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    磁性碳纳米管提取-液相色谱-质谱法测定水中3种苯丙胺类毒品

    LC-MS Determination of Water for 3 Amphetamines with Enrichment by Dispersive SPE with Magnetic Carbon Nanotubes

    • 摘要: 取六水合三氯化铁(FeCl3·6H2O)4.70 g和四水合二氯化铁(FeCl2·4H2O)1.72 g,溶于80℃水280 mL中,加入羧基化多壁碳纳米管(c-MWCNTs)2.00 g,在磁力搅拌下加入氨水(28+72)溶液15 mL,在80℃搅拌30 min。静置,弃去溶液,用水清洗黑色沉积物3次,弃去洗液。将黑色沉淀物置于80℃烘箱干燥过夜,制得磁性碳纳米管复合材料(Fe3O4@c-MWCNTs)。将所制备的磁性材料应用于水样中3种苯丙胺类毒品的分离富集,3种苯丙胺类毒品(甲基苯丙胺、3,4-亚甲二氧基苯丙胺和甲卡西酮)的最佳分析条件:取水样5.0 mL,用1.0 mol·L-1 NaOH溶液0.1 mL调节其pH为12;加入磁性材料10.0 mg,在80 kHz超声提取1 min,静置2 min后,用强磁铁在容器外壁对磁性材料吸附,弃去水溶液,用水2 mL洗涤磁性材料,再次用磁铁吸附并弃去洗液。在吸附了分析物的磁性材料中,用甲醇(每次0.3 mL)在80 kHz条件下超声洗脱2次(每次1 min)。收集并合并2次所得洗脱液,氮吹至干,加入甲醇0.1 mL溶解残渣,经滤膜过滤后按选定条件进行液相色谱-质谱分析。分离时用Hypurity C18色谱柱作为分离柱,用甲醇和5 mmol·L-1乙酸-乙酸铵缓冲溶液(pH 4.0),以体积比为80:20作为流动相进行等度洗脱。质谱中选择电喷雾离子源和选择反应监测模式。上述3种苯丙胺类毒品的线性范围均在0.2~40.0 μg·L-1之间,检出限(3S/N)依次为0.015,0.018,0.020 μg·L-1。测定值的相对标准偏差(n=5)在4.0%~5.8%之间。

       

      Abstract: Magnetic carbon nanotube material (Fe3O4@c-MWCNTs) was prepared by dissolving 4.70 g of FeCl3·6H2O and 1.72 g of FeCl2·4H2O in 280 mL of water at 80℃ and 2.00 g of carboxylated multi-walled carbon nanotubes (c-MWCNTs) were added together with 15 mL of aq. ammonia (28+72), under magnetic stirring and the stirring was continued for 30 min at 80℃. After standing, the solution was discarded and the black precipitate was washed thrice with water. The washings were discarded and the black precipitate was collected and dried in drying oven at 80℃ overnight. The magnetic material obtained was applied to the separation and enrichment of 3 amphetaminesi.e., methamphetamine (MA), 3,4-dimethoxyamphetamine (MDA) and methylcarcinone (MCN) from water sample. 5.0 mL of water sample were taken with its acidity adjusted to pH 12 with 1.0 mol·L-1 NaOH solution (0.1 mL). 10.0 mg of Fe3O4@c-MWCNTs were added and the mixture was stirred ultrasonically for 1 min at 80 kHz, settled for 2 min, and Fe3O4@c-MWCNTs adsorbed with the amphetamines was to be pulled to a magnet placed at the outside wall of the glass vessel. The water solution was discarded and Fe3O4@c-MWCNTs was washed once more with 2 mL of water. After discarding the washing, the analytes on Fe3O4@c-MWCNTs were eluted ultrasonically twice with methanol (0.3 mL for each elution) at 80 kHz for 1 min in each elution. The eluates were combined and evaporated to near dryness by N2-blowing. The residue was dissolved in 0.1 mL of methanol. The solution, after filtering through a membrane, was used for LC-MS analysis. Hypurity C18 chromatographic column was used as the stationary phase and a mixture of methanol and 5 mmol·L-1 acetic acid-ammonium acetate buffer solution (pH 4.0), in the volumic ratio of 80 to 20 was used as mobile phase in equivalent elution. ESI and SRM were adopted in MS. Linearity ranges for the 3 amphetamines were found same between 0.2-40.0 μg·L-1, with detection limits (3S/N) of 0.015, 0.018, 0.020 μg·L-1 respectively. Values of RSDs (n=5) found were in the range of 4.0% to 5.8%.

       

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