OFF-ON型熒光探針的制備及性能研究
發(fā)布時(shí)間：2018-12-05 20:42
【摘要】：近年來識別重金屬離子的熒光探針已經(jīng)成為化學(xué)傳感器的一個(gè)熱點(diǎn)問題。在眾多的重金屬離子中,由于Fe3+作為生物體內(nèi)必需微量元素,Ag+應(yīng)用廣泛性和Hg2+的高毒性,開發(fā)新型的可以識別環(huán)境和生物系統(tǒng)中的Fe3+,Ag+和Hg2+方法是非常必要的。由于具有摩爾消光系數(shù)高光、穩(wěn)定性好、熒光量子產(chǎn)率高、較長的激發(fā)波長和發(fā)射波長等特點(diǎn),羅丹明類熒光探針受到研究人員的關(guān)注。羅丹明螺環(huán)衍生物是無色、無熒光的,當(dāng)金屬離子誘導(dǎo)其開環(huán)后,它們就會恢復(fù)到原來的粉紅色和強(qiáng)烈的熒光。羅丹明螺環(huán)結(jié)構(gòu)的開-閉環(huán)體系為熒光增強(qiáng)型分子探針的設(shè)計(jì)提供了一個(gè)十分優(yōu)秀的平臺。本文圍繞羅丹明‘'OFF-ON"型熒光探針的設(shè)計(jì)、合成和應(yīng)用研究進(jìn)行了如下工作：1.以羅丹明B、乙二胺、2-3-(羥基亞甲基)-1-環(huán)己烯-1-甲醛為原料,設(shè)計(jì)合成了一種含雙羅丹明B內(nèi)酰胺隱色體的熒光探針R1。探針R1對Fe3+具有很好的選擇性與靈敏度,檢測限可達(dá)到3.7×10-7M。探針R1與Fe3+,S2-結(jié)合構(gòu)成禁止門器件,實(shí)現(xiàn)檢測的數(shù)字化。以羅丹明B、乙二胺、三聚氯氰為原料合成羅丹明酰胺三嗪衍生物,通過引入識別基團(tuán)2-氨基吡啶得到探針RC2P。探針RC2P可以在水溶液中檢測Fe3+,從而打破溶液對探針檢測的限制,實(shí)現(xiàn)檢測的便捷與環(huán)保。探針RC2P與Fe3+的結(jié)合常數(shù)為K=4.1×108M-1。此外,探針R1與RC2P可以成功的應(yīng)用于細(xì)胞中Fe3+的成像。2.以羅丹明B、乙二胺、三聚氯氰為原料合成羅丹明酰胺三嗪衍生物,通過連接識別基團(tuán)鄰苯二酚、間苯二酚、對苯二酚合成了五種可以特異性識別Ag+熒光探針。有關(guān)羅丹明類Ag+探針的報(bào)道非常少,本文極大地豐富了羅丹明類探針的應(yīng)用范圍。羅丹明酰胺三嗪衍生物連接對苯二酚得到的探針RP1對Ag+的檢測具有較好的選擇性與抗干擾能力,其對Ag+的檢測限可達(dá)到3.2×10-8M。探針RP1與納濾膜結(jié)合做成了便攜試條,可用于對Ag+的定性與定量檢測。3.以羅丹明B、乙二胺、三聚氯氰為原料合成了羅丹明酰胺三嗪衍生物,再通過連接8-羥基喹啉、咔唑合成兩種熒光增強(qiáng)型Hg2+熒光探針RH與RC。探針RH對Hg2+具有很好的靈敏性,其對Hg2+的最低檢測限為2.2×10-8M。探針RH對Hg2+的高靈敏性,使探針RH可以成功地應(yīng)用于檢測自來水與湖泊水中的Hg2+。4.利用Materials Studio軟件計(jì)算了R1與RC2P的最優(yōu)分子結(jié)構(gòu)、最高占據(jù)分子軌道與最低占據(jù)分子軌道,以及RO1、RM1、RM2、RP1、RP2和RH的最優(yōu)分子結(jié)構(gòu)。探針R1-Fe3+的最高占據(jù)分子軌道的電子勢能為-3.009 ev,最低占據(jù)分子軌道的電子勢能為-2.552 ev。探針RC2P的最高占據(jù)分子軌道的電子勢能為-4.339 ev,最低占據(jù)分子軌道的電子勢能為-2.256 ev。R1、RC2P、RO1、RM1、 RM2、RP1、RP2和RH的最優(yōu)分子結(jié)構(gòu)的獲得對于研究探針分子的空間構(gòu)型對識別金屬離子的影響具有重要意義。
[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.
【學(xué)位授予單位】：天津工業(yè)大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2016
【分類號】：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.
【學(xué)位授予單位】：天津工業(yè)大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2016
【分類號】：O657.3
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