RESUMO
Practical implementation of surfaced enhanced Raman spectroscopy (SERS) sensing is hindered by complexity of real-life samples, which often requires long and costly pretreatment and purification. Here, we present a novel nanopillar-assisted SERS chromatography (NPC-SERS) method for simultaneous quantitation of target molecules and analysis of complex, multicomponent fluids, e.g., human urine spiked with a model drug paracetamol (PAR). Gold-coated silicon nanopillar (AuNP) SERS substrates and a centrifugal microfluidic platform are tactfully combined, which allows (i) a precise and fully automated sample manipulation and (ii) spatial separation of different molecular species on the AuNP substrate. The NPC-SERS technique provides a novel approach for wetting the stationary phase (AuNP) using the "wicking effect", and thus minimizes dilution of analytes. Separation of PAR and the main human urine components (urea, uric acid, and creatinine) has been demonstrated. Quantitative detection of PAR with ultrawide linear dynamic range (0-500 ppm) is achieved by analyzing the spreading profiles of PAR on the AuNP surface. NPC-SERS transforms SERS into a sensing technique with general applicability, facilitating rapid and quantitative detection of analytes in complex biofluids, such as saliva, blood, and urine.
Assuntos
Cromatografia/métodos , Nanopartículas Metálicas/química , Análise Espectral Raman/métodos , Acetaminofen/urina , Ação Capilar , Creatinina/urina , Ouro/química , Humanos , Microfluídica/métodos , Silício/química , Ureia/urina , Ácido Úrico/urinaRESUMO
In this work, we present a dual-functional sensor that can perform surface-enhanced Raman spectroscopy (SERS) based identification and electrochemical (EC) quantification of analytes in liquid samples. A lithography-free reactive ion etching process was utilized to obtain nanostructures of high aspect ratios distributed homogeneously on a 4 in. fused silica wafer. The sensor was made up of three-electrode array, obtained by subsequent e-beam evaporation of Au on nanostructures in selected areas through a shadow mask. The SERS performance was evaluated through surface-averaged enhancement factor (EF), which was â¼6.2 × 105, and spatial uniformity of EF, which was â¼13% in terms of relative standard deviation. Excellent electrochemical performance and reproducibility were revealed by recording cyclic voltammograms. On nanostructured electrodes, paracetamol (PAR) showed an improved quasi-reversible behavior with decrease in peak potential separation (ΔEp â¼ 90 mV) and higher peak currents (Ipa/Ipc â¼ 1), compared to planar electrodes (ΔEp â¼ 560 mV). The oxidation potential of PAR was also lowered by â¼80 mV on nanostructured electrodes. To illustrate dual-functional sensing, quantitative evaluation of PAR ranging from 30 µM to 3 mM was realized through EC detection, and the presence of PAR was verified by its SERS fingerprint.
Assuntos
Técnicas Eletroquímicas/métodos , Nanopartículas Metálicas/química , Análise Espectral Raman/métodos , Acetaminofen/análise , Eletrodos , Ouro/química , Oxirredução , Propriedades de SuperfícieRESUMO
We present a simple, robust, and automated molecule extraction technique based on a centrifugal microfluidic platform. Fast and facile extraction of a food adulterant (melamine) from a complex sample medium (milk) on a SERS substrate is demonstrated. The unique characteristic of the detection method is the obtained "filter paper/chromatographic" effect which combines centrifugal force and wetting properties of the SERS substrate. The work addresses issues related to SERS-based detection of analytes in complex media, which is important for realizing next generation SERS platforms applicable for a broad variety of real-life applications.