Bell-Vlasov Andrea K, Zajda Joanna, Eldourghamy Ayman, Malinowska Elzbieta, Meyerhoff Mark E
Department of Chemistry, University of Michigan , 930 N. University, Ann Arbor, MI 48109-1055, United States.
Anal Chem. 2014 Apr 15;86(8):4041-6. doi: 10.1021/ac500567g. Epub 2014 Apr 1.
A method for the detection of polyions using fully reversible polyion selective polymeric membrane type pulstrodes as detectors in a flow-injection analysis (FIA) system is examined. The detection electrode consists of a plasticized polymeric membrane doped with 10 wt % of tridodecylmethylammonium-dinonylnaphthalene sulfonate (TDMA/DNNS) ion-exchanger salt. The pulse sequence used involves a short (1 s) galvanostatic pulse, an open-circuit pulse (0.5 s) during which the EMF of the cell is measured, and a longer (15 s) potentiostatic pulse to return the membrane to its original chemical composition. It is shown that total pulse sequence times can be optimized to yield reproducible real-time detection of injected samples of protamine and heparin at up to 20 samples/h. Further, it is shown that the same membrane detector can be employed for FIA detection of both polycations at levels ≥10 μg/mL and polyanions at levels of ≥40 μg/mL by changing the direction of the galvanostatic pulse. The methodology described may also be applicable in the detection of polyionic species at low levels in other flowing configurations, such as in liquid chromatography and capillary electrophoresis.
研究了一种在流动注射分析(FIA)系统中使用完全可逆的聚离子选择性聚合物膜型脉冲电极作为检测器来检测聚离子的方法。检测电极由掺杂有10 wt%三月桂基甲基铵-二壬基萘磺酸盐(TDMA/DNNS)离子交换盐的增塑聚合物膜组成。所使用的脉冲序列包括一个短的(1 s)恒电流脉冲、一个在此期间测量电池电动势的开路脉冲(0.5 s)以及一个较长的(15 s)恒电位脉冲,以使膜恢复到其原始化学成分。结果表明,总脉冲序列时间可以优化,以实现对注射的鱼精蛋白和肝素样品进行可重复的实时检测,检测速度高达每小时20个样品。此外,结果表明,通过改变恒电流脉冲的方向,同一膜检测器可用于FIA检测浓度≥10 μg/mL的聚阳离子和浓度≥40 μg/mL的聚阴离子。所述方法也可能适用于在其他流动配置中低水平检测聚离子物种,如在液相色谱和毛细管电泳中。