钯(Ⅱ)-盐酸吗啉胍螯合物与卤代荧光素类染料相互作用的共振瑞利散射光谱及其分析应用

Resonance Rayleigh Scattering Spectra and Analytical Applications of Palladium(Ⅱ)-Moroxydine Hydrochloride-Halide Fluorescein Dyes

在pH值为4.2～4.4的HAc-NaAc介质中,盐酸吗啉胍(ABOB)与Pd(Ⅱ)反应形成螯合阳离子[Pd(ABOB)2]2+,它能进一步与曙红Y(EY)、赤藓红(Ery)和二溴荧光素(DBF)阴离子形成离子缔合物,此时将引起共振瑞利散射(RRS)的急剧增强并产生新的RRS光谱。盐酸吗啉胍与Pd(Ⅱ)和3种染料反应后的产物具有相似的光谱特征,最大RRS波长位于315nm附近。在一定条件下散射增强(ΔI)与ABOB浓度成正比,EY、Ery和DBF这3个体系的线性范围分别为0.012×10-6～1.2×10-6g/mL、0.23×10-6～2.3×10-6g/mL和0.24×10-6～1.5×10-6g/mL。方法具有较高的灵敏度,对于ABOB的检出限依次为0.0036×10-6、0.070×10-6和0.025×10-6g/mL,其中以EY体系灵敏度最高,其次是DBF和Ery。研究了适宜的反应条件和影响因素,表明本方法具有良好的选择性,并以EY体系为例考察了共存物质的影响。据此建立以曙红Y作探针,用RRS技术快速、简便,高灵敏测定ABOB的新方法。文中还对离子缔合物的形成和反应机理进行了讨论。

In a pH 4.2 ～ 4.4 acidic medium, palladium（ Ⅱ ） reacted with moroxydine hydrochloride to form a cationic chelate [ Pd （ ABOB ） 2 ] 2 ＋ , which reacted further with eosin Y （ EY ） , erythrosin （ Ery ） or dibromofluorescein （DBF） to form ion-association complexes, respectively. As a result, the resonance rayleigh scattering（RRS） intensities were enhanced greatly. The maximum RRS peak of three systems were located at 315 nm, RIRS intensity was proportional to the concentration of moroxydine hydrochloride （ABOB） in a range of 0. 012 ×10-6 -1. 2 ×10 -r g/mL （EY）,0.23×10-6～2.3×10-6 g,/mL （Ery） or0.24×10-6～l.5× 10-6g/mL （DBF）, and the detection limit（3o＇） was 0. 003 6 × 10-6 g/mL （EY）, 0. 070 ×10-6 g/mL （Ery） or 0. 025 ×10 -6 g/mL （ DBF）, separately. The optimal conditions of the reaction and the properties of analytical chemistry were investigated. Therefore, a new method for the determination of ABOB by FIRS was developed. The method has a high sensitivity and good selectivity, which has been applied to the determination of ABOB in serum and urine samples with satisfactory results. In addtion, the formation of the ion-associaiation complexes, the reaction mechanism and the reasons of scattering enhanced has been discussed.