基于有机硅的氟离子探针合成与性能研究
发布时间：2018-10-26 07:56
【摘要】：氟元素是所有阴离子中半径最小的,这使得其电荷密度高,有着非常独特的物化性质。同时氟离子与生物体活动也息息相关。所以近年来,设计能够高效灵敏在水溶液中对氟离子进行识别的探针得到了广泛的研究与发展。氟离子探针可以分为氢键型、金属离子配位型等等。但是在所有的氟离子探针当中,硅氧键断裂反应型探针具有得天独厚的优点。因为其可以在含水溶液中高效、专一的识别氟离子。所以本文基于氟离子在水环境中可以诱使硅氧键断裂形成硅氟键的机理,对有机硅体系探针进行了深入而详细的探索。这类反应型探针无论是在稳定性还是识别灵敏度都有助于提升在水溶液中对于氟离子的识别,也为未来的生物应用奠定了一个很好的基础。本论文合成了三个体系共六个氟离子探针,并在此基础上结合氧化石墨烯得到纳米复合探针材料,实现了氟离子敏感识别。体系一:(1)查尔酮/橙酮类化合物1-3体系二:(2)吡啶盐类化合物4和5体系三:(3)荧光素化合物61、化合物合成与表征合成了六个小分子氟离子探针,对其进行了核磁共振氢谱、核磁共振碳谱、质谱和晶体结构的表征。与氧化石墨烯通过π-π堆积得到纳米复合探针材料,对其进行了红外、扫描电子显微镜、EDS等表征,证明了纳米复合材料的成功制备。2、探针对氟离子的识别系统研究了小分子探针在水溶液中对氟离子的识别。由于有机硅基团形成的识别位点的存在,化合物1-6都可以在水溶液中实现专一的识别氟离子。其中化合物1-3和5属于典型的荧光“turn-off”型。在加入氟离子后荧光变化均超过50%,特别是化合物2荧光减弱超过80%,裸眼观察到明显的荧光猝灭。化合物4与6是荧光“turn-on”型,特别是化合物6的纯水溶液加入氟离子之后溶液由无色变为明亮的荧光黄。经过计算发现化合物6的荧光检测限为6.17×10-7μM。结合原位核磁共振氢谱与质谱证明其识别机理为氟离子引发硅氧键的断裂。3、氧化石墨烯纳米探针材料对氟离子的识别为了进一步提高探针分子的氟离子识别灵敏性,在体系中引入了氧化石墨烯。通过大共轭环之间π-π堆积作用制备而成的纳米材料GO-1--6。所得纳米探针复合材料均保留了化合物1-6的吸收荧光特点。除此之外还增加了亲水性、提高灵敏度、降低了响应时间。特别是对比化合物2与GO-2可以发现:GO-2饱和当量数下降了80%,且响应时间从4000s下降到5s左右。可以认为氧化石墨烯优良的活化作用以及亲水性对于提高氟离子的识别是非常有效的。总之,本文设计合成的探针具有很好的水中识别氟离子的特性,为以后生物应用等做了很好的铺垫。
[Abstract]:Fluorine is the smallest of all anions, which makes its charge density high and has very unique physicochemical properties. At the same time, fluorine ion is closely related to biological activity. Therefore, in recent years, the design of a highly efficient and sensitive fluorine ion recognition probe in aqueous solution has been widely studied and developed. Fluorine probe can be divided into hydrogen bond type, metal ion coordination type and so on. However, among all fluorine ion probes, the silicon-oxygen bond breaking reaction probe has unique advantages. Because of its high efficiency in aqueous solutions, the recognition of fluoride ions. Therefore, based on the mechanism that fluorine ions can induce silicon-oxygen bond to break down in water environment, the probe of organosilicon system has been explored in detail. Both the stability and the sensitivity of these reactive probes are helpful to enhance the recognition of fluorine ions in aqueous solutions and lay a good foundation for future biological applications. In this paper, six fluorine ion probes were synthesized in three systems, and based on these, nano-composite probe materials were obtained by combining graphene oxide, and fluorine ion sensitive recognition was realized. System I: (1) Chalcone / Orange compounds 1-3 system 2: (2) pyridine salt compounds 4 and 5 system 3: (3) fluorescein compounds 61. Six small molecular fluorine ion probes were synthesized and characterized. The hydrogen NMR spectra, NMR carbon spectra, mass spectra and crystal structures were characterized. Nanocomposite probe materials were prepared by 蟺-蟺 stacking with graphene oxide. The nanocomposites were characterized by IR, SEM and EDS. The recognition of fluorine ions by small molecular probes in aqueous solution was studied. Due to the existence of recognition sites formed by organosilicon groups, compounds 1-6 can recognize fluorine ions specifically in aqueous solution. Compounds 1-3 and 5 belong to typical fluorescent "turn-off" type. The fluorescence changes of fluorine ions were more than 50, especially the fluorescence of compound 2 weakened by more than 80. Obvious fluorescence quenching was observed with naked eyes. Compounds 4 and 6 are fluorescent "turn-on" type, especially when the pure aqueous solution of compound 6 is added with fluorine ion, the solution changes from colorless to bright fluorescent yellow. The fluorescence detection limit of compound 6 is 6.17 脳 10 ~ (-7) 渭 M. Combined with in situ nuclear magnetic resonance spectroscopy and mass spectrometry, it was proved that the recognition mechanism was that fluorine ion initiated the breaking of silicon oxygen bond. 3. In order to further improve the sensitivity of fluorine ion recognition, graphene oxide nanoprobe material can recognize fluorine ion in order to further improve the sensitivity of fluorine ion recognition. Graphene oxide was introduced into the system. Preparation of nanomaterials GO-1--6. by 蟺-蟺 stacking between large conjugated rings The nanoprobe composites retained the fluorescence absorption characteristics of compound 1-6. In addition, the hydrophilicity is increased, the sensitivity is improved and the response time is reduced. In particular, by comparing compound 2 with GO-2, it can be found that the saturation equivalent number of GO-2 decreases by 80 and the response time decreases from 400 s to 5 s. It can be concluded that the excellent activation and hydrophilicity of graphene oxide are very effective in improving the recognition of fluorine ions. In a word, the probe designed and synthesized in this paper has good characteristics of recognizing fluorine ions in water, which provides a good basis for biological application in the future.
【学位授予单位】：济南大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O657.3
本文编号：2295061
[Abstract]:Fluorine is the smallest of all anions, which makes its charge density high and has very unique physicochemical properties. At the same time, fluorine ion is closely related to biological activity. Therefore, in recent years, the design of a highly efficient and sensitive fluorine ion recognition probe in aqueous solution has been widely studied and developed. Fluorine probe can be divided into hydrogen bond type, metal ion coordination type and so on. However, among all fluorine ion probes, the silicon-oxygen bond breaking reaction probe has unique advantages. Because of its high efficiency in aqueous solutions, the recognition of fluoride ions. Therefore, based on the mechanism that fluorine ions can induce silicon-oxygen bond to break down in water environment, the probe of organosilicon system has been explored in detail. Both the stability and the sensitivity of these reactive probes are helpful to enhance the recognition of fluorine ions in aqueous solutions and lay a good foundation for future biological applications. In this paper, six fluorine ion probes were synthesized in three systems, and based on these, nano-composite probe materials were obtained by combining graphene oxide, and fluorine ion sensitive recognition was realized. System I: (1) Chalcone / Orange compounds 1-3 system 2: (2) pyridine salt compounds 4 and 5 system 3: (3) fluorescein compounds 61. Six small molecular fluorine ion probes were synthesized and characterized. The hydrogen NMR spectra, NMR carbon spectra, mass spectra and crystal structures were characterized. Nanocomposite probe materials were prepared by 蟺-蟺 stacking with graphene oxide. The nanocomposites were characterized by IR, SEM and EDS. The recognition of fluorine ions by small molecular probes in aqueous solution was studied. Due to the existence of recognition sites formed by organosilicon groups, compounds 1-6 can recognize fluorine ions specifically in aqueous solution. Compounds 1-3 and 5 belong to typical fluorescent "turn-off" type. The fluorescence changes of fluorine ions were more than 50, especially the fluorescence of compound 2 weakened by more than 80. Obvious fluorescence quenching was observed with naked eyes. Compounds 4 and 6 are fluorescent "turn-on" type, especially when the pure aqueous solution of compound 6 is added with fluorine ion, the solution changes from colorless to bright fluorescent yellow. The fluorescence detection limit of compound 6 is 6.17 脳 10 ~ (-7) 渭 M. Combined with in situ nuclear magnetic resonance spectroscopy and mass spectrometry, it was proved that the recognition mechanism was that fluorine ion initiated the breaking of silicon oxygen bond. 3. In order to further improve the sensitivity of fluorine ion recognition, graphene oxide nanoprobe material can recognize fluorine ion in order to further improve the sensitivity of fluorine ion recognition. Graphene oxide was introduced into the system. Preparation of nanomaterials GO-1--6. by 蟺-蟺 stacking between large conjugated rings The nanoprobe composites retained the fluorescence absorption characteristics of compound 1-6. In addition, the hydrophilicity is increased, the sensitivity is improved and the response time is reduced. In particular, by comparing compound 2 with GO-2, it can be found that the saturation equivalent number of GO-2 decreases by 80 and the response time decreases from 400 s to 5 s. It can be concluded that the excellent activation and hydrophilicity of graphene oxide are very effective in improving the recognition of fluorine ions. In a word, the probe designed and synthesized in this paper has good characteristics of recognizing fluorine ions in water, which provides a good basis for biological application in the future.
【学位授予单位】：济南大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O657.3
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