Studies on sensitive detection of carbohydrates based on the anodically initiated luminescence of hydroxy compounds

基于羟基化合物阳极发光的碳水化合物灵敏检测研究

• 批准号: 07804047
• 负责人: KARATANI Hajime
• 金额: $ 1.47万
• 依托单位: Kyoto Institute of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1995
• 资助国家: 日本
• 起止时间: 1995 至 1996
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-07804047/
• 关键词: Luminescence; electrooxidation; electrocatalytic oxidation; hydroxy compounds; carbohydrates; luminescence amplification; energy transfer; chromatography analysis; ヒドロキシル基; 電解発光; 電解酸化; アルコール; 電子励起状態; 増感蛍光; 発光スペクトル

We have studied on the mechanism of a novel luminescence initiated by the electrooxidation of hydroxy compounds in alkaline media. Further we have developed the sensitive detection method base on this luminescence.From the characterization of the luminescence elicited as the result of the simple methanol at a glassy carbon anode, it was suggested that formaldehyde in its electronically excited states is formed via the disproportionation of methoxyl radicals generated in the electrooxidation of methoxide ions in alkaline media. The characterization of anodically generated luminescence from various polyols and carbohydrates also suggested that the formation of the excited carbonyl fragments is crucial in the luminescent reaction. Furthermore, in the electrooxidation of hydroxy compounds in the presence of a strongly fluorescent dye, the luminescence was shown to be noticeably amplified via the electronic energy transfer.Unlike the glassy carbon, the anodic process of hydroxy compounds at … More various metal electrodes was found to be the dark process in terms of visible radiation. However, in the case of the Ni electrode, the Ni (III) durface anodically generated on the Ni electrode in alkaline media was demonstrated to be capable of causing the noticeable luminescence upon the electrocatalytic oxidation of hydroxy compounds in the presence of a fluorescent dye. The light emissive species was expected to be a complex formed between the fluorescer added and the excited products converted from the electrocatalytic oxidation of hydroxy compounds.From the analytical characterization of the luminescence mainly using a glassy carbon electrode, it was demonstrated that the linearity between luminescence intensity and substrate concentration exists in the wide concentration range of muM to mM.The luminescence was successfully applied to the detection of pmol level of hydroxy compounds (per injection) in the flowing solution. Furthermore, we newly developed the liquid chromatography system using this luminescence technique for the sensitive detection of various alcohols and carbohydrates. Less

我们研究了碱性介质中羟基化合物电氧化引发的新型发光的机理，并进一步开发了基于这种发光的灵敏检测方法。玻碳阳极，有人认为电子激发态的甲醛是通过碱性介质中甲醇盐离子电氧化产生的甲氧基自由基的歧化形成的。各种多元醇和碳水化合物阳极产生的发光的表征也强烈表明，激发的羰基片段的形成在发光反应中至关重要。此外，在荧光染料存在下的羟基化合物的电氧化中，发光被证明是有效的。通过电子能量转移显着放大。与玻璃碳不同，羟基化合物在各种金属电极上的阳极过程被发现是可见辐射的暗过程。通过对 Ni 电极的研究，在碱性介质中 Ni 电极上阳极生成的 Ni (III) 表面被证明能够在荧光染料存在下对羟基化合物进行电催化氧化时引起明显的发光。预期是添加的荧光剂与羟基化合物电催化氧化转化的激发产物之间形成的络合物。从主要使用玻碳电极的发光分析表征来看，证明发光强度与底物浓度之间在μM至mM的宽浓度范围内存在线性关系。该发光已成功应用于流动溶液中羟基化合物（每次注射）的pmol水平的检测。此外，我们新开发了液相色谱系统利用这种发光技术可灵敏地检测各种醇类和碳水化合物。

项目成果

Hajime Karatani: "Luminescent Electrooxidation of Methanol in Aqueous Alkaline Media" Electrochimica Acta. 41・10. 1667-1676 (1996)

Hajime Karatani：“碱性水溶液中甲醇的发光电氧化”《电化学学报》41・10（1996）。

H.Karatani: "Development and Characterization of Anodically Initiated Luminescence Detection for Alcohols and Carbohydrates." Analytica Chimca Acta. (in press.).

H.Karatani：“醇类和碳水化合物阳极引发发光检测的开发和表征”。

H.Karatani: "Luminescent Electrooxidation of Methanol in Aqueous Alkaline Media." Electrochimica Acta. Vol.41. 1667-1676 (1996)

H.Karatani：“碱性水溶液中甲醇的发光电氧化”。

柄谷肇: "Luminescent Electrooxidation of Methanol in Aquecus Alkaline Media" Electrochimca Acta. 41(印刷中). (1996)

Hajime Karatani：“水碱性介质中甲醇的发光电氧化”Electrochimca Acta 41（出版中）。