MOE Key Laboratory of Bioinorganic and Synthetic Chemistry/KLGHEI of Environment and Energy Chemistry, School of Chemical Engineering and Technology, School of Environmental Science and Engineering, School of Chemistry, Institute of Green Chemistry and Molecular Engineering, Sun Yat-sen University, Guangzhou 510006, China.
Guangdong Provincial Key Laboratory of Emergency Test for Dangerous Chemicals, Guangdong Provincial Key Laboratory of Chemical Measurement and Emergency Test Technology, Guangdong Institute of Analysis (China National Analytical Center Guangzhou), Guangdong Academy of Sciences, Guangzhou 510070, China.
Sci Total Environ. 2024 Jan 1;906:167655. doi: 10.1016/j.scitotenv.2023.167655. Epub 2023 Oct 6.
Tobacco-specific nitrosamines (TSNAs) are probably carcinogenic disinfection byproducts eliciting health risk concerns. The determination and surveillance of TSNAs in water is still cumbersome due to the lack of advanced sample preparation methods. Herein, we prepared a solid phase microextraction (SPME) fiber coated with the molecularly imprinted polymer (MIP) sheathed mesoporous silica tube (MST) composite material, and developed a highly efficient, selective, and sensitive method for the determination of five TSNAs in water. Benefiting from the TSNAs-specific recognition of MIP and the increased specific surface area derived from MST, the MIP@MST fiber exhibited excellent extraction performance for TSNAs, which was much superior to the commercially available SPME fibers. By coupling to high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS), the outstanding analytical merits such as low method detection limits (ranging 0.1-6.7 ng L) and good reproducibility (intra-fiber and inter-fiber relative standard deviations ranging 4.1 %-11.6 % and 3.5 %-12.2 %, respectively) were achieved with the consumption of 8 mL water sample and 100 μL methanol solvent in 50 min. The feasibility of the SPME-HPLC-MS/MS method was demonstrated in tap water and chloraminated source water, with relative recoveries for the five TSNAs ranging from 85.2 % to 108.5 %. In result, none of the TSNAs were found in the tap water samples, while 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone (NNK) and 4-(methylnitrosamino)-1-(3-pyridyl)-1-Butanol (NNAL) were detected in the chloraminated source water samples. The rapid and convenient SPME-HPLC-MS/MS method developed in this study offers a powerful tool for monitoring TSNAs in water.
烟草特异性亚硝胺（TSNAs）可能是致癌的消毒副产物，引起健康风险的关注。由于缺乏先进的样品制备方法，水中 TSNAs 的测定和监测仍然很繁琐。在此，我们制备了一种涂有分子印迹聚合物（MIP）的固相微萃取（SPME）纤维，该纤维包裹着介孔硅管（MST）复合材料，并开发了一种高效、选择性和灵敏的方法来测定水中的五种 TSNAs。受益于 MIP 对 TSNAs 的特异性识别和 MST 带来的增加的比表面积，MIP@MST 纤维对 TSNAs 表现出优异的萃取性能，远优于市售的 SPME 纤维。通过与高效液相色谱-串联质谱（HPLC-MS/MS）联用，该方法具有出色的分析优点，如低方法检测限（范围为 0.1-6.7 ng L）和良好的重现性（纤维内和纤维间相对标准偏差分别为 4.1%-11.6%和 3.5%-12.2%），仅需消耗 8 mL 水样和 100 μL 甲醇溶剂，50 min 即可完成。该 SPME-HPLC-MS/MS 方法在自来水和加氯水源水中的可行性得到了验证，五种 TSNAs 的相对回收率在 85.2%-108.5%之间。结果表明，自来水中未检出 TSNAs，而加氯水源水中检测到 4-（甲基亚硝氨基）-1-（3-吡啶基）-1-丁酮（NNK）和 4-（甲基亚硝氨基）-1-（3-吡啶基）-1-丁醇（NNAL）。本研究中开发的快速便捷的 SPME-HPLC-MS/MS 方法为监测水中的 TSNAs 提供了有力工具。
