负载金纳米粒子的纳米纤维膜SERS基底的制备及其在毒品检测中的应用  

Gold Nanoparticles Functionalized Cellulose Nanofiber-based SERS Nano-membrane and the Application for Determination of Illicit Drugs

作　　者：姚慧芳[1] 叶泽霖 周吉[2] 陶涛[3] 高吭 叶勇[2] YAO Huifang;YE Zelin;ZHOU Ji;TAO Tao;GAO Hang;YE Yong(Hubei Key Laboratory of the Forensic Science,Hubei University of Police,Wuhan 430034;College of Chemistry and Chemical Engineering,Hubei University,Wuhan 430062;Drug Inspection and Identification Center,Huangshi City Public Security Bureau,Huangshi 435000)

机构地区：[1]湖北警官学院,法庭科学湖北省重点实验室,湖北武汉430034 [2]湖北大学化学化工学院,湖北武汉430062 [3]黄石市公安局毒品检验鉴定中心,湖北黄石435002

出　　处：《分析科学学报》2023年第3期251-259,共9页Journal of Analytical Science

基　　金：公安部公安理论及软科学研究计划项目(批准号:2019LLYJHBST047);法庭科学湖北省重点实验室开放基金(批准号:2018KFKT06,KFKT2019009);司法鉴定技术应用与社会治理学科创新基地重点项目(批准号:FSSGL2021B-03)。

摘　　要：在水热条件下将纤维素纳米纤维(CNF)同时用作还原剂和稳定剂与氯金酸反应,制备了负载金纳米粒子(Au NPs)的纳米纤维素溶胶。采用真空抽滤的方法在微孔滤膜上一步沉积制备了金/纳米纤维素复合膜,复合膜中纤维束相互交错堆叠成多层三维结构,允许大量金纳米粒子在膜层中均匀分散。以罗丹明6G(R6G)和4-巯基吡啶(4-MPy)为探针分子对该复合膜的SERS性能进行了考察。结果显示,该SERS基底具有高的检测灵敏度和良好的光谱重复性,对R6G和4-MPy的检测限分别达到1×10^(-8) mol/L和1×10^(-7) mol/L,相对标准偏差为7.8%。利用该复合膜对苯丙胺类毒品进行了分析和鉴定,其对甲基苯丙胺的检测浓度可低至1×10^(-7) mol/L,检测灵敏度明显优于实验室自制的两种三维结构的纤维柔性SERS基底。同时,将该SERS基底应用于毛发检材中痕量甲基苯丙胺的快速筛查,并采用气相色谱(GC)方法验证结果。结果显示,5份不同添加量的甲基苯丙胺的毛发样品均在1000和1030 cm^(-1)出现甲基苯丙胺明显的特征峰,且随浓度升高拉曼特征峰变强,说明SERS技术能快速筛查出毛发样本中痕量的甲基苯丙胺,GC验证也表明该方法具有较好的准确性,有望进一步推进该方法用于涉毒现场快速检测。Cellulose nanofiber(CNF),as a reducing agent and stabilizer,was allowed to directly react with chloroauric acid to prepare nanocellulose gold sol under hydrothermal conditions.The nanocellulose gold sol was deposited on the surface of the filter membrane by one-step vacuum filtration to fabricate gold/nanocellulose composite film.In the composite film,the fiber bundles are interleaved and stacked to form a multi-layer three-dimensional structure,which allows a large number of gold nanoparticles to be uniformly dispersed in the film layer.Rhodamine 6G(R6G)and 4-mercaptopyridine(4-MPy)were used as probe molecules to evaluate the SERS performance of the substrate.The SERS substrate showed high detection sensitivity and good spectral repeatability,with detection limits of 1×10^(-8)and 1×10^(-7)mol/L for R6G and 4-MPy,respectively,with a relative standard deviation of 7.8%.The substrate was further applied to the identification of amphetamine.The results showed that the detection concentration can be as low as 1×10^(-7)mol/L for methamphetamine.The detection sensitivity is significantly better than that of the other two 3D-structured fibrous flexible SERS substrates made in the laboratory.Meanwhile,the SERS substrate was applied to the rapid screening of trace methamphetamine in hair samples,and the results were verified by gas chromatography(GC)method.The results showed that five hair samples with different added amounts of methamphetamine all showed obvious characteristic peaks of methamphetamine at 1001 and 1030 cm^(-1),and the Raman characteristic peaks became stronger with the increasement of concentration,indicating that SERS technology could quickly screen trace amounts of methamphetamine in hair samples,and GC validation also showed good accuracy.Therefore,it is expected to further promote the SERS method for rapid screening and identification of drugs on site.

关 键 词：纳米纤维素 金纳米粒子 甲基苯丙胺 表面增强拉曼光谱 毛发检材 

分 类 号：O657.37[理学—分析化学]