Fluorescein Tri-Aldehyde Promotes the Selective Detection of Homocysteine
Fluorescein Tri-Aldehyde Promotes the Selective Detection of Homocysteine
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DOI：
10.1007/s10895-015-1762-3
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发表时间：
2016-03-01
影响因子：
2.7
通讯作者：
Strongin, Robert M.
中科院分区：
文献类型：
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作者：
Barve, Aabha;Lowry, Mark;Strongin, Robert M.
同型半胱氨酸水平升高是众所周知的心血管疾病的独立危险因素。迄今为止，用于同型半胱氨酸检测的选择性荧光探针的报道相对较少。传感试剂的缺乏和剩余的挑战很大程度上源于灵敏度和/或选择性问题。例如，同型半胱氨酸是更丰富（约20-25倍）的氨基硫醇半胱氨酸的结构同系物，区别仅在于额外的亚甲基侧链。本文所述的荧光素三醛被设计和合成为灵敏且选择性的荧光团，用于检测人血浆样品中的同型半胱氨酸。它通过光诱导电子转移 (PET) 抑制过程选择性地响应分析物，该过程由可预测的分析物-染料产物杂交和电离状态调节。荧光素三醛及其反应产物的 Mulliken 群体分析表明，同型半胱氨酸衍生的杂环的多个阳离子的特征形成导致荧光团的近端酚氧上相对负电荷的增加，这是选择性发射增强的一个促成因素。
Elevated homocysteine levels are a well-known independent risk factor for cardiovascular disease. To date, relatively few selective fluorescent probes for homocysteine detection have been reported. The lack of sensing reagents and remaining challenges largely derive from issues of sensitivity and/or selectivity. For example, homocysteine is a structural homologue of the more abundant (ca, 20-25 fold) aminothiol cysteine, differing only by an additional methylene group side chain. Fluorescein tri-aldehyde, described herein, has been designed and synthesized as a sensitive and selective fluorophore for the detection of homocysteine in human plasma samples. It responds to analytes selectively via a photoinduced electron transfer (PET) inhibition process that is modulated by predictable analyte-dye product hybridization and ionization states. Mulliken population analysis of fluorescein tri-aldehyde and its reaction products reveals that the characteristic formation of multiple cationic of homocysteine-derived heterocycles leads to enhanced relative negative charge build up on the proximal phenolate oxygen of the fluorophore as a contributing factor to selective emission enhancement.