Fabrication of novel gold nanorod/polymer nanocomposite fibers and their application in heavy metal ion sensing

Abstract

Metallic nanoparticles (MNPs), which exhibit fascinating optical, electronic and catalytic properties, have been recognized as essential building blocks for the development of advanced nanodevices. Production of MNP assemblies on a pre-designed substrate is a crucial step towards the exploration of their ensemble properties as well as their potential applications. Despite the diverse assembly strategies reported in the literature, the lack of a generic MNP immobilization strategy with applicability to MNPs and substrates with various shapes and chemical compositions remains an unsolved problem. To this end, we proposed an electrostatic attraction-driven assembly strategy and applied it to the fabrication of a novel nanocomposite material composed of gold nanorod (AuNR) assemblies supported on electrospun polycaprolactone (PCL) fibers. In order to utilize electrostatic attraction as the driving force, opposite surface charges on the AuNRs and the PCL fibrous substrate were developed via polyelectrolyte decoration. UV-Vis studies on the AuNR immobilization process revealed that the AuNR density on the fiber surface can be effectively tuned by changing the immersion time. The as-fabricated AuNR/PCL nanocomposite fibers were further employed as substrates for surface enhanced Raman scattering (SERS) measurements and they exhibited high activity as well as excellent reproducibility for both chemisorbed and physisorbed analyte molecules. In addition, a comparison experiment on the SERS performance of the 3D AuNR/PCL fibrous substrate and its 2D counterpart--a AuNR/PCL film, demonstrated that the former provided superior SERS activity due to the enhanced surface area. With the demonstration on the high SERS efficacy, we moved one step further towards the development of a SERS-based environmental sensor targeting the detection of highly toxic heavy metal ions of Hg2+ and Cu 2+ . The SERS detection of Hg2+ and Cu2+ was achieved through the functionalization of AuNR/PCL fibers with metal ion binding ligands of 2,5-dimercapto-1,3,4-thiadiazole dimer and trimercaptotriazine, respectively. The changes in the SERS spectral features of the ligands before and after heavy metal ion coordination were indicative for the detection of target ions. Based on the above design, the resultant sensors exhibited not only high selectivity, but also the capability for quantitative analysis of the target ion concentration.