We show a new type of elastic surface-enhanced Raman spectroscopy (SERS) platform made of poly(ethylene terephthalate) (PET) covered with a layer of indium tin oxide (ITO). This composite is subjected to dielectric barrier discharge (DBD) that develops the active surface of the PET/ITO foil. To enhance the Raman signal, a modified composite was covered with a thin layer of silver using the physical vapor deposition (PVD) technique. The SERS platform was used for measurements of para-mercaptobenzoic acid (p-MBA) and popular pesticides, i.e., Thiram and Carbaryl. The detection and identification of pesticides on the surface of fruits and vegetables is a crucial issue due to extensive use of those chemical substances for plant fungicide and insecticide protection. Therefore, the developed PET/ITO/Ag SERS platform was dedicated to quantitative analysis of selected pesticides, i.e., Thiram and Carbaryl from fruits. The presented SERS platform exhibits excellent enhancement and reproducibility of the Raman signal, which enables the trace analysis of these pesticides in the range up to their maximum residues limit. Based on the constructed calibration curves, the pesticide concentrations from the skin of apples was estimated as 2.5 µg/mL and 0.012 µg/mL for Thiram and Carbaryl, respectively. Additionally, the PET/ITO/Ag SERS platform satisfies other spectroscopic properties required for trace pesticide analysis e.g., ease, cost-effective method of preparation, and specially designed physical properties, especially flexibility and transparency, that broaden the sampling versatility to irregular surfaces.
The circulating tumor cells (CTCs) isolation and characterization has a great potential for non-invasive biopsy. In the present research, the surface–enhanced Raman spectroscopy (SERS)-based assay utilizing magnetic nanoparticles and solid SERS-active support integrated in the external field assisted microfluidic device was designed for efficient isolation of CTCs from blood samples. Magnetic nanospheres (Fe2O3) were coated with SERS-active metal and then modified with p-mercaptobenzoic acid (p-MBA) which works simultaneously as a Raman reporter and linker to an antiepithelial-cell-adhesion-molecule (anti-EpCAM) antibodies. The newly developed laser-induced SERS-active silicon substrate with a very strong enhancement factor (up to 108) and high stability and reproducibility provide the additional extra-enhancement in the sandwich plasmonic configuration of immune assay which finally leads to increase the efficiency of detection. The sensitive immune recognition of cancer cells is assisted by the introducing of the controllable external magnetic field into the microfluidic chip. Moreover, the integration of the SERS-active platform and p-MBA-labeled immuno-Ag@Fe2O3 nanostructures with microfluidic device offers less sample and analytes demand, precise operation, increase reproducibly of spectral responses, and enables miniaturization and portability of the presented approach. In this work, we have also investigated the effect of varying expression of the EpCAM established by the Western Blot method supported by immunochemistry on the efficiency of CTCs’ detection with the developed SERS method. We used four target cancer cell lines with relatively high (human metastatic prostate adenocarcinoma cells (LNCaP)), medium (human metastatic prostate adenocarcinoma cells (LNCaP)), weak (human metastatic prostate adenocarcinoma cells (LNCaP)), and no EpCAM expressions (cervical cancer cells (HeLa)) to estimate the limits of detection based on constructed calibration curves. Finally, blood samples from lung cancer patients were used to validate the efficiency of the developed method in clinical trials.
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