Department of Chemistry, Lomonosov Moscow State University, Leninskie Gory, 1-3, GSP-1, Moscow, 119991, Russia.
Department of Chemistry, Lomonosov Moscow State University, Leninskie Gory, 1-3, GSP-1, Moscow, 119991, Russia; A.N. Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, Leninsky Prospect, 31, GSP-1, Moscow, 119071, Russia.
Chemosphere. 2021 Oct;280:130747. doi: 10.1016/j.chemosphere.2021.130747. Epub 2021 May 3.
In this work, simple, rapid and highly sensitive method of hazardous chemical 1,1-dimethylhydrazine (unsymmetrical dimethylhydrazine, UDMH) determination based on pre-column derivatization with unsubstituted aromatic aldehydes and reversed-phase high performance liquid chromatography-ultraviolet-tandem mass spectrometry (RP HPLC-UV-MS/MS) has been developed. Along with benzaldehyde, commercially available aromatic aldehydes, namely: 2-naphthaldehyde, 2-pyridinecarboxaldehyde, and 2-quinolinecarboxaldehyde, were used as derivatizing reagents in the analysis of hydrazines for the first time. The reactions were studied in a wide pH range by varying reaction time and other conditions. A slightly alkaline pH 9 was shown to be optimal for the derivatization of UDMH by aromatic aldehydes. The quantitative yield of derivatization products under the established conditions was confirmed by HPLC analysis with amperometric detection. For all studied reagents, wide linear ranges of concentrations (0.01-1000 μg/L) in natural water samples were observed. The limits of detection for UDMH in natural water were in the 3.7-130 ng/L range. 2-Quinolinecarboxaldehyde was selected as the most appropriate reagent for HPLC-UV-MS/MS determination of UDMH. In case of using this reagent, the accuracy was in the range of 97-102%, and precision, expressed as RSD was less than 8%. The developed approach does not require laborious stages of pre-concentration and isolation of UDMH from natural water components.
本工作建立了一种基于未取代芳香醛柱前衍生化-反相高效液相色谱-紫外-串联质谱（RP HPLC-UV-MS/MS）测定危险化学品 1,1-二甲基肼（偏二甲肼，UDMH）的简单、快速、高灵敏方法。首次以商业可得的芳香醛（苯甲醛）以及 2-萘醛、2-吡啶甲醛和 2-喹啉甲醛作为衍生化试剂，用于肼类化合物的分析。通过改变反应时间和其他条件，研究了这些反应在较宽的 pH 范围内的情况。结果表明，芳香醛衍生化 UDMH 的最佳 pH 值略呈碱性，为 9。在建立的条件下，通过安培检测的 HPLC 分析确认了衍生化产物的定量产率。对于所有研究的试剂，在天然水样中均观察到浓度（0.01-1000μg/L）的宽线性范围。在天然水中 UDMH 的检出限为 3.7-130ng/L。2-喹啉甲醛被选为用于 HPLC-UV-MS/MS 测定 UDMH 的最适宜试剂。使用该试剂时，准确度在 97-102%范围内，精密度（表示为 RSD）小于 8%。所建立的方法不需要从天然水成分中费力地进行 UDMH 的预浓缩和分离。
