基于有機硅的氟離子探針合成與性能研究
發(fā)布時間：2018-10-26 07:56
【摘要】：氟元素是所有陰離子中半徑最小的,這使得其電荷密度高,有著非常獨特的物化性質(zhì)。同時氟離子與生物體活動也息息相關(guān)。所以近年來,設(shè)計能夠高效靈敏在水溶液中對氟離子進行識別的探針得到了廣泛的研究與發(fā)展。氟離子探針可以分為氫鍵型、金屬離子配位型等等。但是在所有的氟離子探針當(dāng)中,硅氧鍵斷裂反應(yīng)型探針具有得天獨厚的優(yōu)點。因為其可以在含水溶液中高效、專一的識別氟離子。所以本文基于氟離子在水環(huán)境中可以誘使硅氧鍵斷裂形成硅氟鍵的機理,對有機硅體系探針進行了深入而詳細(xì)的探索。這類反應(yīng)型探針無論是在穩(wěn)定性還是識別靈敏度都有助于提升在水溶液中對于氟離子的識別,也為未來的生物應(yīng)用奠定了一個很好的基礎(chǔ)。本論文合成了三個體系共六個氟離子探針,并在此基礎(chǔ)上結(jié)合氧化石墨烯得到納米復(fù)合探針材料,實現(xiàn)了氟離子敏感識別。體系一:(1)查爾酮/橙酮類化合物1-3體系二:(2)吡啶鹽類化合物4和5體系三:(3)熒光素化合物61、化合物合成與表征合成了六個小分子氟離子探針,對其進行了核磁共振氫譜、核磁共振碳譜、質(zhì)譜和晶體結(jié)構(gòu)的表征。與氧化石墨烯通過π-π堆積得到納米復(fù)合探針材料,對其進行了紅外、掃描電子顯微鏡、EDS等表征,證明了納米復(fù)合材料的成功制備。2、探針對氟離子的識別系統(tǒng)研究了小分子探針在水溶液中對氟離子的識別。由于有機硅基團形成的識別位點的存在,化合物1-6都可以在水溶液中實現(xiàn)專一的識別氟離子。其中化合物1-3和5屬于典型的熒光“turn-off”型。在加入氟離子后熒光變化均超過50%,特別是化合物2熒光減弱超過80%,裸眼觀察到明顯的熒光猝滅�；衔�4與6是熒光“turn-on”型,特別是化合物6的純水溶液加入氟離子之后溶液由無色變?yōu)槊髁恋臒晒恻S。經(jīng)過計算發(fā)現(xiàn)化合物6的熒光檢測限為6.17×10-7μM。結(jié)合原位核磁共振氫譜與質(zhì)譜證明其識別機理為氟離子引發(fā)硅氧鍵的斷裂。3、氧化石墨烯納米探針材料對氟離子的識別為了進一步提高探針分子的氟離子識別靈敏性,在體系中引入了氧化石墨烯。通過大共軛環(huán)之間π-π堆積作用制備而成的納米材料GO-1--6。所得納米探針復(fù)合材料均保留了化合物1-6的吸收熒光特點。除此之外還增加了親水性、提高靈敏度、降低了響應(yīng)時間。特別是對比化合物2與GO-2可以發(fā)現(xiàn):GO-2飽和當(dāng)量數(shù)下降了80%,且響應(yīng)時間從4000s下降到5s左右�？梢哉J(rèn)為氧化石墨烯優(yōu)良的活化作用以及親水性對于提高氟離子的識別是非常有效的。總之,本文設(shè)計合成的探針具有很好的水中識別氟離子的特性,為以后生物應(yīng)用等做了很好的鋪墊。
[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.
【學(xué)位授予單位】：濟南大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O657.3
本文編號：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.
【學(xué)位授予單位】：濟南大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O657.3
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