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用于在水缓冲液和细胞中检测焦磷酸和硫化氢的吡啶-双喹啉-金属配合物。

Pyridine-biquinoline-metal complexes for sensing pyrophosphate and hydrogen sulfide in aqueous buffer and in cells.

机构信息

CAS Key Laboratory of Soft Matter Chemistry, Department of Chemistry, University of Science and Technology of China , Hefei, Anhui 230026, China.

出版信息

Anal Chem. 2015 Mar 3;87(5):2678-84. doi: 10.1021/ac504536q. Epub 2015 Feb 23.

DOI:10.1021/ac504536q
PMID:25673091
Abstract

Herein, we report a new pyridine-biquinoline-derivative fluorophore L for effectively sensing pyrophosphate (PPi) and monohydrogen sulfide (HS(-)) in aqueous buffer and in living cells. L could selectively coordinate with metal ions (M(n+)) in Groups IB and IIB to form L-M(n+) complexes with 1:1 stoichiometry, resulting in fluorescence quenching via photoinduced electron transfer (PET) mechanism. L-Zn(2+) complex was applied to competitively coordinate with PPi to form a new "ate"-type complex, turning on the fluorescence by a 21-fold-increase. The limit of detection (LOD) of this assay for PPi detection in aqueous buffer is 0.85 μM. L-Cu(2+) complex was applied for highly selective detection of HS(-) with an excellent sensitivity by 25-fold decomplexation-induced fluorescence increase. LOD of L-Cu(2+) complex for HS(-) detection in aqueous buffer is 2.24 μM. With the in vitro data obtained, we successfully applied these two complexes for sequential imaging Zn(2+) and PPi, Cu(2+) and HS(-) in living cells, respectively. Since PPi and HS(-) occur in vascular calcification in positive correlation, our multifunctional probe L might help doctors to more precisely diagnose this disease in vivo in the future. For example, we could use radioactive tracer L-(64)Cu for qualitative and quantitative positron emission tomography/computed tomography (PET/CT) imaging of HS(-) in vivo.

摘要

在此,我们报告了一种新的吡啶-双喹啉衍生荧光团 L,可有效感应焦磷酸盐 (PPi) 和一价氢硫化物 (HS(-)) 在水缓冲液和活细胞中。L 可以选择性地与 IB 族和 IIB 族的金属离子 (M(n+)) 配位,形成 1:1 化学计量比的 L-M(n+) 配合物,通过光诱导电子转移 (PET) 机制导致荧光猝灭。L-Zn(2+) 配合物被应用于与 PPi 竞争配位,形成新的“内盐”型配合物,通过 21 倍的荧光增强来开启荧光。该测定法在水缓冲液中检测 PPi 的检测限 (LOD) 为 0.85 μM。L-Cu(2+) 配合物通过 25 倍的解络合诱导荧光增强,对 HS(-) 具有优异的选择性和高灵敏度检测。L-Cu(2+) 配合物在水缓冲液中检测 HS(-)的 LOD 为 2.24 μM。根据体外数据,我们成功地将这两种配合物分别用于活细胞中 Zn(2+) 和 PPi、Cu(2+) 和 HS(-) 的顺序成像。由于 PPi 和 HS(-) 在血管钙化中呈正相关,我们的多功能探针 L 将来可能有助于医生更精确地在体内诊断这种疾病。例如,我们可以使用放射性示踪剂 L-(64)Cu 对 HS(-)进行定性和定量的正电子发射断层扫描/计算机断层扫描 (PET/CT) 成像。

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