Ordered Mesoporous Electrodes for Sensing Applications.

Electrochemical sensors have become increasingly relevant in fields such as medicine, environmental monitoring, and industrial process control. Selectivity, specificity, sensitivity, signal reproducibility, and robustness are among the most important challenges for their development, especially when the target compound is present in low concentrations or in complex analytical matrices. In this context, electrode modification with Mesoporous Thin Films (MTFs) has aroused great interest in the past years. MTFs present high surface area, uniform pore distribution, and tunable pore size. Furthermore, they offer a wide variety of electrochemical signal modulation possibilities through molecular sieving, electrostatic or steric exclusion, and preconcentration effects which are due to mesopore confinement and surface functionalization. In order to fully exploit these advantages, it is central to develop reproducible routes for sensitive, selective, and robust MTF-modified electrodes. In addition, it is necessary to understand the complex mass and charge transport processes that take place through the film (particularly in the mesopores, pore surfaces, and interfaces) and on the electrode in order to design future intelligent and adaptive sensors. We present here an overview of MTFs applied to electrochemical sensing, in which we address their fabrication methods and the transport processes that are critical to the electrode response. We also summarize the current applications in biosensing and electroanalysis, as well as the challenges and opportunities brought by integrating MTF synthesis with electrode microfabrication, which is critical when moving from laboratory work to in situ sensing in the field of interest.

Modification of electrodes with polymer nanocomposites: Application to the simultaneous determination of Zn(II), Cd(II), and Cu(II) in water samples.

Currently, there is a need for fast and sensitive analytical methods for monitoring metals in water due to the progressive increase in the presence of metal ions in the environment. These metals reach the environment mainly from industrial activity and heavy metals are non-biodegradable. The present work evaluates different polymeric nanocomposites to carry out the simultaneous electrochemical determination of Cu, Cd, and Zn in water samples. Screen-printed carbon electrodes (SPCE) were modified with the nanocomposites, which were obtained by a mixture of graphene, graphite oxide, and polymers, such as polyethyleneimide, gelatin, and chitosan. These polymers have amino groups in their matrix, giving the nanocomposite the ability to retain divalent cations. However, the availability of these groups plays a fundamental role in the retention of these metals. The modified SPCEs were characterized by scanning electron microscopy, Fourier-transform infrared spectroscopy, electrochemical impedance spectroscopy, and cyclic voltammetry. The electrode that presented the best performance was selected to determine the concentration of metal ions in water samples by square-wave anodic stripping voltammetry. The obtained detection limits were 0.23 µg L-1, 0.53 µg L-1, and 1.52 µg L-1 for Zn(II), Cd(II), and Cu(II), respectively, with a lineal range of 0.1-50 µg L-1. The obtained results made it possible to conclude that the method developed using the SPCE modified with the polymeric nanocomposite presented adequate LODs, reasonable sensitivity, selectivity, and reproducibility. Besides, this platform is an excellent tool for developing devices to simultaneously determine heavy metals in environmental samples.

Novel solid inks based on beeswax, graphite and graphene applied to the fabrication of paper-based sensor for galactose determination.

In this study, we present for the first time a simple and novel method for the fabrication of paper-based electrochemical sensors. The device development was carried out in a single stage with a standard wax printer. Hydrophobic zones were delimited with commercial solid ink, while electrodes were generated using new composite solid inks of graphene oxide/graphite/beeswax (GO/GRA/beeswax) and graphite/beeswax (GRA/beeswax). Subsequently, the electrodes were electrochemically activated by applying an overpotential. Various experimental variables for the GO/GRA/beeswax composite synthesis and electrochemical system obtention were evaluated. The activation process was examined by SEM, FTIR, cyclic voltammetry, electrochemical impedance spectroscopy and contact angle measurement. These studies showed morphological and chemical changes in the electrode active surface. As a result, the activation stage considerably improved the electron transfer on the electrode. The manufactured device was successfully applied for galactose (Gal) determination. This method presented a linear relation in the Gal concentration range from 84 to 1736 µmol L-1, with a LOD of 0.1 µmol L-1. The variation within and between-assay coefficients were 5.3% and 6.8%, respectively. The strategy here exposed for paper-based electrochemical sensors design is an unprecedented alternative system and represents a promising tool for mass production of economic analytical devices.

Paper surface modification strategies employing N-SBA-15/polymer composites in bioanalytical sensor design.

In this work, different paper surface modification strategies were compared to obtain an amine functionalized SBA-15 (N-SBA-15) composite for paper-based device development. The synthesized N-SBA-15 was characterized by N2 adsorption-desorption isotherm, and infrared spectroscopy (FTIR), and it was incorporated to different polymer matrices (κ-carrageenan (CA), polyvinyl alcohol (PVA) and polyethylenimine (PEI)) for the development of the composite modified paper-based device. The retention, interactions, and morphology of the obtained composites were investigated by absorbance measurement, FTIR and scanning electron microscopy (SEM), respectively. To demonstrate the applicability of the modified paper-based device, ascorbic acid (AA) quantification was carried out. Horseradish peroxidase (HRP) was immobilized onto the modified paper surface. HRP in the presence of H2O2 catalyzes the oxidation of 10-acetyl-3,7-dyhidroxyphenoxazine (ADHP) to highly fluorescent resorufin, which was measured by LIF detector. Thus, when AA was added to the solution, it decreases the relative fluorescence signal proportionally to the AA concentration. The linear range from 50 nmol L-1 to 1500 nmol L-1 and a detection limit of 15 nmol L-1 were obtained for AA quantitation. The obtained results allowed us to conclude that N-SBA-15/PEI composite could be considered an excellent choice for the paper-based device modification procedure due to its inherent simplicity, low cost, and sensitivity.

Novel electrochemical sensing platform based on a nanocomposite of PVA/PVP/RGO applied to IgG anti- Toxoplasma gondii antibodies quantitation.

This article describes the development of a new electrochemical platform composed by a polymer mixture and graphene oxide (GO). The working electrode of a screen-printed carbon electrode (SPCE) was modified with nanocomposite constituted by poly-vinyl alcohol (PVA), poly-vinylpyrrolidone (PVP) and GO, which was electrochemically reduced to obtain PVA/PVP/RGO/SPCE. The interactions and morphology of the PVA/PVP/GO nanocomposite were investigated by SEM, FTIR and UV-Vis. SEM images indicated an excellent dispersion of the GO sheets in the polymer matrix. Besides, FTIR and visible UV studies revealed strong interactions between polymer mixture and GO sheets. According to electrochemical studies, the new platform increased the electroactive surface area by a factor of 20.46 compared to the unmodified SPCE. Also, the PVA/PVP/RGO/SPCE had a fast electron kinetics transfer process with a value of ks = 9.6 s-1. The modified electrode was applied to the determination of IgG anti-T. gondii antibodies for the serological diagnosis of toxoplasmosis. The IgG anti-T. gondii antibodies quantification showed a detection limit of 0.012 U mL-1, and the coefficients of variation intra-day and inter-day assays were lower than 4.5% and 6.2%, respectively. The electrochemical platform proved to be a sensitive and easily applicable tool applied to the serological diagnosis of toxoplasmosis. Therefore, the developed nanocomposite represents an excellent alternative for the electrochemical biosensor fabrication.

Novel Electrochemical Paper-Based Immunocapture Assay for the Quantitative Determination of Ethinylestradiol in Water Samples.

We report a novel and innovative electrochemical paper-based immunocapture assay (EPIA) to address the need for ultrasensitive detection of emerging pollutants without regulatory status and whose effects on environment and human health are not completely yet understood. In particular, we present the application of this system toward highly sensitive detection of the emerging pollutant ethinyl estradiol (EE2). The EPIA approach is based on the use of paper microzones modified with silica nanoparticles (SNs) and anti-EE2 specific antibodies for capture and preconcentration of EE2 from river water samples. After the preconcentration procedure, the paper microzones are placed onto a screen-printed carbon electrode modified with electrochemically reduced graphene (RG). The bound EE2 is subsequently desorbed adding a diluted solution of sulfuric acid on the paper microzones. Finally, recovered EE2 is electrochemically detected by OSWV. The proposed novel methodology showed an appropriate LOD and linear range for the quantification of EE2 for water samples with different origins. The nonsophisticated equipment required, the adequate recovery values obtained (from 97% to 104%, with a RSD less than 4.9%), and the appropriate LOD and linear range value (0.1 ng L-1 and 0.5-120 ng L-1, respectively) achieved by our immunocapture sensor present significant analytical figures of merit, particularly when the routine quantification of EE2 is considered. In addition, our system was based on electrochemical paper-based technology, which allows obtainment of portable, easy-to-use, inexpensive, and disposable devices. The EPIA can also serve as a general-purpose immunoassay platform applicable to quantitation of other drugs and emerging pollutants in environmental samples.