title: Lanthanide complex-based luminescent probes for highly sensitive time-gated luminescence detection of hypochlorous acid.
abstract: Two novel lanthanide complex-based luminescent probes, ANMTTA-Eu(3+) and ANMTTA-Tb(3+) {ANMTTA, [4'-(4-amino-3-nitrophenoxy)methylene-2,2':6',2"-terpyridine-6,6"-diyl] bis(methylenenitrilo) tetrakis(acetic acid)}, have been designed and synthesized for the highly sensitive and selective time-gated luminescence detection of hypochlorous acid (HOCl) in aqueous media. The probes are almost nonluminescent due to the photoinduced electron transfer (PET) process from the 4-amino-3-nitrophenyl moiety to the terpyridine-Ln(3+) moiety, which quenches the lanthanide luminescence effectively. Upon reaction with HOCl, the 4-amino-3-nitrophenyl moiety is rapidly cleaved from the probe complexes, which affords strongly luminescent lanthanide complexes HTTA-Eu(3+) and HTTA-Tb(3+) {HTTA, (4'-hydroxymethyl-2,2':6',2"-terpyridine-6,6"-diyl) bis(methylenenitrilo) tetrakis(acetic acid)}, accompanied by the remarkable luminescence enhancements. The dose-dependent luminescence enhancements show good linearity with detection limits of 1.3 nM and 0.64 nM for HOCl with ANMTTA-Eu(3+) and ANMTTA-Tb(3+), respectively. In addition, the luminescence responses of ANMTTA-Eu(3+) and ANMTTA-Tb(3+) to HOCl are pH-independent with excellent selectivity to distinguish HOCl from other reactive oxygen/nitrogen species (ROS/RNS). The ANMTTA-Ln(3+)-loaded HeLa and RAW 264.7 macrophage cells were prepared, and then the exogenous HOCl in HeLa cells and endogenous HOCl in macrophage cells were successfully imaged with time-gated luminescence mode. The results demonstrated the practical applicability of the probes for the cell imaging application.
authors.affiliation: State Key Laboratory of Fine Chemicals, School of Chemistry, Dalian University of Technology, Dalian 116024, China.
authors.forename: Yunna
authors.initials: Y
authors.lastname: Xiao
authors.forename: Run
authors.initials: R
authors.lastname: Zhang
authors.forename: Zhiqiang
authors.initials: Z
authors.lastname: Ye
authors.forename: Zhichao
authors.initials: Z
authors.lastname: Dai
authors.forename: Huaying
authors.initials: H
authors.lastname: An
authors.forename: Jingli
authors.initials: J
authors.lastname: Yuan
mesh_terms: D000818:Animals; D006367:HeLa Cells; D006801:Humans; D006997:Hypochlorous Acid / Q000032:analysis / Q000737:chemistry*; D028581:Lanthanoid Series Elements / Q000737:chemistry*; D049408:Luminescent Agents / Q000032:analysis / Q000737:chemistry*; D008163:Luminescent Measurements / Q000379:methods*; D051379:Mice; D013997:Time Factors
chemical_list: D028581:Lanthanoid Series Elements; D049408:Luminescent Agents; D006997:Hypochlorous Acid