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过氧一碳酸酯的在线制备及其在能量转移化学发光用于镧系无机配位配合物研究中的应用。

On-line preparation of peroxymonocarbonate and its application for the study of energy transfer chemiluminescence to lanthanide inorganic coordinate complexes.

作者信息

Liu Meilin, Cheng Xianglei, Zhao Lixia, Lin Jin-Ming

机构信息

State Key Laboratory of Environmental Chemistry and Ecotoxicology, Research Centre for Eco-Environmental Sciences, Chinese Academy of Sciences, PO Box 2871, 100085 Beijing, China.

出版信息

Luminescence. 2006 May-Jun;21(3):179-85. doi: 10.1002/bio.903.

DOI:10.1002/bio.903
PMID:16645954
Abstract

It has been shown that peroxymonocarbonate ion (HCO(4) (-)) is a potent oxidant. In this study, a flow-injection system was developed in order to prepare on-line HCO(4) (-) ion and the optimum conditions for the on-line preparation of HCO(4) (-) were studied in detail. We used 99% (13)C-enriched NaHCO(3) to examine peroxymonocarbonate by (13)C-NMR at 25 degrees C. An ultra-weak chemiluminescence (CL) was observed after mixing H(2)O(2) and sodium bicarbonate in an organic co-solvent that can accelerate the formation of HCO(4) (-) ion. When lanthanide inorganic coordinate complex, Eu(II)-EDTA, was added into this HCO(4) (-) system, the CL intensity was significantly enhanced. The CL mechanism was investigated by various methods. The experimental results indicate that peroxymonocarbonate oxidizes Eu(II) to Eu(III) and produces singlet oxygen; meanwhile, the energy originating from dimers of singlet oxygen is accepted by the Eu(III)-EDTA(-) complex. The excited Eu(III) ions undergo radiative deactivation and emit CL.

摘要

已表明过一碳酸根离子(HCO(4) (-))是一种强氧化剂。在本研究中,开发了一种流动注射系统以在线制备HCO(4) (-)离子,并详细研究了在线制备HCO(4) (-)的最佳条件。我们使用99%富集(13)C的NaHCO(3)在25℃下通过(13)C-NMR检测过一碳酸根。在能加速HCO(4) (-)离子形成的有机共溶剂中将H(2)O(2)和碳酸氢钠混合后,观察到了超微弱化学发光(CL)。当将镧系元素无机配位络合物Eu(II)-EDTA添加到该HCO(4) (-)体系中时,CL强度显著增强。通过各种方法研究了CL机理。实验结果表明,过一碳酸根将Eu(II)氧化为Eu(III)并产生单线态氧;同时,源于单线态氧二聚体的能量被Eu(III)-EDTA(-)络合物接受。激发态的Eu(III)离子发生辐射失活并发出CL。

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