棉织物负载纳米粒子自组装阵列基底构建及其SERS应用研究  

Fabrication of Cotton fabrics@densely-packed nanoparticle arrays based on self-assembly and its SERS application

作　　者：韩亚雪 李亚玲 周吉[1] 叶勇[1] HAN Yaxue;LI Yaling;ZHOU Ji;YE Yong(College of Chemistry and Chemical Engineering,Hubei University,Wuhan 430062,China;College of Criminal Justice,Zhongnan University of Economies and Law,Wuhan 430073,China)

机构地区：[1]湖北大学化学化工学院,湖北武汉430062 [2]中南财经政法大学刑事司法学院,湖北武汉430073

出　　处：《湖北大学学报（自然科学版）》2024年第5期648-657,共10页Journal of Hubei University：Natural Science

基　　金：司法鉴定技术应用与社会治理学科创新引智基地重点项目(FSSGL2021B-03)资助。

摘　　要：纤维基柔性表面增强拉曼光谱(SERS)基底的设计与开发是当前SERS研究实用化的热点。构建用于不规则固体表面上分析物的可靠痕量检测的柔性SERS基底仍具有挑战性。实现柔性多孔渗透性纤维表面大面积无缺陷的纳米颗粒单层膜的组装是解决SERS可靠性的要素之一。本研究采用三相界面自组装技术,成功在多孔渗透性棉织物上组装了大面积密排的金属纳米颗粒单层膜,通过调控纳米粒子表面包裹剂的浓度和类型,对球状金纳米粒子、板状银纳米粒子和棒状金纳米粒子实现了普适性组装和转移,得到了均匀表面且覆盖率高的棉织物SERS基底。以罗丹明6G(R6G)为探针分子,探究了各向异性金属纳米粒子复合SERS棉织物的增强能力。结果表明负载球状金纳米粒子自组装阵列的SERS棉织物具有更高的检测灵敏度和更好的均匀性,检测限低至1×10^(-9)mol/L,峰强度间的相对标准偏差为6.79%。对探针分子4-巯基吡啶(4-MPy)和4-氨基苯硫酚(4-ATP)的检测限分别为1×10^(-12)mol/L和1×10^(-10)mol/L。进一步地,用该棉织物SERS基底开展了痕量福美双的检测研究,其检测限低至0.005 mg/kg,在0.01~1000 mg/kg浓度区间内,福美双浓度的对数与SERS强度具有良好的线性关系。采用简单的“擦拭-吸附”法可直接提取苹果表面残留的福美双并检测,检测限低至0.2 ng/cm^(2),满足检测需求。由此可见,发展基于棉织物表面纳米粒子组装方法对柔性SERS基底的实用化研究具有重要的意义和应用前景。The design and development of practical SERS substrates is a hot spot in SERS research.It is still challenging to construct flexible SERS substrates for reliable trace detection of analytes on irregular solid surfaces.The assembly of a large area densely-packed nanoparticle arrays on the surface of flexible porous permeable fabrics is one of the key factors to solve the analysis reliability.In this paper,the three-phase interface self-assembly technology was used to construct a large area of densely-packed arrays of metallic nanoparticles on cotton fabric.By adjusting the concentration and species of capping agent on the surface of the nanoparticles,the universal assembly and transfer of spherical gold nanoparticles,plate-shaped silver nanoparticles and rod-shaped gold nanoparticles were realized.The SERS base of cotton fabric with uniform surface and high coverage was obtained.Using Rhodamine 6G(R6G)as the probe molecule,the enhancement ability of SERS fabric loaded with anisotropic metallic nanoparticles was investigated.The results showed that the SERS fabric loaded with spherical gold nanoparticles array showed the higher detection sensitivity and better uniformity,the detection limit was as low as 1×10^(-9)mol/L,and the relative standard deviation between peak intensities was 6.79%.The detection limits of 4-mercaptopyridine(4-MPy)and 4-aminophenthiophenol(4-ATP)were 1×10^(-12)and 1×10^(-10)mol/L,respectively.Furthermore,the SERS fabric was used for the detection of trace thiram.The detection limit was as low as 0.005 mg/kg.Within the concentration range of 0.01~1000 mg/kg,the logarithm of the concentration had a good linear relationship with SERS intensity.The simple“wipe-and-adsorption”method was adopted to directly extract and detect residual thiram on apple surface,and the detection limit is as low as 0.2 ng/cm^(2),which could meet the detection requirements.Therefore,it is of great significance and application prospect to develop the SERS fabrics based on the self-assembly method for the practical

关 键 词：纤维素 金属纳米粒子 三相界面自组装 表面增强拉曼 农药 

分 类 号：O657.37[理学—分析化学]