Hg2+ detection by new anthracene pendant-arm derivatives of mixed N/S- and N/S/O-donor macrocycles: fluorescence, matrix-assisted laser desorption/ionization time-of-flight mass spectrometry and density functional theory studies.
The optical response of four new anthracenylmethyl pendant-arm derivatives (L1-L4) of the macrocyclic ligands [12]aneNS(3), [12]aneNS(2)O, [15]aneNS(2)O(2), and [12]aneN(2)SO toward the metal ions Zn(2+), Cd(2+), Pb(2+), Cu(2+), Hg(2+), Ag(+), Fe(2+), Co(2+), Ni(2+), Mn(2+), Ca(2+), Na(+), Mg(2+), and K(+) was investigated in 1:1 (v/v) MeCN/H(2)O solutions. A strong chelation enhancement of quenching effect was observed on the fluorescent emission intensity of L2 as a consequence of the host-guest interaction with Hg(2+) and the formation of a 1:2 metal-to-ligand complex. Density functional theory calculations confirmed the formation of a sandwich-type complex between L2 and Hg(2+) as a favorable process. A matrix-assisted laser desorption/ionization (MALDI) time-of-flight mass spectrometry study using the four ligands as active MALDI probes was also performed. L1-L4 have also been explored as fluorescence chemosensors in microsamples using NANODROP technology.
Mameli
Marta
M
Dipartimento di Chimica Inorganica ed Analitica, Università degli Studi di Cagliari, S.S. 554 Bivio per Sestu, 09042 Monserrato, Italy.
Lippolis
Vito
V
Caltagirone
Claudia
C
Capelo
José Luis
JL
Faza
Olalla Nieto
ON
Lodeiro
Carlos
C
D000042:Absorption; D000873:Anthracenes / Q000737:chemistry*; D001372:Aza Compounds / Q000737:chemistry; D002623:Chemistry Techniques, Analytical / Q000295:instrumentation*; D008024:Ligands; D047028:Macrocyclic Compounds / Q000737:chemistry*; D008628:Mercury / Q000032:analysis* / Q000737:chemistry; D008958:Models, Molecular; D008968:Molecular Conformation; D009584:Nitrogen / Q000737:chemistry; D010100:Oxygen / Q000737:chemistry; D011789:Quantum Theory; D013050:Spectrometry, Fluorescence / Q000379:methods*; D019032:Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization; D013455:Sulfur / Q000737:chemistry
D000873:Anthracenes; D001372:Aza Compounds; D008024:Ligands; D047028:Macrocyclic Compounds; D013455:Sulfur; C034020:anthracene; D008628:Mercury; D009584:Nitrogen; D010100:Oxygen