改性纤维素纸基萃取材料的制备及其对水中芬太尼类化合物的富集应用

Preparation of Modified Cellulose Paper-Based Extraction Material and Its Application in Enrichment of Fentanyl Compounds in Water

关键词:  二苯基甲烷二异氰酸酯(MDI)  芬太尼类化合物  纸基萃取  高效液相色谱-串联质谱

Key Words:Diphenylmethane diisocyanate (MDI)  Fentanyl-like compounds  Paper-based extraction  High-performance liquid chromatography - tandem mass spectrometry

摘要:为了实现水环境中痕量芬太尼类化合物的高效富集与检测，本文通过化学接枝法制备了二苯基甲烷二异氰酸酯（MDI）改性纤维素纸基萃取材料，结合高效液相色谱-串联质谱（HPLC-MS/MS）分析技术，构建了水中7种芬太尼类化合物的高效提取与定量检测方法。扫描电镜（SEM）、红外光谱（FT-IR）和热重分析（TGA）表明，MDI与纤维素表面的羟基成功发生反应并生成氨基甲酸酯（聚氨酯）结构。该萃取材料借助于疏水性和π-π相互作用对芬太尼类化合物进行吸附。确立了最佳萃取条件为：样品pH为9.0，洗脱溶剂为丙酮，吸附平衡时间为40 min。在1-100 μg?L-1的浓度范围内，所有芬太尼类化合物的HPLC-MS/MS线性良好，相关系数R2＞0.99。在3种加标浓度下，7种芬太尼在实际水样中的平均加标回收率为53.0%～106%，检出限（LOD）为0.02～0.07 μg?L-1。这些结果表明，该MDI-纤维素纸基萃取材料在提取芬太尼类化合物方面展现出优异的吸附与富集性能。

Abstract:In order to achieve efficient enrichment and detection of trace fentanyl-like compounds in water environment, this paper prepared a cellulose paper-based extraction material modified by diphenylmethane diisocyanate (MDI) through chemical grafting method. Combined with high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) analysis technology, a highly efficient extraction and quantitative detection method for 7 fentanyl-like compounds in water was constructed. Scanning electron microscopy (SEM), infrared spectroscopy (FT-IR) and thermogravimetric analysis (TGA) indicated that MDI successfully reacted with the hydroxyl groups on the cellulose surface and formed an amine carbamate (polyurethane) structure. This extraction material adsorbs fentanyl-like compounds through hydrophobicity and π-π interactions. The optimal extraction conditions were determined as follows: the sample pH was 9.0, the elution solvent was acetone, and the adsorption equilibrium time was 40 min. All fentanyl-like compounds exhibited good linearity in the HPLC-MS/MS analysis within the concentration range of 1–100 μg·L?¹, with correlation coefficients R² > 0.99. At three spiked concentrations, the average spiked recovery of the seven fentanyl-like compounds in actual water samples ranged from 53.0% to 106%, with detection limits (LOD) between 0.02 and 0.07 μg·L?¹. These results indicate that the MDI-cellulose paper-based extraction material exhibits excellent adsorption and enrichment performance for fentanyl derivatives.