Berni Emanuela, Gosse Isabelle, Badocco Denis, Pastore Paolo, Sojic Neso, Pinet Sandra
Université Bordeaux , ENSCPB, Groupe Nanosystèmes Analytiques, Institut des Sciences Moléculaires, UMR 5255 CNRS, 16 avenue Pey-Berland, 33607 Pessac, France.
Chemistry. 2009;15(20):5145-52. doi: 10.1002/chem.200802544.
A new guanidinium 3,3'-functionalized bipyridylruthenium(II) complex has been prepared for the differential sensing of L-glutamate and dihydrogenphosphate anions depending on the luminescent detection scheme. The effects of such anions on the photoluminescent (PL) and electrochemiluminescent (ECL) properties of the complex have been investigated and compared. The PL intensity increases up to fourfold in the presence of L-glutamate. The increase of intensity in the presence of dihydrogenphosphate is weaker and no change in PL intensity is observed in presence of acetate, iodide, or chloride anions. With n-tripropylamine, ECL emission of the Ru(II) complex is initiated at 1.45 V versus Ag/AgCl/KCl and the ECL intensity increases only in the presence of dihydrogenphosphate. Indeed, L-glutamate is already oxidized at the relatively high potential required for ECL generation and thus it does not affect the ECL signal. The comparison of the competitive ECL and PL assays in a mixture of anions confirms the differential detection of L-glutamate and of dihydrogenphosphate. Thus, both sensing channels (i.e., PL and ECL) show different selectivities depending on the nature and on the electroactivity of the target anions. Multianion analysis is demonstrated in competitive assays using complementary detection methods.
一种新型胍盐3,3'-官能化联吡啶钌（II）配合物已被制备出来，用于根据发光检测方案对L-谷氨酸和磷酸二氢根阴离子进行差异传感。研究并比较了这些阴离子对该配合物的光致发光（PL）和电化学发光（ECL）性质的影响。在L-谷氨酸存在下，PL强度增加了四倍。在磷酸二氢根存在下强度的增加较弱，而在乙酸根、碘离子或氯离子存在下未观察到PL强度的变化。使用三丙胺时，Ru（II）配合物的ECL发射在相对于Ag/AgCl/KCl为1.45 V时开始，并且ECL强度仅在磷酸二氢根存在下增加。实际上，L-谷氨酸在产生ECL所需的相对较高电位下已经被氧化，因此它不影响ECL信号。在阴离子混合物中对竞争性ECL和PL分析的比较证实了对L-谷氨酸和磷酸二氢根的差异检测。因此，两个传感通道（即PL和ECL）根据目标阴离子的性质和电活性表现出不同的选择性。使用互补检测方法的竞争性分析证明了多阴离子分析。
