基于氨基喹啉席夫碱Al~(3+)荧光探针的合成与表征
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摘要
工业飞速发展所带来的金属离子污染问题已经影响到人类的生存环境及身体健康,为了探究环境及生物体内的金属离子含量,荧光传感器脱颖而出,成为对金属离子定量与定性分析的有力工具.喹啉同时具有荧光和识别性能,我们通过引入席夫碱结构,增加其共轭体系和络合金属能力.以2-甲基-8-氨基喹啉为起始原料与不同结构的芳醛合成了三个席夫碱类化合物L-1,L-2,L-3,所得产物的结构均经红外光谱、高分辨质谱以及核磁共振氢谱和碳谱验证.我们利用X射线衍射分析确定了单晶L-2的晶体结构,结果表明,合成产物属于单斜晶系,P 2_1/n空间群,晶胞参数为:a=6.625 9(2)nm,b=15.168 9(5)nm,c=16.858 3(6) nm,α=90.00°,β=98.602(2)°,γ=90.00°,V=1 675.33(10)nm~3,Z=4,μ=0.084 mm~(-1),F(000)=676.0,Data completeness=0.997,Theta(max)=28.291°,R(reflections)=0.416 3(3 078),wR_2(reflections)=0.794 2(4 154).因席夫碱结构中-C=N-异构化和分子内电荷转移(ICT)过程使化合物本身只有微弱荧光,在与不同金属离子结合后可抑制这一过程并释放出不同的荧光信号,从而达到离子选择性检测效果.我们初步对L-1,L-2和L-3进行了金属离子检测筛选,发现它们均对Al~(3+)有特异性荧光增强响应,并计算得到它们对Al~(3+)的检出限分别为0.02、0.10和0.14μmol·L~(-1).
The problem of pollution of the metal ions caused by the rapid development of industry has affected the living environment and health of human beings. In order to explore the metal ions content in the environment and living organisms, fluorescent sensors have emerged as a powerful tool for qualitative and quantitative analysis of metal ions. Quinoline has both fluorescence and recognition properties. By introducing Schiff base structure its conjugated system and complex metal ability were increased. So we used 2-methyl-8-aminoquinoline as starting material with various aromatic aldehydes to synthesize three different structures L-1, L-2, L-3, the structures of which were verified by IR, HRMS, ~1H NMR and ~(13)C NMR. The crystal structure of L-2 was determined by X-ray single crystal diffraction, and the result showed that the synthesized product belonged to monoclinic system, P 2_1/n space group and the unit cell parameters: a= 6.625 9(2) nm, b=15.168 9(5) nm, c=16.858 3(6) nm, α= 90.00°, β=98.602(2)°, γ=90.00°, V=1 675.33(10) nm~3, Z=4, μ=0.084 mm~(-1), F(000)=676.0, Data completeness=0.997, Theta(max)=28.291°, R(reflections)=0.416 3(3 078), wR_2(reflections)= 0.794 2( 4 154).The-C=N-isomerization and intramolecular charge transfer(ICT) processes in the introduced Schiff base structure allowed the compounds itself to appear only weak fluorescence, which inhibited the processes and released different fluorescent signals when combined with different metal ions. We initially screened the metal ions of L-1, L-2 and L-3 and the results appeared that they all had specific fluorescence enhancement responses to Al~(3+) ion. Their detection limits for Al~(3+) were calculated to be 0.02、 0.10 and 0.14 μmol·L~(-1), respectively.
The problem of pollution of the metal ions caused by the rapid development of industry has affected the living environment and health of human beings. In order to explore the metal ions content in the environment and living organisms, fluorescent sensors have emerged as a powerful tool for qualitative and quantitative analysis of metal ions. Quinoline has both fluorescence and recognition properties. By introducing Schiff base structure its conjugated system and complex metal ability were increased. So we used 2-methyl-8-aminoquinoline as starting material with various aromatic aldehydes to synthesize three different structures L-1, L-2, L-3, the structures of which were verified by IR, HRMS, ~1H NMR and ~(13)C NMR. The crystal structure of L-2 was determined by X-ray single crystal diffraction, and the result showed that the synthesized product belonged to monoclinic system, P 2_1/n space group and the unit cell parameters: a= 6.625 9(2) nm, b=15.168 9(5) nm, c=16.858 3(6) nm, α= 90.00°, β=98.602(2)°, γ=90.00°, V=1 675.33(10) nm~3, Z=4, μ=0.084 mm~(-1), F(000)=676.0, Data completeness=0.997, Theta(max)=28.291°, R(reflections)=0.416 3(3 078), wR_2(reflections)= 0.794 2( 4 154).The-C=N-isomerization and intramolecular charge transfer(ICT) processes in the introduced Schiff base structure allowed the compounds itself to appear only weak fluorescence, which inhibited the processes and released different fluorescent signals when combined with different metal ions. We initially screened the metal ions of L-1, L-2 and L-3 and the results appeared that they all had specific fluorescence enhancement responses to Al~(3+) ion. Their detection limits for Al~(3+) were calculated to be 0.02、 0.10 and 0.14 μmol·L~(-1), respectively.
引文
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[20] WANICHACHEVA N,HANMENG O,KRAITHONG S,et al.Dual optical Hg2+-selective sensing through FRET system of fluorescein and rhodamine B fluorophores[J].Journal of Photochemistry and Photobiology A,Chemistry,2015,278:75-81.
[21] GREENFIELD J L,RIZZUTO F J,GOLDBERGA I,et al.Self-assembly of conjugated metallopolymers with tunable length and controlled regiochemistry[J].Angewandte Chemie Intrnational Edition,2017,56:7541-7545.
[2] LIU X Y,FU J X,YAO K,et al.Phenanthroline-based fluorescence sensors for Eu3+ ion and subsequent enantioselective discriminating of malate[J].Supramolecular Chemistry,2018,30:994-1003.
[3] KIM H N,REN W X,KIM J S,et al.Fluorescent and colorimetric sensors for detection of lead,cadmium,and mercury ions[J].Chemical Society Reviews,2012,41:3210-3244.
[4] CHANG Y X,FU J X,YAO K,et al.Novel fluorescent probes for sequential detection of Cu2+ and citrate anion and application in living cell imaging[J].Dyes and Pigments,2018,161:331-340.
[5] ARAGAY G,PONS J,MERKOCI A.Recent trends in macro-,micro-,and nanomaterial-based tools and strategies for heavy-metal detection[J].Chemical Reviews,2011,111:3433-3458.
[6] WU J,LIU W,GE J,et al.New sensing mechanisms for design of fluorescent chemosensors emerging in recent years[J].Chemical Society Reviews,2011,40:3483-3495.
[7] WANG P,FU J X,YAO K,et al.A novel quinoline-derived fluorescent “turn-on” probe for Cu2+ with highly selectivity and sensitivity and its application in cell imaging[J].Sensors and Actuators B:Chemical,2018,273:1070-1076.
[8] NOH J Y,PARK G J,NA Y J,et al.A colorimetric “naked-eye” Cu(II) chemosensor and pH indicator in 100% aqueous solution[J].Dalton Transactions,2014,43:5652-5656.
[9] ERDEMIR S,TABAKCI B,TABAKCI M.A highly selective fluorescent sensor based on calix[4] arene appended benzothiazole units for Cu2+,S2- and HSO-4 ions in aqueous solution[J].Sensors and Actuators B:Chemical,2016,228:109-116.
[10] ERDEMIR S,KOCYIGIT O,KARAKURT S.A new perylene bisimide-armed calix[4]-aza-crown as turn on fluorescent sensor for Hg2+ ion and its application to living cells[J].Sensors and Actuators B:Chemical,2015,220:381-388.
[11] CHEN Y,CHEN B,HAN Y.A novel rhodamine-based fluorescent probe for the fluorogenic and chromogenic detection of Pd2+ ions and its application in live-cell imaging[J].Sensors and Actuators B:Chemical,2016,237:1-7.
[12] PARK G J,PARK D Y,PARK K,et al.Solvent-dependent chromogenic sensing for Cu2+,and fluorogenic sensing for Zn2+,and Al3+:a multifunctional chemosensor with dual-mode[J].Tetrahedron,2014,70:7429-7438.
[13] WANG L,QIN W,LIU W.A sensitive Schiff-base fluorescent indicator for the detection of Zn[J].Inorganic Chemistry Communications,2010,13:1122-1125.
[14] WANG F,MOON J H,NANDHAKUMAR R,et al.Zn2+-induced conformational changes in a binaphthyl-pyrene derivative monitored by using fluorescence and CD spectroscopy[J].Chemical Communications,2013,49:7228-7230.
[15] GOGOI A,SAMANTA S,DAS G.A benzothiazole containing CHEF based fluorescence turn-ON sensor for Zn2+,and Cd2+,and subsequent sensing of H2PO-4,and P4O,in physiological pH[J].Sensors and Actuators B:Chemical,2014,202:788-794.
[16] SURESH M,MANDAL A K,SAHA S,et al.Azine-based receptor for recognition of Hg2+ ion:crystallographic evidence and imaging application in live cells[J].Organic Letters,2010,12:5406-5409.
[17] YAO K,FU J X,CHANG Y X,et al.A selective fluorescent probe for relay detection of Zn2+ and tartrate:Application to logic circuit and living cell imaging[J].Spectrochimica Acta Part A:Molecular and Biomolecular Spectroscopy,2018,205:410-418
[18] AZADBAKHT R,RASHIDI S.A new fluorescent chemosensor for Al3+ ion based on schiff base naphthalene derivatives[J].Spectrochimica Acta Part A:Molecular and Biomolecular Spectroscopy,2014,127:329-334.
[19] GONCALVES A C,PILLA V,OLIVEIRA E,et al.The interaction of Hg2+ and trivalent ions with two new fluorescein bio-inspired dual colorimetric/fluorimetric probes[J].Dalton Transactions,2016,45:9513-95122.
[20] WANICHACHEVA N,HANMENG O,KRAITHONG S,et al.Dual optical Hg2+-selective sensing through FRET system of fluorescein and rhodamine B fluorophores[J].Journal of Photochemistry and Photobiology A,Chemistry,2015,278:75-81.
[21] GREENFIELD J L,RIZZUTO F J,GOLDBERGA I,et al.Self-assembly of conjugated metallopolymers with tunable length and controlled regiochemistry[J].Angewandte Chemie Intrnational Edition,2017,56:7541-7545.
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