Ratiometric Time-Gated Luminescence Probe for Hydrogen Sulfide Based on Lanthanide Complexes

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• 作者：Zhichao Dai ; Lu Tian ; Bo Song ; Zhiqiang Ye ; Xiangli Liu ; Jingli Yuan
• 刊名：Analytical Chemistry
• 出版年：2014
• 出版时间：December 2, 2014
• 年：2014
• 卷：86
• 期：23
• 页码：11883-11889
• 全文大小：359K
• ISSN：1520-6882

文摘

Developments of ratiometric bioprobes are highly appealing due to the superiority of their self-calibration capability for the quantitative biotracking. In this work, we designed and synthesized a novel lanthanide complex-based ratiometric luminescence probe, [4鈥?(2,4-dinitrophenyloxy)-2,2鈥?6鈥?2鈥?terpyridine-6,6鈥?diyl]bis(methylenenitrilo) tetrakis(acetate)-Eu³⁺/Tb³⁺ (NPTTA-Eu³⁺/Tb³⁺), for the specific recognition and quantitative time-gated luminescence detection of hydrogen sulfide (H₂S) in aqueous and living cell samples. Due to the presence of the photoinduced electron transfer (PET) process from the terpyridine-Eu³⁺/Tb³⁺ moiety to 2,4-dinitrophenyl (DNP), the probe itself is weakly luminescent. In physiological pH aqueous media, the reaction of NPTTA-Eu³⁺/Tb³⁺ with H₂S leads to the cleavage of DNP moiety from the probe molecule, which affords the deprotonated (4鈥?hydroxy-2,2鈥?6鈥?2鈥?terpyridine-6,6鈥?diyl)bis(methylenenitrilo) tetrakis(acetate)-Eu³⁺/Tb³⁺ and terminates the PET process. Meanwhile, the intensity of Tb³⁺ emission at 540 nm is remarkably increased, while that of the Eu³⁺ emission at 610 nm is slightly decreased. After the reaction, the intensity ratio of Tb³⁺ emission to Eu³⁺ emission, I₅₄₀/I₆₁₀, was 鈭?20-fold increased, and the dose-dependent enhancement of I₅₄₀/I₆₁₀ showed a good linearity upon the increase of H₂S concentration with a detection limit of 3.5 nM. This unique luminescence response allowed NPTTA-Eu³⁺/Tb³⁺ to be conveniently used as a ratiometric probe for the time-gated luminescence detection of H₂S with I₅₄₀/I₆₁₀ as a signal. In addition, the applicability of the probe for the quantitative time-gated luminescence imaging of intracellular H₂S in living cells was investigated. The results demonstrated the efficacy and advantage of the new probe for the time-gated luminescence cell imaging application.