RESUMO
In this work, we present a multiphysics modeling approach capable of simulating electrochemical impedance spectroscopy (EIS) responses of screen-printed electrodes (SPEs) modified with self-assembled monolayers of 11-Mercaptoundecanoic acid (MUA). Commercially available gold SPEs are electrochemically characterized through experimental cyclic voltammetry and EIS measurements with 10 mM [Fe(CN)6]3-/4- redox couple in phosphate buffered saline before and after the surface immobilization of MUA at different concentrations. We design the multiphysics model through COMSOL Multiphysics® based on the 3D geometry of the devices under test. The model includes four different physics considering the metal/solution interface electrochemical phenomena, the ion and electron potentials and currents, and the measurement set-up. The model is calibrated through a set of experimental measurements, allowing the tuning of the parameters used by the model. We use the calibrated model to simulate the EIS response of MUA-modified SPEs, comparing the results with experimental data. The simulations fit the experimental curves well, following the variation of MUA concentration on the surface from 1 µM to 100 µM. The EIS parameters, retrieved through a CPE-modified Randles' circuit, confirm the consistency with the experimental data. Notably, the simulated surface coverage estimates and the variation of charge transfer resistance due to MUA-immobilization are well matched with their experimental counterparts, reporting only a 2% difference and being consistent with the experimental electrochemical behavior of the SPEs.
RESUMO
Surface plasmon resonance (SPR) is a common and useful measurement technique to perform fast and sensitive optical detection. SPR instrumentations usually comprise optical systems of mirrors and lenses which are quite expensive and impractical for point-of-care applications. In this work, we presented a novel and compact SPR device called SPECTRA, designed as a spectrophotometer add-on with a grating coupling configuration. The device is conceived as a marketable solution to perform quick SPR measurements in grating configuration without the requirement of complex instrumentation. The device can be customized either in a vertical structure to reach lower incident light angles, or in a horizontal configuration, which is suitable for SPR analysis using liquid solutions. The SPECTRA performance was evaluated through SPR measurements in typical applications. The vertical SPECTRA system was employed to detect different functionalization molecules on gold 720 nm-period grating devices. Meanwhile, the horizontal SPECTRA configuration was exploited to carry out fluid-dynamic measurements using a microfluidic cell with glycerol solutions at increasing concentrations to account for different refractive indexes. The experimental tests confirmed that the SPECTRA design is suitable for SPR measurements, demonstrating its capability to detect the presence of analytes and changes in surface properties both in static and dynamic set-ups.
RESUMO
The blood ammonia (NH3) level is one of the most important hepatic biomarkers for the diagnosis and monitoring of liver pathologies and infections. In this work, we developed an optimized optical biosensing method to extract and quantify the ammonia contained in complex-matrix samples emulating the blood serum. First, the approach was tested with solutions of phosphate-buffered saline (PBS) and ammonia chloride. Then, further trials were carried out with solutions of fetal bovine serum (FBS). The ammonia was extracted from the tested samples through a customized cell, and it was optically quantified by exploiting the indophenol reaction. The extraction cell included a cation-exchange membrane in Nafion, which was chemically pre-treated through cleaning procedures of sulfuric acid and hydrogen peroxide to keep a basic pH in the ammonia solution and to avoid contaminants in the membrane. From the NH3 solution, the indophenol reaction produced light-reactive indophenol dye molecules, which were used as colorimetric indicators. Through absorbance measurements of the indophenol dye solution at 670 nm wavelength, we were able to detect and quantify the ammonia level in the samples both with a spectrophotometer and a customized miniaturized read-out system, obtaining a detection limit of 0.029 µmol/mL.