,I-,CH_3COO-,HSO4-,H_2PO4-这19种阴、阳离子进行选择性和抗干扰性检测,发现探针L5分子对铈离子的检测具有较高选择性和抗干扰性,在这19种阴、阳离子存在的情况下,对其检测铈离子没有任何有效性影响。
[Abstract]:Coumarin compounds as fluorescent probes have become a hot topic because of their many excellent properties. Fluoride ion is a necessary trace element in human body. Proper intake of fluoride ion is beneficial to the health of teeth and bones. Too much or too little fluoride ion intake will have adverse effects on human body. Therefore, the detection of fluorine ions is of great significance. Fluorine ion fluorescence probe with coumarin as parent was synthesized selectively in this paper. The main contents of this paper are as follows: (1) using coumarin as parent and tert Ding Ji dimethyl chlorosilane as the reagent of introducing silica ether, four fluorine fluorescent probe compounds L _ (1) L _ (2) and L _ (3) C _ (4) containing Si-O bond have been synthesized. The detection mechanism is to utilize the strong affinity between F and Si. The Si-O key is broken to produce recognition. The yields were 40% and 45%, respectively. (2) the solvent, catalyst, reagent, temperature, time and so on were taken into account with coumarin as the parent, and p-toluene isocyanate was selected as the reaction reagent. Two novel cerium ion fluorescent probe compounds L _ 5N _ L _ 6 with coumarin as parent were synthesized. The yields were 90 and 79 respectively. (3) compound L1 was selected as probe molecule and its fluorescence properties were tested. It was found that the probe L1 molecule had the best detection performance for fluorine ion in the solution with the ratio of acetonitrile to water at 1:9, and the probe L1 molecule had high sensitivity. The lowest detection limit can reach 0.1 渭 M. By comparing the UV absorption and fluorescence emission spectra of the probe L1 at different pH conditions, it is found that it can be used in the range of pH 2-10, and it is more stable and suitable for detection in this range. In a solution with the ratio of acetonitrile to water at 1:9, the selective and anti-interference properties of the probe L1 molecule for fluorine ion detection were found to be highly selective and anti-interference by adding Cl-nil Br-tir I-Che CH3COO-HSO4-H2PO4- these six kinds of anions as interference ions. In the presence of these six ions, there was no effect on the detection of fluorine ions. (4) the related fluorescence properties of L5 as probe molecule were studied. It is found that the probe L5 has the best detection performance for cerium ion in the solution with the ratio of acetonitrile to water at 1:9, and still has a high sensitivity when the detection limit is 0.1 渭 M. By comparing the UV absorption and fluorescence emission spectra of the probe L5 at different pH conditions, it is found that the probe can be applied in the range of pH 4-7, and is stable and suitable for detection in the solution with the ratio of acetonitrile to water at 1:9. By adding Li Li Zn ~ (2) O _ (2) Sr ~ (2) O _ (2) Co ~ (2) Co ~ (2) O _ (2) Fe ~ (2) O _ (2) H _ g ~ (2) O _ (2) Hg ~ (2) O _ (2) O _ (3) Cr ~ (3) O _ (3) Fe ~ (3) O _ (3) Fe ~ (3) O _ (3) Fe ~ (3) O _ (3) -Fe ~ (3) O _ (3) -Fe ~ (3) O _ (3) F ~ (2) O ~ (3) O _ (3) -BrI-CH3COO-HSO _ 4-H2PO _ (4), 19 anion, cations were tested for selectivity and anti-interference of cerium ion. In the presence of cations, there is no effect on the detection of cerium ions.
【学位授予单位】：东华大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O657.3

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