香豆素类希夫碱型金属离子荧光探针的合成及性能研究

发布时间：2018-03-20 11:40

本文选题：荧光探针　切入点：香豆素　出处：《海南师范大学》2017年硕士论文　论文类型：学位论文

【摘要】：金属离子对动植物的代谢活动和环境有着非常重要的影响,有些金属离子对某些生物是有益的而对其他的生物不但没有益处反而有害,有些金属离子在适当的浓度范围内对生物体有益,但低于或超出相应的浓度范围就对生物体的生命活动构成威胁,所以,对生物体内以及其生活的环境内的金属离子的检测和监测是非常有必要的。荧光分子探针检测金属离子、阴离子、蛋白质等技术比色谱法、光谱法、滴定法、伏安法、电位法等技术较为成熟,其选择性高、灵敏度高、操作简单的特性也是人们为之青睐的原因。以香豆素为母体的分子探针是检测金属离子的重要的研究方向之一,香豆素类金属离子荧光探针价格低廉、易于合成、低毒性和操作简单而广受好评。香豆素具有苯并-α-吡喃酮结构,其结构易于修饰且杂环上的羰基碳可以参与金属离子的配位,在可见光范围内具有光稳定性好,荧光性强,Stokes位移大等优点。因此,香豆素类荧光探针被广泛应用,其已经被用作DNA和RNA、酶胺、氨基酸、蛋白质、阴离子和金属离子等的检测。一般而言,希夫碱分子探针单元由于C=N键的自由转动经常呈现出较弱或者没有荧光,香豆素类希夫碱探针含有氧或氮供体可以结合金属离子以及作为一个荧光单元。本论文是基于7-二乙氨基香豆素作为母体,设计合成了一系列的香豆素希夫碱型化合物,其中有五种新化合物对某些金属离子有特定的选择性。合成了一种香豆素希夫碱型Zn~(2+)荧光探针L1,这种荧光探针对Zn~(2+)的检测表现出良好的选择性,较高的灵敏度和较强的抗干扰能力,且探针L1与Zn~(2+)以1:2摩尔比络合。在5-溴噻吩-2-甲酰肼与7-二乙胺基-3-甲酰基香豆素反应生成的希夫碱型荧光探针L2的乙腈溶液中,加入钴离子和镍离子后荧光强度显著降低,实现对两种离子的检测,并且L2分别与钴离子和镍离子形成摩尔比都是2:1的络合物。在4-二乙氨基水杨醛与7-二乙氨基香豆素-3-甲酰肼反应生成的希夫碱型荧光探针L3的乙腈溶液中,对Hg2+的检测表现出良好的选择性和抗干扰能力,且探针L3与Hg2+以1:2摩尔比络合。7-二乙氨基香豆素-3-甲酰肼分别与7-二乙氨基-3-甲酰基香豆素和吡咯-2-甲醛反应生成的希夫碱型探针L5和L4,均表现出对Cu~(2+)的高度选择性且都是荧光增强型香豆素希夫碱荧光探针,L4和L5与Cu~(2+)的络合比都是1:2。
[Abstract]:Metal ions have a very important effect on the metabolic activities of plants and animals and on the environment. Some metal ions are beneficial to some organisms and are harmful to others rather than to others. Some metal ions are beneficial to the organism within the appropriate concentration range, but below or above the corresponding concentration range pose a threat to the life activities of the organism, so, It is necessary to detect and monitor metal ions in organisms and in the environment in which they live. Fluorescent molecular probes are used to detect metal ions, anions, proteins, etc., compared with chromatography, spectrophotometry, titration, voltammetry, etc. The potential method is more mature, with high selectivity, high sensitivity and simple operation. The molecular probe with coumarin as the parent is one of the important research directions in the detection of metal ions. Coumarin metal ion fluorescence probe is cheap, easy to synthesize, low toxicity and easy to operate. Coumarin has a benzo-伪-pyranone structure, its structure is easy to modify and carbonyl carbon on heterocyclic can participate in the coordination of metal ions. Therefore, coumarin fluorescent probes have been widely used as DNA and RNAs, enzyme amines, amino acids, proteins, etc. The detection of anions and metal ions. Generally speaking, the Schiff base molecular probe units often exhibit weak or no fluorescence due to the free rotation of the Con N bond. Coumarin Schiff base probes containing oxygen or nitrogen donors can bind metal ions and act as a fluorescent unit. A series of coumarin Schiff base compounds were designed and synthesized based on 7-diethylaminocoumarin as parent. Five of the new compounds have specific selectivity for certain metal ions. A coumarin Schiff base Zn~(2) fluorescent probe L _ 1 has been synthesized, which exhibits good selectivity for the detection of Zn~(2). The probe L1 complexed with Zn~(2 at the molar ratio of 1: 2. In the acetonitrile solution of Schiff base fluorescent probe L2, which was formed by the reaction of 5-bromothiophene -2-formyl hydrazide with 7-diethylamino-3-formylcoumarin, The fluorescence intensity of cobalt ion and nickel ion decreased significantly, and the detection of the two ions was realized. And the molar ratio of L _ 2 to Co ~ (2 +) and Ni ~ (2 +) is 2: 1. In acetonitrile solution of Schiff base fluorescent probe L3, which reacts with 4-diethylamino salicylic aldehyde and 7-diethylaminocoumarin -3-formyl hydrazine, The detection of Hg2 shows good selectivity and anti-jamming ability. The Schiff base probes L5 and L4 formed by the reaction of the probe L3 with Hg2 at the molar ratio of 1: 2. 7-diethylaminocoumarin -3-formyl hydrazide reacted with 7-diethylamino -3-formylcoumarin and pyrrole-2-formaldehyde, both showed a high degree to Cu~(2). The complexation ratios of selective and fluorescent enhanced coumarin Schiff base fluorescent probes L4 and L5 with Cu~(2) are both 1: 2.
【学位授予单位】：海南师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O657.3

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