Sensitive Determination of Barbiturates in Biological Matrix by Capillary Electrophoresis Using Online Large-Volume Sample Stacking

: In China, some forensic cases are caused by barbiturates. Thus, the determination of trace level barbiturates in body fluid is important for the poisoning investigation. In this study, an online large‐volume sample stacking (LVSS) with polarity switching in capillary electrophoresis (CE) was applied for the sensitive determination of barbiturates. This technique involves injecting a large volume of sample into a capillary and removing the sample matrix plug out of the capillary by reversing the polarity. Quantitation limit obtained was 0.048, 0.057, 0.039, and 0.015 μg/mL for secobarbital, amobarbital, barbital, and phenobarbital (signal‐to‐noise ratio = 9). By using LVSS, the stacking was simply achieved at 171.7‐, 169.7‐, 202.7‐, and 169.1‐fold for the above four barbiturates. The relative standard deviation values of intraday and interday were