Department of Chemistry, Taizhou University, 605 Dongfang Road, Linhai 317000, China.
Anal Chem. 2012 Jun 5;84(11):4915-20. doi: 10.1021/ac300512b. Epub 2012 May 10.
The development of highly sensitive and selective detection techniques for the discrimination of relevant toxic benzenethiols and biologically active aliphatic thiols is of considerable importance in the fields of chemical, biological, and environmental sciences. In this article, we describe a new design of reaction-based fluorescent probe for discrimination of thiophenols over aliphaticthiols through intramolecular charge transfer pathways using N-butyl-4-amino-1,8-naphthalimide as a fluorophore, the strongly electron-withdrawing 2,4-dinitrobenzenesulfonamide group as a recognition unit, and 2,3-dihydroimidazo-[1,2-a] pyridine moiety as a linker. This rational design not only affords finely tunable spectroscopic properties by adding 2,3-dihydroimidazo-[1,2-a] pyridine moiety but also provides the chance to regulate the selectivity and sensitivity of the probe due to the formation of a new type of potentially reversible sulfonamide bond through 4-dimethylaminopyridine-like resonance. The developed probe displayed high off/on signal ratios, good selectivity, and sensitivity with a detection limit of 20 nM and a relative standard deviation of 1.7% for 11 replicate detections of 0.33 μM thiophenol and was successfully applied to the determination of thiophenols in water samples with quantitative recovery (from 94% to 97%) demonstrating its application prospect for thiophenols sensing in environmental and biological sciences.
发展高灵敏度和选择性的检测技术，以区分相关的有毒苯硫酚和生物活性脂肪硫醇，在化学、生物和环境科学领域具有重要意义。本文描述了一种新的基于反应的荧光探针设计，该探针使用 N-丁基-4-氨基-1,8-萘二甲酰亚胺作为荧光团，强吸电子 2,4-二硝基苯磺酰胺基团作为识别单元，2,3-二氢咪唑并[1,2-a]吡啶部分作为连接体，通过分子内电荷转移途径来区分苯硫酚和脂肪硫醇。这种合理的设计不仅通过添加 2,3-二氢咪唑并[1,2-a]吡啶部分赋予了精细可调的光谱性质，而且由于通过 4-二甲氨基吡啶样共振形成了一种新型潜在可逆的磺酰胺键，还提供了调节探针选择性和灵敏度的机会。所开发的探针具有高的开/关信号比、良好的选择性和灵敏度，检测限为 20 nM，对 0.33 μM 苯硫酚的 11 次重复检测的相对标准偏差为 1.7%，并成功应用于水样中苯硫酚的定量测定，回收率为 94%至 97%，证明了其在环境和生物科学中用于苯硫酚传感的应用前景。
