基于苯并咪唑萘酰亚胺衍生物离子探针的合成及性能研究
发布时间：2018-11-23 12:10
【摘要】：本论文合成了 10种苯并咪唑萘酰亚胺的衍生物,都是以苯并咪唑并苯并异喹啉酮为母体,在C-10、C-11、C-12位上引入不同基团而设计合成,分别为N-(正丁基)苯并咪唑并苯并异喹啉酮-11-硫代酰胺(D1)、12-((叔丁基二苯基甲硅烷基)氧基)苯并咪唑并苯并异喹啉酮(D2)、10-(2-亚胺基硫脲-2-苯基)苯并咪唑并苯并异喹啉酮(D3)、11-(2-亚胺基硫脲-2-苯基)苯并咪唑并苯并异喹啉酮(D4)、10-(2-(2-硝基苯肼)亚甲基-2-苯基)苯并咪唑并苯并异喹啉酮(D5)、11-(2-(2-硝基苯肼)亚甲基-2-苯基)苯并咪唑并苯并异喹啉酮(D6)、10-(2-(4-硝基苯肼)亚甲基-2-苯基)苯并咪唑并苯并异喹啉酮(D7)、11-(2-(4-硝基苯肼)亚甲基-2-苯基)苯并咪唑并苯并异喹啉酮(D8)、10-(2-(2,4-二硝基苯肼)亚甲基-2-苯基)苯并咪唑并苯并异喹啉酮(D9)和11-(2-(2,4-二硝基苯肼)亚甲基-2-苯基)苯并咪唑并苯并异喹啉酮(D10)。以上10种苯并咪唑萘酰亚胺衍生物及其中间体均利用1HNMR、HRMS-ESI和13CNMR等多种分析方法验证了其结构正确性。另外,通过荧光发射光谱和紫外吸收光谱对合成的10种化合物进行了光学性质的研究,发现D1-D6这6种化合物可以作为Hg2+、F-荧光探针。在乙腈/水(7/3)的缓冲体系中,D1与Hg2+接触时,荧光增强,属于荧光“打开”型探针。D1属于反应型荧光探针,Hg2+会与探针D1上的C=S发生反应,生成HgS,诱导C=S变为C=O。探针D1对Hg2+表现出了较强选择性和抗干扰性,不受其他金属离子干扰,可以很好的检测Hg2+。并通过pH对探针的影响性实验,得出探针D1可以在pH 7.0-11.0范围内检测Hg2+。在DMSO溶液中,D2可以作为F--“关闭”型荧光探针,溶液由浅黄色变为蓝色(△λ = 225 nm)。D2也属于反应型荧光探针,与F-接触时,F-就会与探针D2上的Si发生反应,诱导Si-O断裂。探针D2对F-表现出了较强选择性和抗干扰性,可以很好的检测F-。在相同溶液中,探针D3和D4在与F-接触时,相应的在可见光下体系下D3由浅黄色变为橘黄色,D4由浅黄色变为紫红色,在紫外灯下荧光强度表现为由强变弱。通过将F-和HSO4-滴加到D3和D4的DMSO溶液中,相应的颜色变化可以交替变化,这表明探针D3和D4可以以可逆的方式使用。在DMSO溶液中,探针D5和D6在与F-接触时,相应的紫外吸收光谱分别显示最大红移为155 nm和195 nm,相应的在可见光下体系下D5和D6都是由浅黄色变为蓝绿色,荧光强度表现为荧光增强。在相同溶液中,D7-D10对F-的选择性识别能力要弱。CN-也可以引起D7和D8紫外吸收光谱不同程度的变化;在D9和D10的DMSO溶液中,加入CN-、AcO-、H2PO4-都可引起紫外吸收光谱的变化。
[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.
【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：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.
【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
【参考文献】
相关期刊论文 前1条
1 孟令芝,梅功雄,何永炳,曾振亚,刘顺英;新型四酰胺杯[4]氮杂冠醚的合成及对阴离子的光化学传感性质研究[J];化学学报;2005年05期
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