Popiel Stanisław, Nawała Jakub, Dziedzic Daniel, Söderström Martin, Vanninen Paula
Military University of Technology , Institute of Chemistry, 2 Kaliskiego Street, 00-908 Warsaw, Poland.
Anal Chem. 2014 Jun 17;86(12):5865-72. doi: 10.1021/ac500656g. Epub 2014 Jun 6.
A method for detecting mustard gas degradation products thiodiglycol (TDG) and thiodiglycol sulfoxide (TDGO) in water and sediment samples using gas chromatography-tandem mass spectrometry (GC-MS/MS) after derivatization with 1-(trifluoroacetyl)imidazole (TFAI) was described. Selected reaction monitoring mode (SRM) of tandem mass spectrometry was developed for analysis of TDG and TDGO derivatives while analysis by gas chromatography-atomic emission detector (GC-AED) was performed using the 181 nm sulfur canal. TFAI derivatization conditions were optimized and the method validated. Two derivatization agents were compared, TFAI and N,O-bis(trimethylsilyl) trifluoroacetamide (BSTFA), where derivatization using TFAI occurred quicker and under milder conditions than using BSTFA. Water samples containing TDG and TDGO were evaporated to dryness under nitrogen, dissolved in organic solvent followed by reaction with TFAI. The limit of detection (LOD) for TDG and TDGO were 0.01 and 5 ng/mL, respectively. The limit of detection for TDG was decreased by two orders of magnitude if TFAI is used for derivatization rather than silyl derivatizing agents (e.g., BSTFA). TFAI has three major advantages in comparison to BSTFA, the first is much higher sensitvity, the second is a very clean background of chromatograms, and the last one is very mild conditions of derivatization. Moreover, by-products are not formed during derivatization of TDGO by TFAI in comparison to derivatization by silylating agents.
描述了一种使用气相色谱 - 串联质谱法（GC - MS/MS）在经过1 - （三氟乙酰基）咪唑（TFAI）衍生化后检测水和沉积物样品中芥子气降解产物硫二甘醇（TDG）和硫二甘醇亚砜（TDGO）的方法。开发了串联质谱的选择反应监测模式（SRM）用于分析TDG和TDGO衍生物，同时使用181nm硫通道通过气相色谱 - 原子发射检测器（GC - AED）进行分析。对TFAI衍生化条件进行了优化并验证了该方法。比较了两种衍生化试剂，TFAI和N，O - 双（三甲基硅基）三氟乙酰胺（BSTFA），其中使用TFAI衍生化比使用BSTFA更快且条件更温和。含有TDG和TDGO的水样在氮气下蒸发至干，溶解于有机溶剂中，然后与TFAI反应。TDG和TDGO的检测限分别为0.01和5 ng/mL。如果使用TFAI而不是硅烷基衍生化试剂（例如BSTFA）进行衍生化，TDG的检测限降低了两个数量级。与BSTFA相比，TFAI有三个主要优点，第一个是灵敏度高得多，第二个是色谱图背景非常干净，最后一个是衍生化条件非常温和。此外，与硅烷化试剂衍生化相比，TFAI衍生化TDGO时不会形成副产物。
