A high-sensitive sensor with HEPES-enhanced electrochemiluminescence of benzo[3]uril for Fe3+ and its application in human serum.

An electrochemiluminescence (ECL) sensor based on a benzo[3]uril-modified glassy carbon electrode with sensitized luminescence, with the coexistence of 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid (HEPES) as the coreactant, was successfully constructed. The sensitization mechanism was proposed by analyzing the results of the control experiments for establishing the relationship of the luminescence effect with the concentration of HEPES. Under the optimized conditions, the fabricated sensor system was applied for the detection of Fe3+ in an aqueous solution with good sensitivity and selectivity. A low detection limit of 0.41 nM was achieved, indicating superior sensor performance over the previous analytical methods. The ECL sensor system was employed for the detection of Fe3+ in human serum samples to produce excellent recoveries ranging from 96.17% to 101.81%.

Recognition of silver cations by multifarene[2,2] chemosensors with unexpected fluorescence response.

Fluorescent chemosensors based on a new macrocyclic compound, multifarene[2,2], with modification by triazole-linked pyrene or anthracene were synthesized. These macrocyclic sensors exhibited high affinity and selectivity toward Ag+ over other metal ions, with ratiometric or enhanced response of their fluorescence emissions depending upon the substituent species for coordination to Ag+, and an unexpected response to a concentration threshold of the metal cations was discovered. The experimental evidences of fluorescence spectra, 1H NMR titration, IR spectra, and high-resolution mass spectra suggested the coordination behaviors of the sensors with Ag+, that is, the 1:1 complexes were formed with moderate association constants of about 105 L·mol-1, and the sulfur atoms on macrocyclic ligand should affinite to the metal cations. Energy-minimized structures and frontier orbitals were estimated by quantum chemical calculations with a view to rationalizing the fluorescence response of the multifarene[2,2] sensors upon binding to Ag+.