合成了罗丹明类Cu2+荧光增强型分子探针3′,6′-双(二乙氨基)-2-(N-乙叉基氨基)螺[异吲哚-1,9′-占吨]-3-酮(RA),研究了它的光谱性能及对铜离子的识别作用.在CH3CN/H2O(体积比1∶1)介质中加入Cu2+后,探针RA显玫瑰红色,荧光强度显著增强,最大吸收波长为548 nm,最大发射波长为571 nm,而其它常见离子如Na+,K+,Mg2+,Ca2+,Mn2+,Cd2+,Cr3+,Co2+,Ni2+,Ag+,Pb2+,Zn2+,Fe3+和Hg2+不引起或引起很小的紫外-可见或荧光光谱变化.RA的选择性荧光增强主要是由于Cu2+诱导分子中的酰胺闭环结构发生开环,导致分子结构的共轭程度增大所致.在6.5×10-8-2.9×10-6mol/L浓度范围内,RA可以有效检测Cu2+,检出限为5.0×10-8mol/L.实验结果表明,RA对Cu2+的识别过程不可逆,而且RA对pH不敏感,可在较宽的pH(4.1-10.5)范围内高灵敏、高选择性地检测Cu2+.
In this paper,Cu2+ fluorescence enhancement probe 3′,6′-bis(diethylamino)-2-(N-ethylideneamino) spiro[isoindoline-1,9′-xanthen]-3-one(RA) based on rhodamine B was synthesized.It was found that the fluorescence intensity of RA increased with the addition of Cu2+ in acetonitrile/water(1∶1,volume ratio) solution.The maximum absorption wavelength was 548 nm.The maximum emission wavelength was 571 nm.The addition of Cu2+ ion led to an obvious color change to pink as well as significantly enhanced fluorescence,while other common metal ions such as Na+,K+,Mg2+,Ca2+,Mn2+,Cd2+,Cr3+,Co2+,Ni2+,Ag+,Pb2+,Zn2+,Fe3+and Hg2+ induced no or much smaller color/fluorescent spectral changes.The selective fluorescence enhancement of RA attributed to the spirolactam ring being opened upon the addition of Cu2+ to RA,and a highly delocalized conjugated structure of RA was formed.The sensor was useful for measuring Cu2+ at concentrations ranging from 6.5×10-8 to 2.9×10-6 mol/L with a detection limit of 5.0×10-8 mol/L.The recognition of Cu2+ was not reversible,and compound RA was pH-insensitive Cu2+ fluorescent probe,which would detect Cu2+ effectively in a relatively wide pH range(4.1—10.5).