Surface-enhanced
Raman spectroscopy (SERS) can be applied for biological
detection because of its high sensitivity and noninvasiveness for
analytes. Herein, we engineer plasmonic free-standing substrates composed
of Ag nanoparticles (NPs) supported on polyacrylonitrile (PAN) electrospinning
nanofibrous felts as sensors for bacterial detection. Ag NPs are evenly
distributed on PAN nanofibers after preimpregnation and impregnation
of PAN nanofibers in Tollens’ reagent. The size and loading
density of Ag NPs are tunable by adjusting the reaction time of glucose
and Tollens’ reagent, thereby allowing the tuning of the surface
plasmon resonance. Using 4-mercaptophenol (4-MPh) and 4-mercaptobenzoic
acid (4-MBA) as probe molecules, SERS effects of Ag@PAN composite
nanofibers are investigated, and the substrates allow the detection
of 4-MPh and 4-MBA at a low concentration of 10
–9
mol/L. Importantly, the substrates exhibit a high sensitivity of
SERS performance for bacterial identification without a specific bacteria–aptamer
conjugation. The SERS substrates also show good uniformity of SERS
response for bacterial organelles. Furthermore, the antimicrobial
property was evaluated, and the results indicate that the sample of
Ag@PAN nanofiber mats possesses excellent antibacterial properties
against
Escherichia coli
and
Staphylococcus aureus
.
In this paper, a convenient method to fabricate flexible and free-standing surface-enhanced Raman scatting (SERS) substrates for direct bacteria detection without aptamer bonding is presented. SiO2 nanofibers were prepared via electrospinning and calcination by using tetraethyl orthosilicate as the precursor. Subsequently, it was coated with polydopamine (PDA) by self-polymerization. Finally, Ag@PDA@SiO2 nanofibrous membranes were obtained through in situ growth of Ag nanoparticles in Tollens’ reagents. The as-prepared Ag@PDA@SiO2 composite nanofibrous membranes were characterized by techniques of scanning electron microscopy, transmission electron microscopy, X-ray powder diffraction, energy-dispersive x-ray spectroscopy and thermo gravimetric analysis. The flexibility of the as-prepared nanofibrous membranes were verified simply through manual folding. Small molecule probes of 4-mercaptophenol (4-MPh) and 4-mercaptobenzoic acid (4-MBA) were chosen to investigate the SERS sensitivity of the as-prepared Ag@PDA@SiO2 as free-standing substrates. Furthermore, Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus), as typical strains of Gram-negative and Gram-positive bacteria, were performed to directly SERS detection by dropping bacteria suspension onto the fibrous membranes without any previous treatment, such as aptamer combination. In addition, the antimicrobial properties of the as-prepared Ag@PDA@SiO2 electrospinning nanofibrous membranes were tested by inhibition zone and turbidity methods. The results show that Ag nanoparticles with an average diameter of 50 nm are uniformly deposited on the surface of electrospinning nanofibers, and the as-prepared Ag@PDA@SiO2 nanofibrous membranes are flexible. As SERS substrates, it shows a rather high detection limitation of 10−11 mol l−1 for 4-MPh and 4-MBA. More importantly, this substrate can be applied for bacteria label-free SERS detection, i.e., complicated procedures are avoided. Meanwihile, the as-prepared Ag@PDA@SiO2 nanofibrous membranes exhibit excellent antibacterial properties. Thus, it has application prospects in trace bacteria detection and water purification.
In this paper, we propose a facile and cost-effective electrospinning technique to fabricate surface-enhanced Raman scattering (SERS) substrates, which is appropriate for multiple analytes detection. First of all, HAuCl4∙3H2O was added into the TEOS/PVP precursor solution, and flexible SiO2 nanofibers incorporated with gold nanoparticles (SiO2@Au) were prepared by electrospinning and calcination. Subsequently, the nanofibrous membranes were immersed in the tannic acid and 3-aminopropyltriethoxysilane solution for surface modification through Michael addition reaction. Finally, the composite nanofibers (Ag@T-A@SiO2@Au) were obtained by the in-situ growth of Ag nanoparticles on the surfaces of nanofibers with tannic acid as a reducing agent. Due to the synergistic enhancement of Au and Ag nanoparticles, the flexible and self-supporting composite nanofibrous membranes have excellent SERS properties. Serving as SERS substrates, they are extremely sensitive to the detection of 4-mercaptophenol and 4-mercaptobenzoic acid, with an enhancement factor of 108. Moreover, they could be utilized to detect analytes such as pesticide thiram at a low concentration of 10−8 mol/L, and the substrates retain excellent Raman signals stability during the durability test of 60 days. Furthermore, the as-fabricated substrates, as a versatile SERS platform, could be used to detect bacteria of Staphylococcus aureus without a specific and complicated bacteria-aptamer conjugation procedure, and the detection limit is up to 103 colony forming units/mL. Meanwhile, the substrates also show an excellent repeatability of SERS response for S. aureus organelles. Briefly, the prime novelty of this work is the fabrication of Au/Ag bimetallic synergetic enhancement substrates as SERS platform for versatile detection with high sensitivity and stability.
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