新型七甲川吲哚菁类荧光探针的设计合成及CN~-检测性能研究
发布时间：2019-03-28 07:18
【摘要】：氰化物在工业生产中起着非常重要的作用,广泛应用于金矿开采、电镀、树脂及纤维合成等领域。但是,氰根离子是剧毒物,可以通过肺,皮肤,受污染的食物和受污染的饮用水摄入人体内。因此,在环境及生物体内对氰化物进行有效迅速的检测非常重要。本论文设计并合成了三种基于七甲川吲哚菁的近红外氰根离子荧光探针,研究了探针的氰根离子检测性能,具体内容如下:(1)基于七甲川吲哚菁染料的荧光探针P1和P2的设计合成及氰根离子检测性能研究。通过吲哚嗡盐与2-氯-1-甲酰基-3-羟次甲基环己烯的缩合反应制备了探针P1和P2,通过1H NMR、13C NMR和MALDI-TOF质谱表征了探针的分子结构。通过紫外可见吸收光谱和荧光发射光谱研究了探针P1和P2的氰根离子检测性能,结果表明:随着氰根离子的加入,探针P1在776 nm和探针P2在795 nm处的吸收峰逐渐降低,并在短波区域出现新的吸收峰,溶液颜色由绿色转变为淡黄色;同时,探针P1在802 nm和探针P2在817 nm处的荧光发射峰强度逐渐降低,常见阴离子对探针的紫外吸收和荧光发射光谱几乎没有干扰;在一定浓度范围内,探针P1和P2的荧光强度与氰根离子浓度存在良好的线性关系,其最低检测限分别为0.017μM和0.20μM;通过1H NMR,MALDI-TOF质谱和Job’s曲线证实了探针与氰根离子的亲核加成反应机理;此外,探针P2实现了在生物体内对氰根离子的有效检测。(2)基于三苯胺-七甲川吲哚菁染料的荧光探针P3设计合成及氰根离子检测性能研究。在探针P1的基础上,通过改进的Sukuzi偶联反应,在探针P1的中位引入电子给体三苯胺合成了探针P3,通过1H NMR、13C NMR和MALDI-TOF质谱表征了探针P3的分子结构。通过紫外可见吸收光谱和荧光发射光谱研究了探针P3的氰根离子检测性能,结果表明:随着氰根离子的加入,探针P3在750nm吸收峰逐渐降低,并在416 nm处出现新的吸收峰,溶液颜色由翠绿色转变为亮黄色;同时,探针P3在780 nm处的荧光发射峰强度逐渐降低,常见阴离子对探针的紫外吸收和荧光发射光谱几乎没有干扰;在乙腈溶液中,探针P3的荧光强度与氰根离子浓度(0-5μM)存在良好的线性关系,其最低检测限为0.014μM;通过1H NMR,MALDI-TOF质谱和Job’s曲线证实了探针P3的氰根离子检测机理为亲核加成反应;此外,基于P3的测试纸可以更方便检测CN ,并且通过生物荧光成像实现了探针P3在细胞L929中对氰根离子的有效检测。
[Abstract]:Cyanide plays a very important role in industrial production. It is widely used in gold mining, electroplating, resin and fiber synthesis. But cyanide ions are highly toxic and can be ingested into the human body through the lungs, skin, contaminated food and contaminated drinking water. Therefore, it is very important to detect cyanide effectively and rapidly in the environment and organism. In this paper, we designed and synthesized three kinds of near infrared cyanine ion fluorescence probes based on heptachuan indole cyanine, and studied the performance of cyanogen ion detection of the probes. The main contents are as follows: (1) the design and synthesis of fluorescent probes P1 and P2 based on heptachuan indocyanine dyes and the performance of cyanogen ion detection were studied. The probes P1 and P2were prepared by condensation of indole salt with 2-chloro-1-formyl-3-hydroxymethylcyclohexene. The molecular structures of the probes were characterized by 1H NMR,13C NMR and MALDI-TOF mass spectrometry. The detection performance of probe P1 and P2 was studied by UV visible absorption spectrum and fluorescence emission spectrum. The results showed that the absorption peak of probe P1 at 776 nm and probe P2 at 795 nm decreased gradually with the addition of cyano ion. A new absorption peak appeared in the shortwave region, and the color of the solution changed from green to yellowish. At the same time, the intensity of fluorescence emission peaks of probe P1 at 802 nm and probe P2 at 817 nm decreased gradually, and the ultraviolet absorption and fluorescence emission spectra of the probes were almost undisturbed by anions. Within a certain concentration range, there was a good linear relationship between the fluorescence intensity of the probes P1 and P2 and the concentration of cyanide ion, and the minimum detection limits were 0.017 渭 M and 0.20 渭 M, respectively. The nucleophilic addition mechanism of the probe with cyanogen ion was confirmed by 1H NMR,MALDI-TOF mass spectrometry and Job's curve. In addition, the probe P2 realized the effective detection of cyanogen ions in organisms. (2) Design and synthesis of fluorescence probe P3 based on triphenylamine-heptachlorocyanic indocyanine dye and study on the performance of cyanogen ion detection. On the basis of the probe P1, the probe P3 was synthesized by introducing electron donor triphenylamine into the middle position of the probe P1 by improved Sukuzi coupling reaction. The molecular structure of the probe P3 was characterized by 1H NMR,13C NMR and MALDI-TOF mass spectrometry. The detection performance of probe P3 was studied by UV visible absorption spectrum and fluorescence emission spectrum. The results showed that with the addition of cyano ion, the absorption peak of probe P3 decreased gradually in 750nm, and a new absorption peak appeared at 416nm. The color of the solution changed from emerald green to bright yellow. At the same time, the intensity of fluorescence emission peak of probe P3 at 780 nm decreased gradually, and the ultraviolet absorption and fluorescence emission spectra of probe P3 were almost undisturbed by anions. In acetonitrile solution, the fluorescence intensity of probe P3 has a good linear relationship with the concentration of cyanide ion (0-5 渭 M), and the detection limit is 0.014 渭 M. 1H NMR,MALDI-TOF mass spectrometry and Job's curve confirmed that the mechanism of cyanogen ion detection of probe P3 was nucleophilic addition reaction. In addition, the P3-based test paper is more convenient to detect CN, and the probe P3 can be used to detect cyanogen ions in L929 cells by bioluminescence imaging.
【学位授予单位】：湘潭大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O657.3
[Abstract]:Cyanide plays a very important role in industrial production. It is widely used in gold mining, electroplating, resin and fiber synthesis. But cyanide ions are highly toxic and can be ingested into the human body through the lungs, skin, contaminated food and contaminated drinking water. Therefore, it is very important to detect cyanide effectively and rapidly in the environment and organism. In this paper, we designed and synthesized three kinds of near infrared cyanine ion fluorescence probes based on heptachuan indole cyanine, and studied the performance of cyanogen ion detection of the probes. The main contents are as follows: (1) the design and synthesis of fluorescent probes P1 and P2 based on heptachuan indocyanine dyes and the performance of cyanogen ion detection were studied. The probes P1 and P2were prepared by condensation of indole salt with 2-chloro-1-formyl-3-hydroxymethylcyclohexene. The molecular structures of the probes were characterized by 1H NMR,13C NMR and MALDI-TOF mass spectrometry. The detection performance of probe P1 and P2 was studied by UV visible absorption spectrum and fluorescence emission spectrum. The results showed that the absorption peak of probe P1 at 776 nm and probe P2 at 795 nm decreased gradually with the addition of cyano ion. A new absorption peak appeared in the shortwave region, and the color of the solution changed from green to yellowish. At the same time, the intensity of fluorescence emission peaks of probe P1 at 802 nm and probe P2 at 817 nm decreased gradually, and the ultraviolet absorption and fluorescence emission spectra of the probes were almost undisturbed by anions. Within a certain concentration range, there was a good linear relationship between the fluorescence intensity of the probes P1 and P2 and the concentration of cyanide ion, and the minimum detection limits were 0.017 渭 M and 0.20 渭 M, respectively. The nucleophilic addition mechanism of the probe with cyanogen ion was confirmed by 1H NMR,MALDI-TOF mass spectrometry and Job's curve. In addition, the probe P2 realized the effective detection of cyanogen ions in organisms. (2) Design and synthesis of fluorescence probe P3 based on triphenylamine-heptachlorocyanic indocyanine dye and study on the performance of cyanogen ion detection. On the basis of the probe P1, the probe P3 was synthesized by introducing electron donor triphenylamine into the middle position of the probe P1 by improved Sukuzi coupling reaction. The molecular structure of the probe P3 was characterized by 1H NMR,13C NMR and MALDI-TOF mass spectrometry. The detection performance of probe P3 was studied by UV visible absorption spectrum and fluorescence emission spectrum. The results showed that with the addition of cyano ion, the absorption peak of probe P3 decreased gradually in 750nm, and a new absorption peak appeared at 416nm. The color of the solution changed from emerald green to bright yellow. At the same time, the intensity of fluorescence emission peak of probe P3 at 780 nm decreased gradually, and the ultraviolet absorption and fluorescence emission spectra of probe P3 were almost undisturbed by anions. In acetonitrile solution, the fluorescence intensity of probe P3 has a good linear relationship with the concentration of cyanide ion (0-5 渭 M), and the detection limit is 0.014 渭 M. 1H NMR,MALDI-TOF mass spectrometry and Job's curve confirmed that the mechanism of cyanogen ion detection of probe P3 was nucleophilic addition reaction. In addition, the P3-based test paper is more convenient to detect CN, and the probe P3 can be used to detect cyanogen ions in L929 cells by bioluminescence imaging.
【学位授予单位】：湘潭大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O657.3
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