Lin Jin-Ming, Liu Meilin
The Key Laboratory of Bioorganic Phosphorus Chemistry & Chemical Biology, Department of Chemistry, Tsinghua University, Beijing 100084, China.
Spectrochim Acta A Mol Biomol Spectrosc. 2009 Feb;72(1):126-32. doi: 10.1016/j.saa.2008.08.019. Epub 2008 Sep 30.
The decomposition of peroxymonocarbonate (HCO(4)(-)) has been investigated by flow-injection chemiluminescence (CL) method. An ultraweak CL was observed during mixing the bicarbonate and hydrogen peroxide solution in organic cosolvent. An appropriate amount of fluorescent organic compounds, such as dichlorofluorescein (DCF), was added to the HCO(4)(-) solution, a strong CL was recorded. Based on studies of the spectrum of fluorescence, CL and UV-vis spectra, electron spin trapping (ESR) technique, mass spectra (MS) and comparison with H(2)O(2)/hypochlorite (ClO(-)) and H(2)O(2)/molybdate (MoO(4)(-)) systems, the CL mechanism was proposed. The reaction is initiated by unimolecular homolysis of the peroxo O-O bond in HO-OCOO(-) molecule. It was suggested that the bond rearrangement within radicals yield superoxide ion (O(2)(-)). The interaction of superoxide ion with perhydroxyl radical produces singlet oxygen ((1)O(2)). The energy transfers from singlet oxygen to DCF forming an excited energy acceptor (DCF). Luminescence (lambda(max)=509 nm) was emitted during the relaxation of the energy acceptor to the ground state.
采用流动注射化学发光（CL）法研究了过氧一碳酸根（HCO(4)(-)）的分解。在有机助溶剂中将碳酸氢盐溶液与过氧化氢溶液混合时观察到了超微弱化学发光。向HCO(4)(-)溶液中加入适量的荧光有机化合物，如二氯荧光素（DCF），记录到了强烈的化学发光。基于对荧光光谱、化学发光光谱和紫外可见光谱的研究、电子自旋捕获（ESR）技术、质谱（MS）以及与H(2)O(2)/次氯酸盐（ClO(-)）和H(2)O(2)/钼酸盐（MoO(4)(-)）体系的比较，提出了化学发光机理。该反应由HO - OCOO(-)分子中过氧O - O键的单分子均裂引发。研究表明，自由基内的键重排产生超氧离子（O(2)(-)）。超氧离子与过羟基自由基的相互作用产生单线态氧（(1)O(2)）。单线态氧的能量转移至DCF形成激发态能量受体（DCF）。能量受体弛豫至基态时发出荧光（λ(max)=509 nm）。
