ABSTRACT
Diabetes is a common chronic metabolic disease. The frequent fluctuation of glucose is the main cause of most diabetes complications, which in turn causes harm to the health of patients. Surface-enhanced Raman scattering (SERS) spectroscopy has attracted much attention in the rapid detection of glucose due to its unique molecular fingerprinting ability, ultra-high sensitivity and fast response. However, due to the low affinity between glucose and SERS substrate, poor signal, susceptibility to complex environmental interference, and poor stability of SERS detection, it is still a challenge for SERS to accurately and sensitively determine glucose in complex environments. In this work, we encapsulated 4-mercaptobutyronitrile (4-MBN) as an internal standard (IS) in Au@Ag NRs inside and then Au@4-MBN@Ag NRs, Leucomalachite Green (LMG), glucose oxidase (GOx) and horseradish peroxidase (HPR) were encapsulated in ZIF-8 to prepare a tandem enzyme catalytic ratiometric SERS sensor Au@4-MBN@Ag@LMG@ZIF-8(GOx, HPR) for the detection of glucose in saliva. Because ZIF-8 enhanced the catalytic activity of the enzyme, the ability of glucose enrichment, and weakens the aggregation of Ag NRs. The internal standard signal molecule improves the accuracy and sensitivity of detection. The ratiometric Raman signal I412/I2233 of glucose has a good linear relationship with the concentration in the range of 0.1-100 µM, and the limit of detection (LOD) could be down to 0.03 µM. At the same time, it has excellent selectivity, repeatability and accuracy. The recovery rate of glucose in saliva is 96.50%-105.56 %, which proves the feasibility of the method. The Au@4-MBN@Ag@LMG@ZIF-8(GOx, HPR) sensor prepared in this study showed excellent SERS performance, which was able to detect glucose quickly, sensitively and accurately. This work provides a new strategy for the design of enzyme-catalyzed SERS sensors.
Subject(s)
Glucose , Spectrum Analysis, Raman , Humans , Spectrum Analysis, Raman/methods , Glucose Oxidase/chemistryABSTRACT
In recent research, anisotropic plasmonic core-shell nanomaterials have gained a lot of attention in surface-enhanced Raman scattering (SERS) due to their brilliant uniformity and optical properties. Herein, a bimetallic core-molecule-shell (CMS) composite nanorod SERS substrate nanomaterial (Au NB-DT@Ag NRs) was designed and synthesized under precise regulation. The inner core is gold nanobipyramids (Au NBs), which possess superior plasmonic properties. Uniform Au NBs of five different sizes were fabricated via a penta-twinned gold seed mediated growth method. The length varied from 160 to 62 nm and the corresponding diameter varied from 60 to 23 nm while the longitudinal surface plasmonic resonance (SPR) changed from 908 to 715 nm. The SERS activity of five Au NBs were compared and the optimally sized one with a length of 78 nm and width of 28 nm was set as the inner core. After modification with the Raman reporter (DT), different amounts of silver were deposited on the surface of Au NB-DTs to form an Au NB-DT@Ag nanocomposite. The shape of the nanostructure gradually became a rod and lengthened while the longitudinal SPR wavelength varied from 733 nm to 664 nm with an increase in the amount of silver nitrate added. The Au NB-DT@Ag NRs with the best SERS activity (b-3) could realize the quantitative detection of the toxic dyes malachite green (MG) and crystal violet (CV) of concentrations as low as 5 × 10-9 M, showing good reproducibility and stability. This work offers a new design strategy for a SERS substrate for reliable quantitative SERS detection applications.
ABSTRACT
The p53 gene is a known cancer marker. We report a novel protocol for the SERS tandem strategy to detect the p53 gene with high sensitivity. Herein, the click reaction between azide and alkyne was catalyzed by utilizing copper oxide nanoparticles (CuONPs), which were enriched by a T-DNA-triggered hybridization chain reaction (HCR). The T-DNA signal was amplified by establishing the correlation between the T-DNA signal and the concentration of CuONPs in a nonenzymatic isothermal environment. In contrast to other Raman reporters, we used alkynyl compounds as Raman reporters, which showed excellent characteristics in the Raman-silent region (1800-2800 cm-1). Therefore, the highly sensitive and highly selective SERS signals could be obtained in complex biological matrices. Due to utilizing multistep amplification strategies, including the nanoparticle-modified HCR polymer and "click" reaction, the limit of detection (LOD) and the limit of quantification (LOQ) of this sensor could be as low as 0.0174 pM and 0.0583 pM, respectively. The accuracy of the strategy expressed as the RSD was in the range of 3.14%-6.21%. The results indicated that the constructed sensor has excellent performance for the detection of the p53 gene in serum samples in a low concentration range, which suggests that the proposed enzyme-free SERS analytical sensor has good clinical application prospects.
