基于苯并咪唑萘酰亞胺衍生物離子探針的合成及性能研究
發(fā)布時間：2018-11-23 12:10
【摘要】：本論文合成了 10種苯并咪唑萘酰亞胺的衍生物,都是以苯并咪唑并苯并異喹啉酮為母體,在C-10、C-11、C-12位上引入不同基團而設計合成,分別為N-(正丁基)苯并咪唑并苯并異喹啉酮-11-硫代酰胺(D1)、12-((叔丁基二苯基甲硅烷基)氧基)苯并咪唑并苯并異喹啉酮(D2)、10-(2-亞胺基硫脲-2-苯基)苯并咪唑并苯并異喹啉酮(D3)、11-(2-亞胺基硫脲-2-苯基)苯并咪唑并苯并異喹啉酮(D4)、10-(2-(2-硝基苯肼)亞甲基-2-苯基)苯并咪唑并苯并異喹啉酮(D5)、11-(2-(2-硝基苯肼)亞甲基-2-苯基)苯并咪唑并苯并異喹啉酮(D6)、10-(2-(4-硝基苯肼)亞甲基-2-苯基)苯并咪唑并苯并異喹啉酮(D7)、11-(2-(4-硝基苯肼)亞甲基-2-苯基)苯并咪唑并苯并異喹啉酮(D8)、10-(2-(2,4-二硝基苯肼)亞甲基-2-苯基)苯并咪唑并苯并異喹啉酮(D9)和11-(2-(2,4-二硝基苯肼)亞甲基-2-苯基)苯并咪唑并苯并異喹啉酮(D10)。以上10種苯并咪唑萘酰亞胺衍生物及其中間體均利用1HNMR、HRMS-ESI和13CNMR等多種分析方法驗證了其結構正確性。另外,通過熒光發(fā)射光譜和紫外吸收光譜對合成的10種化合物進行了光學性質的研究,發(fā)現(xiàn)D1-D6這6種化合物可以作為Hg2+、F-熒光探針。在乙腈/水(7/3)的緩沖體系中,D1與Hg2+接觸時,熒光增強,屬于熒光“打開”型探針。D1屬于反應型熒光探針,Hg2+會與探針D1上的C=S發(fā)生反應,生成HgS,誘導C=S變?yōu)镃=O。探針D1對Hg2+表現(xiàn)出了較強選擇性和抗干擾性,不受其他金屬離子干擾,可以很好的檢測Hg2+。并通過pH對探針的影響性實驗,得出探針D1可以在pH 7.0-11.0范圍內檢測Hg2+。在DMSO溶液中,D2可以作為F--“關閉”型熒光探針,溶液由淺黃色變?yōu)樗{色(△λ = 225 nm)。D2也屬于反應型熒光探針,與F-接觸時,F-就會與探針D2上的Si發(fā)生反應,誘導Si-O斷裂。探針D2對F-表現(xiàn)出了較強選擇性和抗干擾性,可以很好的檢測F-。在相同溶液中,探針D3和D4在與F-接觸時,相應的在可見光下體系下D3由淺黃色變?yōu)殚冱S色,D4由淺黃色變?yōu)樽霞t色,在紫外燈下熒光強度表現(xiàn)為由強變弱。通過將F-和HSO4-滴加到D3和D4的DMSO溶液中,相應的顏色變化可以交替變化,這表明探針D3和D4可以以可逆的方式使用。在DMSO溶液中,探針D5和D6在與F-接觸時,相應的紫外吸收光譜分別顯示最大紅移為155 nm和195 nm,相應的在可見光下體系下D5和D6都是由淺黃色變?yōu)樗{綠色,熒光強度表現(xiàn)為熒光增強。在相同溶液中,D7-D10對F-的選擇性識別能力要弱。CN-也可以引起D7和D8紫外吸收光譜不同程度的變化;在D9和D10的DMSO溶液中,加入CN-、AcO-、H2PO4-都可引起紫外吸收光譜的變化。
[Abstract]:In this paper, ten derivatives of benzimidazole-naphthalimide were synthesized and synthesized using benzimidazole-benzo-isoquinolinone as parent, and different groups were introduced at C-10C ~ (11) C ~ (12). N- (n-Ding Ji) benzimidazolidazolinone-11-thioamides (D1), 12- (tert-Ding Ji dimethylsilyl) oxy) benzimidazolidazobenzo-isoquinolinone (D2), 10- (2-iminitrothiourea-2-phenyl) benzimidazole benzisoquinolinone (D3), 11- (2-iminitrothiourea-2-phenyl) benzimidazolidazolinone (D4), 10- (2- (2-nitrophenyl hydrazine) methylene 2-phenyl) benzimidazolidazolinone (D5), 11- (2- (2-nitrophenyl hydrazine) methylene-2-phenyl) benzimidazolidazolinone (D6), 10- (2- (4-nitrophenyl hydrazine) methylene 2-phenyl) benzimidazolidazolinone (D7), 11- (2- (4-nitrophenyl hydrazine) methylene-2-phenyl) benzimidazolidazolinone (D8), 10- (2- (2- (2-) -dinitrophenylhydrazine) methyl-2-phenyl) benzimidazolidazobenzo-isoquinolinone (D9) and 11- (2- (2- (2- (2- (2-) -dinitrophenylhydrazine) methylene -2-phenyl) benzimidazolidazobenzene isoquinolinone (D10). The structures of the 10 benzimidazole-naphthalimide derivatives and their intermediates were verified by 1HNMR-HRMS-ESI and 13CNMR. In addition, the optical properties of 10 compounds were studied by fluorescence emission spectra and UV absorption spectra. It was found that the six compounds of D1-D6 can be used as Hg2, F- fluorescence probes. In acetonitrile / water (7 / 3) buffer system, the fluorescence of D1 in contact with Hg2 is enhanced and belongs to fluorescence "open" type probe. D1 belongs to reactive fluorescence probe, and Hg2 reacts with Con S on probe D1 to form HgS, to induce Con S into Con. Probe D1 shows strong selectivity and anti-interference to Hg2 and can be used to detect Hg2 without interference from other metal ions. The results showed that probe D1 could be used to detect Hg2 in the range of 7.0-11.0 by pH. In DMSO solution, D2 can be used as a F- "closed" type fluorescence probe. The solution changes from light yellow to blue (位 = 225 nm). D2 is also a reactive fluorescent probe. When exposed to F-, F- reacts with Si on probe D2. Si-O breaks were induced. Probe D2 shows strong selectivity and anti-interference to F-, and it can be used to detect F -. In the same solution, when the probes D3 and D4 were in contact with F-, D3 changed from light yellow to orange, D4 changed from light yellow to purplish red in the system of visible light, and the fluorescence intensity of probe D3 and D4 decreased from strong to weak under ultraviolet lamp. By dropping F- and HSO4- into DMSO solution of D3 and D4, the corresponding color changes can be changed alternately, which indicates that the probes D3 and D4 can be used in a reversible manner. In DMSO solution, the corresponding UV absorption spectra of probe D5 and D6 in contact with F- showed that the maximum red shift was 155 nm and 195 nm, respectively, and D5 and D6 changed from light yellow to turquoise under visible light, respectively. The intensity of fluorescence was enhanced. In the same solution, the selective recognition ability of D7-D10 to F- is weak. CN- can also cause the changes of D7 and D8 UV absorption spectra. In DMSO solution of D9 and D10, the addition of CN-,AcO-,H2PO4- can cause the change of UV absorption spectrum.
【學位授予單位】：濟南大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：O657.3
本文編號：2351565
[Abstract]:In this paper, ten derivatives of benzimidazole-naphthalimide were synthesized and synthesized using benzimidazole-benzo-isoquinolinone as parent, and different groups were introduced at C-10C ~ (11) C ~ (12). N- (n-Ding Ji) benzimidazolidazolinone-11-thioamides (D1), 12- (tert-Ding Ji dimethylsilyl) oxy) benzimidazolidazobenzo-isoquinolinone (D2), 10- (2-iminitrothiourea-2-phenyl) benzimidazole benzisoquinolinone (D3), 11- (2-iminitrothiourea-2-phenyl) benzimidazolidazolinone (D4), 10- (2- (2-nitrophenyl hydrazine) methylene 2-phenyl) benzimidazolidazolinone (D5), 11- (2- (2-nitrophenyl hydrazine) methylene-2-phenyl) benzimidazolidazolinone (D6), 10- (2- (4-nitrophenyl hydrazine) methylene 2-phenyl) benzimidazolidazolinone (D7), 11- (2- (4-nitrophenyl hydrazine) methylene-2-phenyl) benzimidazolidazolinone (D8), 10- (2- (2- (2-) -dinitrophenylhydrazine) methyl-2-phenyl) benzimidazolidazobenzo-isoquinolinone (D9) and 11- (2- (2- (2- (2- (2-) -dinitrophenylhydrazine) methylene -2-phenyl) benzimidazolidazobenzene isoquinolinone (D10). The structures of the 10 benzimidazole-naphthalimide derivatives and their intermediates were verified by 1HNMR-HRMS-ESI and 13CNMR. In addition, the optical properties of 10 compounds were studied by fluorescence emission spectra and UV absorption spectra. It was found that the six compounds of D1-D6 can be used as Hg2, F- fluorescence probes. In acetonitrile / water (7 / 3) buffer system, the fluorescence of D1 in contact with Hg2 is enhanced and belongs to fluorescence "open" type probe. D1 belongs to reactive fluorescence probe, and Hg2 reacts with Con S on probe D1 to form HgS, to induce Con S into Con. Probe D1 shows strong selectivity and anti-interference to Hg2 and can be used to detect Hg2 without interference from other metal ions. The results showed that probe D1 could be used to detect Hg2 in the range of 7.0-11.0 by pH. In DMSO solution, D2 can be used as a F- "closed" type fluorescence probe. The solution changes from light yellow to blue (位 = 225 nm). D2 is also a reactive fluorescent probe. When exposed to F-, F- reacts with Si on probe D2. Si-O breaks were induced. Probe D2 shows strong selectivity and anti-interference to F-, and it can be used to detect F -. In the same solution, when the probes D3 and D4 were in contact with F-, D3 changed from light yellow to orange, D4 changed from light yellow to purplish red in the system of visible light, and the fluorescence intensity of probe D3 and D4 decreased from strong to weak under ultraviolet lamp. By dropping F- and HSO4- into DMSO solution of D3 and D4, the corresponding color changes can be changed alternately, which indicates that the probes D3 and D4 can be used in a reversible manner. In DMSO solution, the corresponding UV absorption spectra of probe D5 and D6 in contact with F- showed that the maximum red shift was 155 nm and 195 nm, respectively, and D5 and D6 changed from light yellow to turquoise under visible light, respectively. The intensity of fluorescence was enhanced. In the same solution, the selective recognition ability of D7-D10 to F- is weak. CN- can also cause the changes of D7 and D8 UV absorption spectra. In DMSO solution of D9 and D10, the addition of CN-,AcO-,H2PO4- can cause the change of UV absorption spectrum.
【學位授予單位】：濟南大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：O657.3
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相關期刊論文 前1條
1 孟令芝,梅功雄,何永炳,曾振亞,劉順英;新型四酰胺杯[4]氮雜冠醚的合成及對陰離子的光化學傳感性質研究[J];化學學報;2005年05期
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