Novel Reversible Zn2+-Assisted Biological Phosphate 鈥淭urn-On鈥?Probing through Stable Aryl-hydrazone Salicylaldimine Conjugation That Attenuates Ligand Hydrolysis

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• 作者：Olga G. Tsay ; Sudesh T. Manjare ; Hyungjun Kim ; Kang Mun Lee ; Yoon Sup Lee ; David G. Churchill
• 刊名：Inorganic Chemistry
• 出版年：2013
• 出版时间：September 3, 2013
• 年：2013
• 卷：52
• 期：17
• 页码：10052-10061
• 全文大小：600K
• 年卷期：v.52,no.17(September 3, 2013)
• ISSN：1520-510X

文摘

A novel reversible zinc(II) chemosensing ensemble (2路Zn²⁺) allows for selective 鈥渢urn-on鈥?fluorescence sensing of ATP and PPi in aqueous media (detection limits: 2.4 and 1.0 渭M, respectively) giving selective binding patterns: ATP PPi > ADP AMP > monophosphates 鈮?remaining ions tested. The conjugated hydrazone [C鈺怤鈥?i>NH鈥擱] resists hydrolysis considerably, compared to the imine [C鈺怤鈥?i>CH₂鈥擱, pyridin-2-ylmethanamine] functionality, and generalizes to other chemosensing efforts. Prerequisite Zn²⁺路[O_phenolN_imineN_pyr] binding is selective, as determined by UV鈥搗is and NMR spectroscopy; ATP or PPi extracts Zn²⁺ to regenerate the ligand鈥揻luorophore conjugate (PPi: turn-on, 512 nm; detection limit, 1.0 渭M). Crystallography, 2-D NMR spectroscopy, and DFT determinations (B3LYP/631g*) support the nature of compound 2. 2-Hydrazinyl-pyridine-salicylaldehyde conjugation is unknown, as such; a paucity of chemosensing-Zn²⁺ binding reports underscores the novelty of this modifiable dual cation/anion detection platform. A combined theoretical and experimental approach reported here allows us to determine both the potential uniqueness as well as drawbacks of this novel conjugation.