配位环境和pH值在调节铕（II）氧化速率中的作用
The Role of Coordination Environment and pH in Tuning the Oxidation Rate of Europium(II).
作者信息
Ekanger Levi A, Basal Lina A, Allen Matthew J
机构信息
Department of Chemistry, Wayne State University, 5101 Cass Avenue, Detroit, MI, 48202, USA.
出版信息
Chemistry. 2017 Jan 23;23(5):1145-1150. doi: 10.1002/chem.201604842. Epub 2016 Dec 19.
Abstract
The Eu redox couple offers metal-based oxidation-sensing with magnetic resonance imaging making the study of Eu oxidation chemistry important in the design of new probes. Accordingly, we explored oxidation reactions with a set of Eu -containing complexes. Superoxide formation from the reaction between Eu and dioxygen was observed using electron paramagnetic resonance spectroscopy. Additionally, oxidation kinetics of three Eu -containing complexes with bromate and glutathione disulfide at pH values, including 5 and 7, is reported. In the reaction with bromate, the oxidation rate of two of the complexes increased by 7.3 and 6.7 times upon decreasing pH from 7 to 5, but the rate increased by 17 times for a complex containing amide functional groups over the same pH range. The oxidation rate of a fluorobenzo-functionalized cryptate was relatively slow, indicating that the ligand used to impart thermodynamic oxidative stability might also be useful for controlling oxidation kinetics.
摘要
铕氧化还原对可通过磁共振成像实现基于金属的氧化传感，这使得铕氧化化学的研究在新型探针设计中具有重要意义。因此，我们用一组含铕配合物探索了氧化反应。利用电子顺磁共振光谱观察到铕与氧气反应生成了超氧化物。此外，还报道了三种含铕配合物在pH值为5和7时与溴酸盐和谷胱甘肽二硫化物的氧化动力学。在与溴酸盐的反应中，当pH值从7降至5时，其中两种配合物的氧化速率分别提高了7.3倍和6.7倍，但在相同pH范围内，一种含酰胺官能团的配合物的速率提高了17倍。氟代苯官能化穴合物的氧化速率相对较慢，这表明用于赋予热力学氧化稳定性的配体可能也有助于控制氧化动力学。
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