新型基于咔唑-氨基硫脲席夫碱识别Cu~(2+)的探针
|
摘要
合成出了3个新型基于咔唑-氨基硫脲席夫碱衍生物.利用裸眼、紫外-可见光谱、荧光光谱和质谱研究了代表2-[(N-庚烷-咔唑-3-基)甲叉基]肼硫代甲酰胺(L_2)对阳离子的识别性能.实验结果显示,该化合物水溶性良好,可以在DMSO-H_2O(V∶V=6∶4,Tris-HCl缓冲液,pH=7.0)的体系中使用.当加入Cu~(2+)时,化合物L_2的DMSO-H_2O溶液显示出明显的颜色变化,由无色变为黄色,而其它阳离子无明显颜色变化.这表明,席夫碱L_2可作为裸眼识别Cu~(2+)的探针.荧光光谱分析实验发现,在DMSO-H_2O(V∶V=6∶4,Tris-HCl缓冲液,pH=7.0)溶剂中,探针L_2是对Cu~(2+)具有高选择性和灵敏度的荧光猝灭型探针.探针L_2与Cu~(2+)的结合常数为3.42×104 L·mol~(-1),检测限为8.96×10-6 mol·L~(-1).MS分析显示,L_2与Cu~(2+)的络合比为1∶1.探针L_2对Cu~(2+)的检测限低于世界卫生组织(WHO)规定的饮用水中Cu~(2+)的最大含量20?mol·L~(-1).
Three novel carbazole-thiosemicarbazides based Schiff-base were synthesized. The recognition ability of representive 2-((N-heptane-carbazol-3-yl)methylidene)hydrazine carbothioamide(L_2) to metal ions was investigated by naked-eye, UV-Vis, fluorescence and mass spectra. The experimental results showed that this compound had a good water solubility and can be investigated in DMSO-H2 O(V∶V=6∶4, Tris-HCl buffer, pH=7.0). The compound L_2 in the DMSO-H2 O displayed a distinct color change from colorless to yellow upon the addition of Cu~(2+), other metal ions did not induce significant colour changes, which indicated that Schiff base L_2 can be used as a probe with naked eye detection for Cu~(2+). The fluorescence spectra showed that the probe L_2 was a high selective and sensitive "turn-off" fluorescence probe for Cu~(2+) in DMSO-H2 O(V∶V=6∶4, Tris-HCl buffer, pH=7.0). The association constant between the probe L_2 and Cu~(2+) was detected to be 3.42×104 L·mol~(-1), and the detection limit was calculated to be 8.96×10-6 mol·L~(-1). MS analysis showed a 1∶1 binding stoichiometry between Cu~(2+) and L_2. The detection limit of L_2 for Cu~(2+) was far lower than the maximum allowable level of World Health Organization(WHO) limit(20 ?mol·L~(-1)) for drinking water.
Three novel carbazole-thiosemicarbazides based Schiff-base were synthesized. The recognition ability of representive 2-((N-heptane-carbazol-3-yl)methylidene)hydrazine carbothioamide(L_2) to metal ions was investigated by naked-eye, UV-Vis, fluorescence and mass spectra. The experimental results showed that this compound had a good water solubility and can be investigated in DMSO-H2 O(V∶V=6∶4, Tris-HCl buffer, pH=7.0). The compound L_2 in the DMSO-H2 O displayed a distinct color change from colorless to yellow upon the addition of Cu~(2+), other metal ions did not induce significant colour changes, which indicated that Schiff base L_2 can be used as a probe with naked eye detection for Cu~(2+). The fluorescence spectra showed that the probe L_2 was a high selective and sensitive "turn-off" fluorescence probe for Cu~(2+) in DMSO-H2 O(V∶V=6∶4, Tris-HCl buffer, pH=7.0). The association constant between the probe L_2 and Cu~(2+) was detected to be 3.42×104 L·mol~(-1), and the detection limit was calculated to be 8.96×10-6 mol·L~(-1). MS analysis showed a 1∶1 binding stoichiometry between Cu~(2+) and L_2. The detection limit of L_2 for Cu~(2+) was far lower than the maximum allowable level of World Health Organization(WHO) limit(20 ?mol·L~(-1)) for drinking water.
引文
[1]Zhan,S.S.;Wu,Y.G.;Wang,L.M.;Zhan,X.J.;Liu,P.Biosens.Bioelectron.2016,86,353.
[2]Lee,S.Y.;Bok,K.H.;Kim,J.A.;Kim,S.Y.;Kim,C.Tetrahedron2016,72,5563.
[3]Zhou,H.T.;Sun,L.;Chen,W.;Tian,G.J.;Chen,Y.;Li,Y.R.;Su,J.H.Tetrahedron 2016,72,2300.
[4]Kundu,A.;Hariharan,P.S.;Prabakaran,K.;Anthony,S.P.Sens.Actuators,B:Chem.2015,206,524.
[5]Yang,J.Y.;Chen,L.H.;Zheng,Y.Z.;Dong,X.Y.;Raghunandhan,R.;So,P.L.;Chan,C.C.Sens.Actuators,B:Chem.2016,230,353.
[6]Qin,J.C.;Fan,L.;Yang,Z.Y.Sens.Actuators,B:Chem.2016,228,156.
[7]Feng,Y.;Lia,D.X.;Wang,Q.;Wang,S.X.;Meng,X.M.;Shao,Z.L.;Zhu,M.Z.;Wang,X.Sens.Actuators,B:Chem.2016,225,572.
[8]Zhou,Y.Y.;Tang,L.;Zeng,G.M.;Zhang,C.;Zhang,Y.;Xie,X.Sens.Actuators,B:Chem.2016,223,280.
[9]Kandasamy,K.;Ganesabaskaran,S.;Pachamuthu,M.P.;Maheswari,R.;Ramanathan,A.Spectrochim.Acta,Part A 2015,150,34.
[10]Samanta,S.;Samanta,P.K.;Dutta,S.;Biswas,P.Spectrochim.Acta,Part A 2015,147,262.
[11]Xu,W.J.;Qi,D.Q.;You,J.Z.;Hu,F.F.;Bian,J.Y.;Yang,C.X.;Huang,J.J.Mol.Struct.2015,1091,133.
[12]Wang,E.Z.;Zhou,Y.M.;Huang,Q.;Pang,L.F.;Qiao,H.;Yu,F.;Gao,B.;Zhang,J.L.;Min,Y.H.;Ma,T.S.Spectrochim.Acta,Part A 2016,152,327.
[13]Hu,Y.;Zhang,J.;Lv,Y.Z.;Huang,X.H.;Hu,S.L.Spectrochim.Acta,Part A 2016,157,164.
[14]Bekhradnia,A.;Domehri,E.;Khosravi,M.Spectrochim.Acta,Part A 2016,152,18.
[15]Diao,H.P.;Niu,W.P.;Liu,W.;Feng,L.H.;Xie,J.Spectrochim.Acta,Part A 2017,170,65.
[16]Li,Y.J.;Li,J.Y.;Xu,Y.T.;Jin,K.;Cao,X.Chin.J.Org.Chem.2017,37,896(in Chinese).(李英俊,李继阳,许永廷,靳焜,曹欣,有机化学,2017,37,896.)
[17]Xiong,J.J.;Huang,P.C.;Zhang,C.Y.;Wu,F.Y.Sens.Actuators,B:Chem.2016,226,30.
[18]Feng,L.;Shi,W.;Ma,J.C.;Chen,Y.B.;Kui,F.;Hui,Y.H.;Xie,Z.F.Sens.Actuators,B:Chem.2016,237,563.
[19]Liu,J.L.;Meng,X.;Duan,H.D.;Xu,T.;Ding,Z.Y.;Liu,Y.;Lucia,L.Sens.Actuators,B:Chem.2016,227,296.
[20]Vikneswaran,R.;Syafiq,M.S.;Eltayeb,N.E.;Kamaruddin,M.N.;Ramesh,S.;Yahya,R.Spectrochim.Acta,Part A 2015,150,175.
[21]Ganjali,M.R.;Hosseini,M.;Motalebi,M.;Sedaghat,M.;Mizani,F.;Faridbod,F.;Norouzi,P.Spectrochim.Acta,Part A 2015,140,283.
[22]Zhang,C.H.;Gao,B.Z.;Zhang,Q.Y.;Zhang,G.M.;Shuang,S.M.;Dong,C.Talanta 2016,154,278.
[23]You,G.R.;Lee,J.J.;Choi,Y.W.;Lee,S.Y.;Kim,C.Tetrahedron2016,72,875.
[24]Zhu,W.J.;Yang,L.L.;Fang,M.;Wu,Z.Y.;Zhang,Q.;Yin,F.F.;Huang,Q.;Li,C.J.Lumin.2015,158,38.
[25]Jagadeeswari,S.;Paramaguru,G.;Thennarasu,S.;Renganathan,R.J.Mol.Struct.2014,1060,191.
[26]Jagadeeswari,S.;Paramaguru,G.;Thennarasu,S.;Renganathan,R.J.Mol.Struct.2014,1060,191.
[27]Ramkumar,S.;Manoharan,S.;Anandan,S.Dyes Pigm.2012,94,503.
[28]Budreckiene,R.;Buika,G.;Grazulevicius,J.V.;Jankauskas,V.;Staniskiene,B.J.Photochem.Photobiol.,A 2006,181,257.
[2]Lee,S.Y.;Bok,K.H.;Kim,J.A.;Kim,S.Y.;Kim,C.Tetrahedron2016,72,5563.
[3]Zhou,H.T.;Sun,L.;Chen,W.;Tian,G.J.;Chen,Y.;Li,Y.R.;Su,J.H.Tetrahedron 2016,72,2300.
[4]Kundu,A.;Hariharan,P.S.;Prabakaran,K.;Anthony,S.P.Sens.Actuators,B:Chem.2015,206,524.
[5]Yang,J.Y.;Chen,L.H.;Zheng,Y.Z.;Dong,X.Y.;Raghunandhan,R.;So,P.L.;Chan,C.C.Sens.Actuators,B:Chem.2016,230,353.
[6]Qin,J.C.;Fan,L.;Yang,Z.Y.Sens.Actuators,B:Chem.2016,228,156.
[7]Feng,Y.;Lia,D.X.;Wang,Q.;Wang,S.X.;Meng,X.M.;Shao,Z.L.;Zhu,M.Z.;Wang,X.Sens.Actuators,B:Chem.2016,225,572.
[8]Zhou,Y.Y.;Tang,L.;Zeng,G.M.;Zhang,C.;Zhang,Y.;Xie,X.Sens.Actuators,B:Chem.2016,223,280.
[9]Kandasamy,K.;Ganesabaskaran,S.;Pachamuthu,M.P.;Maheswari,R.;Ramanathan,A.Spectrochim.Acta,Part A 2015,150,34.
[10]Samanta,S.;Samanta,P.K.;Dutta,S.;Biswas,P.Spectrochim.Acta,Part A 2015,147,262.
[11]Xu,W.J.;Qi,D.Q.;You,J.Z.;Hu,F.F.;Bian,J.Y.;Yang,C.X.;Huang,J.J.Mol.Struct.2015,1091,133.
[12]Wang,E.Z.;Zhou,Y.M.;Huang,Q.;Pang,L.F.;Qiao,H.;Yu,F.;Gao,B.;Zhang,J.L.;Min,Y.H.;Ma,T.S.Spectrochim.Acta,Part A 2016,152,327.
[13]Hu,Y.;Zhang,J.;Lv,Y.Z.;Huang,X.H.;Hu,S.L.Spectrochim.Acta,Part A 2016,157,164.
[14]Bekhradnia,A.;Domehri,E.;Khosravi,M.Spectrochim.Acta,Part A 2016,152,18.
[15]Diao,H.P.;Niu,W.P.;Liu,W.;Feng,L.H.;Xie,J.Spectrochim.Acta,Part A 2017,170,65.
[16]Li,Y.J.;Li,J.Y.;Xu,Y.T.;Jin,K.;Cao,X.Chin.J.Org.Chem.2017,37,896(in Chinese).(李英俊,李继阳,许永廷,靳焜,曹欣,有机化学,2017,37,896.)
[17]Xiong,J.J.;Huang,P.C.;Zhang,C.Y.;Wu,F.Y.Sens.Actuators,B:Chem.2016,226,30.
[18]Feng,L.;Shi,W.;Ma,J.C.;Chen,Y.B.;Kui,F.;Hui,Y.H.;Xie,Z.F.Sens.Actuators,B:Chem.2016,237,563.
[19]Liu,J.L.;Meng,X.;Duan,H.D.;Xu,T.;Ding,Z.Y.;Liu,Y.;Lucia,L.Sens.Actuators,B:Chem.2016,227,296.
[20]Vikneswaran,R.;Syafiq,M.S.;Eltayeb,N.E.;Kamaruddin,M.N.;Ramesh,S.;Yahya,R.Spectrochim.Acta,Part A 2015,150,175.
[21]Ganjali,M.R.;Hosseini,M.;Motalebi,M.;Sedaghat,M.;Mizani,F.;Faridbod,F.;Norouzi,P.Spectrochim.Acta,Part A 2015,140,283.
[22]Zhang,C.H.;Gao,B.Z.;Zhang,Q.Y.;Zhang,G.M.;Shuang,S.M.;Dong,C.Talanta 2016,154,278.
[23]You,G.R.;Lee,J.J.;Choi,Y.W.;Lee,S.Y.;Kim,C.Tetrahedron2016,72,875.
[24]Zhu,W.J.;Yang,L.L.;Fang,M.;Wu,Z.Y.;Zhang,Q.;Yin,F.F.;Huang,Q.;Li,C.J.Lumin.2015,158,38.
[25]Jagadeeswari,S.;Paramaguru,G.;Thennarasu,S.;Renganathan,R.J.Mol.Struct.2014,1060,191.
[26]Jagadeeswari,S.;Paramaguru,G.;Thennarasu,S.;Renganathan,R.J.Mol.Struct.2014,1060,191.
[27]Ramkumar,S.;Manoharan,S.;Anandan,S.Dyes Pigm.2012,94,503.
[28]Budreckiene,R.;Buika,G.;Grazulevicius,J.V.;Jankauskas,V.;Staniskiene,B.J.Photochem.Photobiol.,A 2006,181,257.