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基于铱(III)配合物的 HS 电化学发光探针。

Iridium(iii) complex-based electrochemiluminescent probe for HS.

机构信息

Department of Chemistry, Seoul National University, 1 Gwanak-ro, Gwanak-gu, Seoul 08826, Korea.

出版信息

Dalton Trans. 2019 Apr 2;48(14):4565-4573. doi: 10.1039/c8dt04901g.

Abstract

Since abnormal levels of hydrogen sulphide (H2S) correlate with various diseases, simple methods for its rapid and sensitive detection are highly required. Herein, we introduce a new electrochemiluminescent probe 1 for H2S based on a cyclometalated iridium(iii) complex. o-(Azidomethyl)benzoate ester groups on the main ligands of probe 1 react selectively with H2S, resulting in cascade reactions involving H2S-mediated reduction and intramolecular cyclization/ester cleavage. With this structural change induced by H2S, the intrinsic electrochemiluminescence (ECL) of 1 decreased greatly due to the unfavourable electron transfer of a tripropylamine (TPA) radical. Probe 1 showed a high ECL turn-off ratio and good selectivity for H2S over various anions and biothiols. The sensing mechanism of H2S was elucidated using 1H NMR spectroscopy and MALDI-TOF mass spectrometry analyses.

摘要

由于硫化氢 (H2S) 的异常水平与各种疾病相关,因此非常需要快速、灵敏检测 H2S 的简单方法。在此,我们基于金属铱配合物介绍了一种用于 H2S 的新型电化学发光探针 1。探针 1 的主配体上的邻-(叠氮甲基)苯甲酸酯基团可与 H2S 选择性反应,导致涉及 H2S 介导的还原和分子内环化/酯裂解的级联反应。由于 H2S 引起的这种结构变化,1 的固有电化学发光(ECL)由于三丙胺(TPA)自由基的不利电子转移而大大降低。探针 1 对 H2S 表现出高 ECL 关断比和良好的选择性,可用于检测各种阴离子和生物硫醇。使用 1H NMR 光谱和 MALDI-TOF 质谱分析阐明了 H2S 的传感机制。

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