Hsu Ching-Lin, Cheng Chin-Yuan, Lee Chung-Te, Ding Wang-Hsien
Department of Chemistry, National Central University, Chung-Li 32054, Taiwan.
Talanta. 2007 Apr 15;72(1):199-205. doi: 10.1016/j.talanta.2006.10.018. Epub 2006 Nov 27.
This study evaluated the derivatization procedures for detecting the three most commonly monosaccharide anhydrides (MAs) (levoglucosan, mannosan and galactosan) in atmospheric aerosols using gas chromatography-mass spectrometry (GC-MS). Various silylating agents, mainly trimethylsilylating agents (TMS), were compared and the effects of various contents of trimethylchlorosilane (TMCS, as a stimulator) were evaluated to optimize the conditions for detecting these compounds in aerosol samples. Differences among the abundances of the derivatives were caused by the sterical hindrance of three hydroxyl groups in the structures of monosaccharide anhydrides. The effects of the reaction time and temperature were also examined. The optimal reaction time and temperature were 60min and 80 degrees C with 1% TMCS plus 0.2% 1,4-dithioerythritol (DTE). Under these conditions, the percentages of formation of bis-O-TMS derivatives (as by-products) were 23, 29 and 10% for galactosan, mannosan and levoglucosan, respectively. The concentrations of galactosan, mannosan and levoglucosan in particles of smoke samples ranged from 29 to 88, 23 to 69 and 77 to 380ng/m(3), respectively; and in particles of atmospheric aerosols ranged from 0.06 to 0.75, n.d. to 0.49 and 1.6 to 132ng/m(3), respectively. Levoglucosan was the dominant MAs detected in both type of samples. Less than 10% quantitation difference was obtained when bis-O-TMS derivatives were included in the calculation.
本研究评估了使用气相色谱-质谱联用仪(GC-MS)检测大气气溶胶中三种最常见的单糖酐(MAs)(左旋葡聚糖、甘露聚糖和半乳聚糖)的衍生化程序。比较了各种硅烷化试剂,主要是三甲基硅烷化试剂(TMS),并评估了各种含量的三甲基氯硅烷(TMCS,作为促进剂)的影响,以优化在气溶胶样品中检测这些化合物的条件。单糖酐结构中三个羟基的空间位阻导致了衍生物丰度的差异。还研究了反应时间和温度的影响。最佳反应时间和温度为60分钟和80摄氏度,使用1%的TMCS加0.2%的1,4-二硫代赤藓糖醇(DTE)。在这些条件下,半乳聚糖、甘露聚糖和左旋葡聚糖的双-O-TMS衍生物(作为副产物)的形成百分比分别为23%、29%和10%。烟雾样品颗粒中半乳聚糖、甘露聚糖和左旋葡聚糖的浓度分别为29至88、23至69和77至380 ng/m³;大气气溶胶颗粒中的浓度分别为0.06至0.75、未检出至0.49和1.6至132 ng/m³。左旋葡聚糖是两种样品中检测到的主要MAs。当计算中包括双-O-TMS衍生物时,定量差异小于10%。