荧光
三吡啶
肉眼
儿茶酚
硼酸
选择性
化学
光诱导电子转移
猝灭(荧光)
光化学
加合物
组合化学
有机化学
电子转移
色谱法
催化作用
金属
检出限
物理
量子力学
作者
Iván J. Bazany‐Rodríguez,María K. Salomón-Flores,Alejandro O Viviano-Posadas,Marco A. García‐Eleno,Joaquín Barroso‐Flores,Diego Martínez‐Otero,Alejandro Dorazco‐González
出处
期刊:Dalton Transactions
[The Royal Society of Chemistry]
日期:2021-01-01
卷期号:50 (12): 4255-4269
被引量:9
摘要
Biological catecholamines such as l-DOPA and dopamine play vital physiological roles in the brain and are chemical indicators of human diseases. A new range of fluorescent Zn(ii)-terpyridine complexes are described and studied in-depth as chemosensors for catecholamine-based neurotransmitters and nucleosides in pure water. The new Zn-terpyridine-based chemosensors contain a cationic N-isoquinolinium nucleus as the optical indicator covalently linked to three different isomers of strongly acidified phenylboronic acids (ortho-, 2.Zn; meta-, 3.Zn and para-, 4.Zn, substituted derivatives) as catechol binding sites. The addition of l-DOPA, dopamine, epinephrine, l-tyrosine and nucleosides to Zn(ii)-boronic acid chemosensors at physiological pH quenches their blue emission with a pronounced selectivity and an unprecedented high affinity towards l-DOPA (log K = 6.01). This efficient response by l-DOPA was also observed in the presence of coexisting species in blood plasma and urine with a detection limit of 3.0 μmol L-1. A photoinduced electron transfer quenching mechanism with simultaneous chemosensor-l-DOPA complexation in both the excited and ground states is proposed. The fluorescence experimental observations show that the 2.Zn·eosin-Y adduct can be used as a selective naked-eye chemosensing ensemble for l-DOPA with a fast turn-on fluorescent response and color change from blue to green under UV light at the micromolar level. On the basis of multiple spectroscopic techniques (1H, 11B NMR, UV-Vis, and fluorescence), MS-ESI experiments, crystal structures, and DFT calculations, the binding mode between Zn(ii)-chemosensors and l-DOPA is proposed in a 1 : 1 model through a cooperative two-point recognition involving the reversible esterification of the boronic acid moiety with the aromatic diol fragment of l-DOPA together with the coordination of the carboxylate anion to the Zn(ii) atom with strong electrostatic contribution.
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