A Copper(II) Ion-Selective On−Off-Type Fluoroionophore Based on Zinc Porphyrin−Dipyridylamino

Abstract

A new copper(II) fluorescent sensor 5,10,15,20-tetra((p-N,N-bis(2-pyridyl)amino)phenyl)porphyrin zinc (1) has been designed and synthesized by the Ullmann-type condensation of bromoporphyrin zinc with 2,2'-dipyridylamine (dpa) under copper powder as a catalyst as well as with K2CO3 as the base in a DMF solution. It consists of two separately functional moieties: the zinc porphyrin performs as a fluorophore, and the dpa-linked-to-zinc porphyrin acts as a selected binding site for metal ions. It displays a high selectivity and antidisturbance for the Cu2+ ion among the metal ions examined (Na+, Mg2+, Cr3+, Mn2+, Fe2+, Co2+, Ni2+, Cu2+, Ag+, Zn2+, Cd2+, Hg2+, and Fe3+) and exhibits fluorescence quenching upon the binding of the Cu2+ ion with an "on-off"-type fluoroionophoric switching property. The detection limit is found to be 3.3 x 10(-7) M (3s blank) for Cu2+ ion in methanol solution, and its fluorescence can be revived by the addition of EDTA disodium solution. The design strategy and remarkable photophysical properties of sensor 1 help to extend the development of fluorescent sensors for metal ions.

2-Aminotryptanthrin Derivative with Pyrene as a FRET-based Fluorescent Chemosensor for Metal Ions

“…The values of log K of T2NH-P5P with the metal ions are reported in Cu 2+ and Hg 2+ usually behave as fluorescence quenchers via an electron transfer from the excited-state fluorophore to the empty d-orbital [14][15][16] ; therefore, many of the reported molecular systems show a fluorescence-quenching response upon the addition of Cu 2+ and Hg 2+ . [17][18][19] Fluorescence quenching also occurs because of impurity contamination, which leads to inaccurate detection results. Therefore, a fluorescence "emission" chemosensor for Cu 2+ and Hg 2+ is necessary and important.…”

Using 5,10,15,20-tetra(4-nitrophenyl)porphyrin as a fluorescent chemosensor to determine Ru3+

“…The porphyrin macrocycles have been used as fluorophore owing to their high absorption coefficient in the visible range, tunable fluorescence emission, large Stoke shift, which can minimize fluorescence background and high photoand chemical-stability [17][18][19] . In addition, porphyrin metallation can be used as a method to determine metal cations when emission properties of metalloand free base-porphyrin are significantly different 20 .…”

The Composites of Cationic Polyelectrolyte and Glutathione‐capped Quantum Dots for Selective Fluorescence Detection of Cu2+

“…12 Fluorescence quenching based on the formation of Cu 2+ -ligand complexes is an alternative approach for simple and rapid detection of Cu 2+ in an aqueous solution. [14][15][16] In general, the fluorescent sensor consisted of a fluorophore and a complexing unit linked together through an appropriate spacer. Besides, fluorescence resonance energy transfer from the fluorophore to the quencher has been applied to sensing of Cu 2+ with high sensitivity and selectivity.…”