OFF-ON型荧光探针的制备及性能研究
发布时间：2018-12-05 20:42
【摘要】：近年来识别重金属离子的荧光探针已经成为化学传感器的一个热点问题。在众多的重金属离子中,由于Fe3+作为生物体内必需微量元素,Ag+应用广泛性和Hg2+的高毒性,开发新型的可以识别环境和生物系统中的Fe3+,Ag+和Hg2+方法是非常必要的。由于具有摩尔消光系数高光、稳定性好、荧光量子产率高、较长的激发波长和发射波长等特点,罗丹明类荧光探针受到研究人员的关注。罗丹明螺环衍生物是无色、无荧光的,当金属离子诱导其开环后,它们就会恢复到原来的粉红色和强烈的荧光。罗丹明螺环结构的开-闭环体系为荧光增强型分子探针的设计提供了一个十分优秀的平台。本文围绕罗丹明‘'OFF-ON"型荧光探针的设计、合成和应用研究进行了如下工作：1.以罗丹明B、乙二胺、2-3-(羟基亚甲基)-1-环己烯-1-甲醛为原料,设计合成了一种含双罗丹明B内酰胺隐色体的荧光探针R1。探针R1对Fe3+具有很好的选择性与灵敏度,检测限可达到3.7×10-7M。探针R1与Fe3+,S2-结合构成禁止门器件,实现检测的数字化。以罗丹明B、乙二胺、三聚氯氰为原料合成罗丹明酰胺三嗪衍生物,通过引入识别基团2-氨基吡啶得到探针RC2P。探针RC2P可以在水溶液中检测Fe3+,从而打破溶液对探针检测的限制,实现检测的便捷与环保。探针RC2P与Fe3+的结合常数为K=4.1×108M-1。此外,探针R1与RC2P可以成功的应用于细胞中Fe3+的成像。2.以罗丹明B、乙二胺、三聚氯氰为原料合成罗丹明酰胺三嗪衍生物,通过连接识别基团邻苯二酚、间苯二酚、对苯二酚合成了五种可以特异性识别Ag+荧光探针。有关罗丹明类Ag+探针的报道非常少,本文极大地丰富了罗丹明类探针的应用范围。罗丹明酰胺三嗪衍生物连接对苯二酚得到的探针RP1对Ag+的检测具有较好的选择性与抗干扰能力,其对Ag+的检测限可达到3.2×10-8M。探针RP1与纳滤膜结合做成了便携试条,可用于对Ag+的定性与定量检测。3.以罗丹明B、乙二胺、三聚氯氰为原料合成了罗丹明酰胺三嗪衍生物,再通过连接8-羟基喹啉、咔唑合成两种荧光增强型Hg2+荧光探针RH与RC。探针RH对Hg2+具有很好的灵敏性,其对Hg2+的最低检测限为2.2×10-8M。探针RH对Hg2+的高灵敏性,使探针RH可以成功地应用于检测自来水与湖泊水中的Hg2+。4.利用Materials Studio软件计算了R1与RC2P的最优分子结构、最高占据分子轨道与最低占据分子轨道,以及RO1、RM1、RM2、RP1、RP2和RH的最优分子结构。探针R1-Fe3+的最高占据分子轨道的电子势能为-3.009 ev,最低占据分子轨道的电子势能为-2.552 ev。探针RC2P的最高占据分子轨道的电子势能为-4.339 ev,最低占据分子轨道的电子势能为-2.256 ev。R1、RC2P、RO1、RM1、 RM2、RP1、RP2和RH的最优分子结构的获得对于研究探针分子的空间构型对识别金属离子的影响具有重要意义。
[Abstract]:In recent years, fluorescent probes that recognize heavy metal ions have become a hot issue in chemical sensors. Among the many heavy metal ions, it is necessary to develop a new method of recognizing Fe3, Ag and Hg2 in environment and biological system because Fe3 is an essential trace element in organism, Ag is widely used and Hg2 is highly toxic. Because of its high molar extinction coefficient, good stability, high fluorescence quantum yield and long excitation and emission wavelengths, Rhodamine fluorescent probes have attracted much attention. Rhodamine snail ring derivatives are colorless and non-fluorescent. When metal ions induce them to open their rings, they return to the original pink and strong fluorescence. The open-loop system of Rhodamine snail structure provides an excellent platform for the design of fluorescent enhanced molecular probes. In this paper, the design, synthesis and application of Rhodamine 'OFF-ON' fluorescent probe were studied as follows: 1. Using rhodamine B, ethylenediamine, 2-3- (hydroxymethylene) -1-cyclohexene-1-formaldehyde as raw materials, a fluorescent probe R1 containing bisrhodamine B lactam was designed and synthesized. The probe R1 has good selectivity and sensitivity to Fe3, and the detection limit can reach 3.7 脳 10 ~ (-7) M. The probe R 1 combined with Fe3, S 2-is a forbidden gate device to realize the digitization of detection. Rhodamine amide triazine derivatives were synthesized from rhodamine B, ethylenediamine and cyanide chloride. The probe RC2P. was obtained by introducing the recognition group 2-aminopyridine. Probe RC2P can be used to detect Fe3 in aqueous solution, which can break the limit of probe detection and realize the convenience and environmental protection. The binding constant of probe RC2P to Fe3 is 4. 1 脳 108M-1. In addition, probe R1 and RC2P can be successfully used in the imaging of Fe3 in cells. 2. 2. Rhodamine amide triazine derivatives were synthesized from Rhodamine B, ethylenediamine and cyanuric chloride. Five Ag fluorescent probes were synthesized by ligation of catechol, resorcinol and hydroquinone. There are few reports about Rhodamine Ag probes. This paper has enriched the application of Rhodamine probes. The probe RP1 from Rhodamine Amidine triazine Derivatives connected with hydroquinone has good selectivity and anti-interference ability for Ag detection, and its detection limit for Ag can reach 3.2 脳 10 ~ (-8) M. The probe RP1 was combined with nanofiltration membrane to make a portable test strip, which can be used for qualitative and quantitative detection of Ag. Rhodamine amide triazine derivatives were synthesized by using rhodamine B, ethylenediamine and cyanide chloride as raw materials. Two fluorescent enhanced Hg2 fluorescent probes RH and RC. were synthesized by linking 8-hydroxyquinoline with carbazole. The probe RH has good sensitivity to Hg2, and its minimum detection limit for Hg2 is 2.2 脳 10 ~ (-8) M. The high sensitivity of probe RH to Hg2 makes it possible to apply probe RH to the detection of Hg2. 4. 4 in tap water and lake water. The optimal molecular structure of R1 and RC2P, the highest occupied molecular orbital and the lowest occupied molecular orbital, and the optimal molecular structure of RO1,RM1,RM2,RP1,RP2 and RH are calculated by Materials Studio software. The maximum occupied molecular orbital electron potential energy of probe R1-Fe3 is-3.009 ev, the lowest occupied molecular orbital electron potential energy is-2.552 ev.. The maximum occupied molecular orbital electron potential energy of probe RC2P is-4.339 ev, the lowest occupied molecular orbital electron potential energy is-2.256 ev.R1,RC2P,RO1,RM1, RM2,RP1,. Obtaining the optimal molecular structure of RP2 and RH is of great significance in studying the influence of the spatial configuration of probe molecules on the recognition of metal ions.
【学位授予单位】：天津工业大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O657.3
[Abstract]:In recent years, fluorescent probes that recognize heavy metal ions have become a hot issue in chemical sensors. Among the many heavy metal ions, it is necessary to develop a new method of recognizing Fe3, Ag and Hg2 in environment and biological system because Fe3 is an essential trace element in organism, Ag is widely used and Hg2 is highly toxic. Because of its high molar extinction coefficient, good stability, high fluorescence quantum yield and long excitation and emission wavelengths, Rhodamine fluorescent probes have attracted much attention. Rhodamine snail ring derivatives are colorless and non-fluorescent. When metal ions induce them to open their rings, they return to the original pink and strong fluorescence. The open-loop system of Rhodamine snail structure provides an excellent platform for the design of fluorescent enhanced molecular probes. In this paper, the design, synthesis and application of Rhodamine 'OFF-ON' fluorescent probe were studied as follows: 1. Using rhodamine B, ethylenediamine, 2-3- (hydroxymethylene) -1-cyclohexene-1-formaldehyde as raw materials, a fluorescent probe R1 containing bisrhodamine B lactam was designed and synthesized. The probe R1 has good selectivity and sensitivity to Fe3, and the detection limit can reach 3.7 脳 10 ~ (-7) M. The probe R 1 combined with Fe3, S 2-is a forbidden gate device to realize the digitization of detection. Rhodamine amide triazine derivatives were synthesized from rhodamine B, ethylenediamine and cyanide chloride. The probe RC2P. was obtained by introducing the recognition group 2-aminopyridine. Probe RC2P can be used to detect Fe3 in aqueous solution, which can break the limit of probe detection and realize the convenience and environmental protection. The binding constant of probe RC2P to Fe3 is 4. 1 脳 108M-1. In addition, probe R1 and RC2P can be successfully used in the imaging of Fe3 in cells. 2. 2. Rhodamine amide triazine derivatives were synthesized from Rhodamine B, ethylenediamine and cyanuric chloride. Five Ag fluorescent probes were synthesized by ligation of catechol, resorcinol and hydroquinone. There are few reports about Rhodamine Ag probes. This paper has enriched the application of Rhodamine probes. The probe RP1 from Rhodamine Amidine triazine Derivatives connected with hydroquinone has good selectivity and anti-interference ability for Ag detection, and its detection limit for Ag can reach 3.2 脳 10 ~ (-8) M. The probe RP1 was combined with nanofiltration membrane to make a portable test strip, which can be used for qualitative and quantitative detection of Ag. Rhodamine amide triazine derivatives were synthesized by using rhodamine B, ethylenediamine and cyanide chloride as raw materials. Two fluorescent enhanced Hg2 fluorescent probes RH and RC. were synthesized by linking 8-hydroxyquinoline with carbazole. The probe RH has good sensitivity to Hg2, and its minimum detection limit for Hg2 is 2.2 脳 10 ~ (-8) M. The high sensitivity of probe RH to Hg2 makes it possible to apply probe RH to the detection of Hg2. 4. 4 in tap water and lake water. The optimal molecular structure of R1 and RC2P, the highest occupied molecular orbital and the lowest occupied molecular orbital, and the optimal molecular structure of RO1,RM1,RM2,RP1,RP2 and RH are calculated by Materials Studio software. The maximum occupied molecular orbital electron potential energy of probe R1-Fe3 is-3.009 ev, the lowest occupied molecular orbital electron potential energy is-2.552 ev.. The maximum occupied molecular orbital electron potential energy of probe RC2P is-4.339 ev, the lowest occupied molecular orbital electron potential energy is-2.256 ev.R1,RC2P,RO1,RM1, RM2,RP1,. Obtaining the optimal molecular structure of RP2 and RH is of great significance in studying the influence of the spatial configuration of probe molecules on the recognition of metal ions.
【学位授予单位】：天津工业大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O657.3
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