NIR-SERS Spectra Detection of Cytidine on Nano-Silver Films
ZHANG De-qing1, LIU Ren-ming1, 2*, ZHANG Guo-qiang1, ZHANG Yan1, XIONG Yang1, ZHANG Chuan-yun1, LI Lun1, SI Min-zhen1*
1. Yunnan Key Laboratory of Universities for Molecular Spectrum, School of Physics and Electronic Science, Chuxiong Normal University, Chuxiong 675000, China 2. State Key Laboratory of Optoelectronic Materials and Technologies, School of Physics and Engineering, Sun Yat-sen University, Guangzhou 510275, China
Abstract：The polyvinyl alcohol (PVA) protected silver glass-like nanostructure (PVA-Ag-GNS) with high surface-enhanced Raman scattering (SERS) activity was prepared and employed to detect the near-infrared surface enhanced Raman scattering (NIR-SERS) spectra of cytidine aqueous solution (10-2～10-8 mol·L-1). In the work, the near-infrared laser beam (785 nm) was used as the excitation light source. The experiment results show that high-quality NIR-SERS spectra were obtained in the ranges of 300 to 2 000 cm-1 and the detection limit of cytidine aqueous solution was down to 10-7 mol·L-1. Meanwhile, the PVA-Ag-GNS shows a high enhancement factor (EF) of ～108. In order to test the optical reproducibility of PVA-Ag-GNS, ten samples of cytidine aqueous solution (10-2～10-5 mol·L-1) had been dropped onto the surface of PVA-Ag-GNS respectively. Meanwhile, these samples were measured by the portable Raman spectrometer. As a result, the PVA-Ag-GNS demonstrated good optical reproducibility in the detection of cytidine aqueous solution. In addition, to explain the reason of enhancement effect, the ultraviolet-visible (UV-Vis) extinction spectrum and scanning electron microscope (SEM) of cytidine molecules adsorbed on the surface of PVA-Ag-GNS were measured. There is plasmon resonance band at 800 nm in the UV-Vis extinction spectrum of the compound system. Therefore, when the near-infrared laser beam (785 nm) was used as excitation light source, the compound system may produce strongly surface plasmon resonance (SPR). According to the SEM of PVA-Ag-GNS, there are much interstitial between the silver nanoparticles. So NIR-SERS is mainly attributed to electromagnetic (EM) fields associated with strong surface plasmon resonance. At last, the geometry optimization and pre-Raman spectrum of cytidine for the ground states were performed with DFT, B3LYP functional and the 6-311G basis set, and the near-infrared laser with wavelength of 785 nm was employed in the pre-Raman spectrum calculation process. The calculation results without imaginary frequency and the results match pretty well with the experimental Raman spectrum. At the same time, the assignations of Raman bands and adsorption behaviors of cytidine molecules on the surface of PVA-Ag-GNS are also discussed. According to our experiment and calculations, cytidine molecules mainly adsorbed on silver nanoparticles via the ribose moiety and amino group may get close to the local electromagnetic field.
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