A flexible and stable biomimetic SERS substrate was successfully fabricated by depositing gold (Au) nanoislands on the dragonfly wings (DW) via a simple DC magnetron sputtering system. Characterizations of the Au/DW nanostructure indicated that the optimum Au/DW-45 (sputtering time was 45 min) substrate owns high sensitivity, good stability and outstanding reproducibility. The limit of detection (LOD) for Rhodamine 6 G (R6G) was as low as 10−7 M and enhancement factor (EF) was calculated to be 2.8 × 106. 70-day-duration stability tests showed that Raman intensity of R6G reduced only by 12.9% after aging for 70 days. The maximum relative standard deviations (RSD) of SERS intensities from 100 positions of Au/DW-45 substrate were less than 8.3%, revealing outstanding uniformity and reproducibility. Moreover, the flexible Au/DW-45 bioscaffold arrays were employed to solve the vital problem of pesticide residues. By directly sampling from tomato peels via a “press and peel off” approach, cypermethrin has been rapidly and reliably determined with a LOD centered at 10−3 ng/cm2 and a correlation coefficient (R2) of 0.987. The positive results demonstrated that the Au-based DW biomimetic arrays may offer an efficient SERS platform for the identification of various pesticide residues on real samples.
Rapid sampling and multicomponent analysis are vital in pesticide residue detection. In this work, we proposed a SERS platform to detect three kinds of pesticides on apple peels simultaneously by a straightforward “press and peel off” method. The flexible Au/dragonfly wing (Au/DW) substrate was obtained from sputtering Au nanoislands on DW bioscaffold arrays by a simple direct current (DC) magnetron sputtering system. The high-performance substrate exhibited a low limit of detection (LOD) to 4-aminothiophenol (4-ATP) (10−9 M), outstanding reproducibility (less than 12.15%), good stability and suitability in multifold pesticide residues detection. Considering its excellent sample collection efficiency, the Au/DW substrate was employed to solve critical pesticide residue problems for detection of acephate (APT), cypermethrin (CPT), tsumacide (MTMC) and their multiple components on apple peels. The results show that the LOD was 10−3 ng/cm2 for APT obtained on the apple surface with a calculation equation of y = 0.26x + 6.68 and a determination coefficient (R2) of 0.970. Additionally, the LOD values for CPT and MTMC were 10−3 ng/cm2 and 10−4 ng/cm2, respectively. The finding in this work may provide a promising biomimetic SERS platform for on-spot detection of other organic pollutants in the food industry and inenvironmental protection.
28 February 2019 in Beilstein Journal of Nanotechnology
In this work, we report a biomimetic synthesis route of 3D Ag nanofilm/glasswing butterfly wing hybrids (Ag-G.b.) by magnetron sputtering technology. The 3D surface-enhanced Raman scattering (SERS) substrate is fabricated from an original chitin-based nanostructure, which serves as a bio-scaffold for Ag nanofilms to be coated on. The novel crisscrossing plate-like nanostructures of 3D Ag-G.b. nanohybrids with thick Ag nanofilms provide a substantial contribution to SERS enhancement. Measuring the SERS performance with crystal violet (CV), the Ag-G.b. nanohybrids with the sputtering time of 20 min (Ag-G.b.-20) shows the highest enhancement performance with an enhancement factor (EF) of up to 2.96 × 107. The limit of detection (LOD) for CV was as low as 10−11 M, demonstrating the ultrahigh sensitivity of the Ag-G.b.-20 substrate. In addition, the Ag-G.b.-20 substrate has an outstanding reproducibility across the entire area with the maximum value of relative standard deviation (RSD) of less than 10.78%. The nanohybrids also exhibit a long-term stability regarding Raman enhancement, as suggested by a duration stability test over a period of 60 days. Importantly, the high-performance Ag-G.b.-20 substrate is further applied as an ultra-sensitive SERS platform for the trace detection of acephate, showing its great potential application in biochemical sensing and food security.
The recent development of SERS substrates based on irregular nanostructures for directly molecule recognition has aroused increasing attention. By combining the irregular flake-like nanostructures of mantis wings, high SERS performance of Ag nanofilms, and the chemical stability of Au nanoparticles (NPs), an ultra-sensitive and flexible SERS substrate based on Au NPs functionalized Ag nanofilms-mantis wings (Au-Ag-M.w.) hybrid system is successfully fabricated. When 4-aminothiophenol is selected as the probe molecule, the limit of detection (LOD) is as low as 10−13 M and the relative standard deviation (RSD) is lower than 7.15%. This novel SERS platform exhibits high SERS performance in terms of sensitivity, reproducibility and practicability mainly because there are high-density and multi-level “hot spots” in the appropriate nanogaps. Meanwhile, it also systematically compares the differences of the SERS performance of Cu and Ag decorated M.w. hybrids and how these differences can alter their response. Moreover, the proposed substrate is employed to rapidly detect the pesticide residues on apple peels and the LOD for cypermethrin is estimated at 10−10 mg/mL. Therefore, this novel SERS substrate has great potential in rapid sampling of pesticide residues on real samples and expands the investigation to other natural materials for fabricating various SERS platforms.
Rapid sampling and multicomponent analysis are vital in the analysis of pesticide residue detection. In this work, we proposed a SERS platform to simultaneously detect three kinds of pesticides on apple peels by a straightforward “press and peel off” method. The flexible Au/dragonfly wing (Au/DW) substrate was obtained from sputtering Au nanoislands on dragonfly wing bioscaffold arrays by a simple DC magnetron sputtering system. The high-performance substrate exhibited a low limit of detection (LOD) to 4-aminothiophenol (4-ATP) (10-9 M), outstanding reproducibility (less than 12.15%), good stability and suitability in multifold pesticide residues detection. Considering its excellent sample collection efficiency, the Au/DW substrate was employed to solve critical pesticide residues problems for detection of acephate (APT), cypermethrin (CPT), tsumacide (MTMC) and their multiple components on apple peels. The results show that the LOD was 10-3 ng/cm2 for APT obtained on the apple surface with a calculation equation of y=0.26x+6.68 and a correlation coefficient (R2) of 0.970. Additionally, the LOD values for CPT and MTMC were 10-3 ng/cm2 and 10-4 ng/cm2, respectively. The finding in this work may provide a promising biomimetic SERS platform for on-spot detection of other organic pollutants in the food industry and the environmental protection.
In this paper, a surface-enhanced Raman scattering (SERS) sensor with a giant field enhancement factor based on the coupling of surface plasmon polaritons (SPPs) is designed and studied theoretically. The proposed sensor adopts a metal-dielectric layered hybrid slot waveguide structure, combining thin metal (gold) layers and silicon nitride strip waveguides. Unlike other similar sensors, the silicon nitride waveguide structure does not serve as an excitation signal channel, conventionally loaded with the guided modes, but as an auxiliary layer, making it easier to concentrate the light field in the slot. Therefore, the sensor has a higher enhancement factor compared to the pure metal or dielectric slot structure. The results exhibit that we can obtain a maximum enhancement factor exceeding 10^6 under the compact configuration of 510 × 300 × 225nm^3 at the wavelength of 785 nm. By analyzing the dependence of the sensor performance on the structural parameters, we show that the structure of such sensor can directly be applied to SERS spectroscopic analysis as well as integrated with micro-and nano-photonic platform to perform on-chip detection system.