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Fluorescence Sensing of Ionic Analytes in Water: From Transition Metal Ions to Vitamin B13

机译:水中离子分析物的荧光传感:从过渡金属离子到维生素B13

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摘要

The fluorescence chemosensor ATMCA has been realized by appending an anthrylmethyl group to an amino nitrogen of TMCA (2,4,6-triamino-1,3,5-trimethoxycyclohexane), a tripodal ligand selective for divalent first-row transition metal ions in water. The ATMCA ligand can act as a versatile sensor for Zn~(II) and Cu~(II) ions. Its sensing ability can be switched by simply tuning the operating conditions. At pH 5, ATMCA detects copper(II) ions in aqueous solutions by the complexation-in-duced quenching of the anthracene emission. Metal ion concentratins < 1 #mu#M can be readily detected and very little interference is exerted by other metal ions. At pH 7, ATMCA signals the presence of Zn~(II) ions at concentrations < 1 #mu#M by a complexation-induced enhancement of the fluorescence. Again the sensor is selective for Zn~(II) over several divalent metal ions, with the exception of Cu~(II), Co~(II) and Hg~(II). Most interestingly, the [Zn~(II)(atmca)]~(2+) complex can act as a fluorescence sensor for specific organic species, notably selected dicarboxylic acids and nucleotides, by the formation of ternary ligand/zinc/substrate complexes. The oxalate anion is detected in concentratins < 0.1 mM; however, no effects of the system's fluorescence is observed in the presence of monocarboxylic acids and long-chain dicarboxylic acids. Among the nucleotides, those containing an imide or amide function are readily detected and an unprecedented high sensitivity for guanine derivatives allows the determination of this nucleotide for 0.05-0.5 mM solutions. Moreover, [Zn~(II)(atmca)]~(2+) is a very effective and selective sensor in the case of vitamin B13 (orotic acid) in sub-micromolar concentrations. The operative features of the systems investigated are also clearly suitable for intracellular analyses. The factors at the source of organic substrate recognition, here briefly discussed, are of paramount importance for further developments in the applicability of these sensing systems.
机译:荧光化学传感器ATMCA是通过将蒽甲基附加到TMCA(2,4,6-三氨基-1,3,5-三甲氧基环己烷)的氨基氮上实现的,TMCA是对水中二价第一行过渡金属离子具有选择性的三脚架配体。 ATMCA配体可作为Zn〜(II)和Cu〜(II)离子的多功能传感器。只需调整操作条件即可切换其感应能力。在pH 5时,ATMCA通过络合诱导的蒽释放猝灭来检测水溶液中的铜(II)离子。 <1#mu#M的金属离子浓度很容易被检测到,其他金属离子几乎没有干扰。在pH值为7时,ATMCA通过络合诱导的荧光增强,发出浓度<1#mu#M的Zn〜(II)离子信号。同样,传感器对几种二价金属离子中的Zn(II)具有选择性,Cu(II),Co(II)和Hg(II)除外。最有趣的是,[Zn〜(II)(atmca)]〜(2+)配合物可通过形成三元配体/锌/底物配合物而充当特定有机物质(尤其是选定的二羧酸和核苷酸)的荧光传感器。草酸阴离子的浓度<0.1 mM。然而,在单羧酸和长链二羧酸的存在下,没有观察到系统荧光的影响。在这些核苷酸中,含有酰亚胺或酰胺功能的核苷酸很容易被检测到,而且对于鸟嘌呤衍生物空前的高灵敏度使得该核苷酸在0.05-0.5 mM溶液中的测定成为可能。此外,对于亚微摩尔浓度的维生素B13(乳清酸),[Zn〜(II)(atmca)]〜(2+)是非常有效和选择性的传感器。所研究系统的操作特征也显然适用于细胞内分析。在此简要讨论的有机底物识别源头的因素对于这些传感系统的适用性的进一步发展至关重要。

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