Ratiometric Time-Gated Luminescence Probe for Nitric Oxide Based on an Apoferritin-Assembled Lanthanide Complex-Rhodamine Luminescence Resonance Energy Transfer System

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• 作者：Lu Tian ; Zhichao Dai ; Xiangli Liu ; Bo Song ; Zhiqiang Ye ; Jingli Yuan
• 刊名：Analytical Chemistry
• 出版年：2015
• 出版时间：November 3, 2015
• 年：2015
• 卷：87
• 期：21
• 页码：10878-10885
• 全文大小：495K
• ISSN：1520-6882

文摘

Using apoferritin (AFt) as a carrier, a novel ratiometric luminescence probe based on luminescence resonance energy transfer (LRET) between a Tb³⁺ complex (PTTA-Tb³⁺) and a rhodamine derivative (Rh-NO), PTTA-Tb³⁺@AFt-Rh-NO, has been designed and prepared for the specific recognition and time-gated luminescence detection of nitric oxide (NO) in living samples. In this LRET probe, PTTA-Tb³⁺ encapsulated in the core of AFt is the energy donor, and Rh-NO, a NO-responsive rhodamine derivative, bound on the surface of AFt is the energy acceptor. The probe only emits strong Tb³⁺ luminescence because the emission of rhodamine is switched off in the absence of NO. Upon reaction with NO, accompanied by the turn-on of rhodamine emission, the LRET from Tb³⁺ complex to rhodamine occurs, which results in the remarkable increase and decrease of the long-lived emissions of rhodamine and PTTA-Tb³⁺, respectively. After the reaction, the intensity ratio of rhodamine emission to Tb³⁺ emission, I₅₆₅/I₅₃₉, is 鈭?4.5-fold increased, and the dose-dependent enhancement of I₅₆₅/I₅₃₉ shows a good linearity in a wide concentration range of NO. This unique luminescence response allowed PTTA-Tb³⁺@AFt-Rh-NO to be conveniently used as a ratiometric probe for the time-gated luminescence detection of NO with I₅₆₅/I₅₃₉ as a signal. Taking advantages of high specificity and sensitivity of the probe as well as its good water-solubility, biocompatibility, and cell membrane permeability, PTTA-Tb³⁺@AFt-Rh-NO was successfully used for the luminescent imaging of NO in living cells and Daphnia magna. The results demonstrated the efficacy of the probe and highlighted it鈥檚 advantages for the ratiometric time-gated luminescence bioimaging application.