Bipolar Spectroelectrochemistry

Bipolar electrochemistry is receiving growing attention in the last years, not only because it is an important tool for studying electron transfer processes, but also because it is really fruitful in the development of new analytical sensors. Bipolar electrodes show promising applications as a direct analytical tool since oxidation and reduction reactions take place simultaneously on different parts of a single conductor. There are several electrochemical devices that provide information about electron transfer between two immiscible electrolyte solutions, but to the best of our knowledge, this is the first time that a bipolar device is able to record two spectroelectrochemical responses concomitantly at two different compartments. It allows deconvolving the electrochemical signal into two different optical signals related to the electron transfer processes occurring at two compartments that are electrically in contact. The combination of an electrochemical and two spectroscopic responses is indeed very useful, providing essential advantages in the study of a huge variety of systems. The study of three different electrochemical systems, such as reversible redox couples, carbon nanotubes, and conducting polymers has allowed us to validate the new cell and to demonstrate the capabilities of this technique to obtain valuable time-resolved information related to the electron transfer processes

Direct Determination of Ascorbic Acid in a Grapefruit: Paving the Way for In Vivo Spectroelectrochemistry

The study of real samples is more complicated than the study of other systems. However, the inherent advantages of UV–vis absorption spectroelectrochemistry should overcome some difficulties related to direct measurements in complex matrices. For this reason, a singular spectroelectrochemistry device has been fabricated and validated. The novel cell is based on single-walled carbon nanotubes, which are filtered and subsequently press-transferred on a polyethylene terephthalate support using a stencil with a custom design. With this new methodology, working, counter, and reference electrodes are completely flat on the surface, where two optical fibers are fixed in a long optical path length configuration. To demonstrate the usefulness of this device and the power of spectroelectrochemistry techniques to solve problems of the current world, this device is used to quantitatively detect the concentration of ascorbic acid in a complex matrix such as a fruit, directly, without any previous sample pretreatment. The ease to fabricate the device, the advantages related to its use, and the excellent results obtained not only with univariate but also with multivariate analysis, shed more light on the analysis of samples as they occur in nature. According to the particular features of this cell, to the best of our knowledge this is the first spectroelectrochemical sensor that can be inserted directly in a biological matrix, laying the groundwork to perform in vivo measurements in a near future

Simultaneous UV–Visible Absorption and Raman Spectroelectrochemistry

The development of a new device based on the use of UV–vis bare optical fibers in a long optical path length configuration and the measurement of the Raman response in normal arrangement allows us to perform UV–vis and Raman spectroelectrochemistry simultaneously in a single experiment. To the best of our knowledge, this is the first time that a spectroelectrochemistry device is able to record both spectroscopic responses at the same time, which further expands the versatility of spectroelectrochemistry techniques and enables us to obtain much more high-quality information in a single experiment. Three different electrochemical systems, such as ferrocyanide, dopamine, and 3,4-ethylenedioxythiophene, have been studied to validate the cell and to demonstrate the performance of the device. Processes that take place in solution can be properly distinguished from processes that occur on the electrode surface during the electrochemical experiment, providing a whole picture of the reactions taking place at the electrode/solution interface. Therefore, this device allows us to study a larger number of complex electrochemical processes from different points of view taking into account not only the UV–vis spectral changes in the solution adjacent to the electrode but also the Raman signal at any location. Furthermore, complementary information, which could not be unambiguously extracted without considering together the two spectroscopic signals and the electrochemical response, is obtained in a novel way

Spectroelectrochemistry at Screen-Printed Electrodes: Determination of Dopamine

A new device to perform spectroelectrochemical measurements in the UV/visible spectral region using screen-printed electrodes has been developed. Neurotransmitter dopamine has been selected as a proof of concept of the capabilities of the new device. The results obtained have allowed us both to study the oxidation mechanism of dopamine and to carry out the spectroelectrochemical detection of this neurotransmitter. Differences in dopamine oxidation mechanism have been observed depending on the initial concentration. Thus, dopamine concentrations lower than 10^–3 M led to a higher generation of dopaminochrome and its derivatives with a band centered at 305 nm, which was the best wavelength to determine dopamine spectrophotometrically at these concentrations. However, if dopamine concentration is higher than 10^–3 M, dopaminoquinone is stable enough to use its maximum of absorbance, 395 nm, to detect this neurotransmitter. Dopamine concentration can also be calculated from the electrochemical data in spectroelectrochemistry, the results being comparable to that obtained from spectroscopic data. Comparison between spectrophotometric and electrochemical determinations demonstrates that the two methods measure this analyte indistinctively, proving that spectroelectrochemistry represents an autovalidated technique. Partial least-squares regression has also been used, obtaining good results in the full dopamine concentration range. Finally, as spectroelectrochemistry is an intrinsically trilinear technique, PARAFAC has been used to study the effect of probable interfering species

Development of a Novel Bidimensional Spectroelectrochemistry Cell Using Transfer Single-Walled Carbon Nanotubes Films as Optically Transparent Electrodes

A really easy method to transfer commercial single-walled carbon nanotubes (SWCNTs) to different substrates is proposed. In this paper, a homogeneous transference of SWCNTs films to nonconductor and transparent supports, such as polyethylene terephthalate, glass, and quartz, and to conductor supports, such as indium tin oxide, aluminum, highly ordered pyrolytic graphite, and glassy carbon, was achieved using a very fast, reproducible, and clean methodology. In order to test these transferences, SWCNTs films transferred on quartz were used as working optically UV–vis transparent electrodes due to their optimal electrical and optical properties. A new easy-to-use, homemade optical fiber based cell for bidimensional spectroelectrochemistry was developed, offering the possibility to measure in normal and parallel configuration. The cell was tested with ferrocenemethanol, a compound widely used in electrochemistry but scarcely studied by spectroelectrochemistry, covering the UV–vis spectral region

Study of Adenine and Guanine Oxidation Mechanism by Surface-Enhanced Raman Spectroelectrochemistry

Metal nanoparticles are systems largely employed in surface-enhanced Raman spectroscopy (SERS). In particular, gold nanoparticles are one of the best substrates used in this field. In this work, the optimal conditions for gold nanoparticles electrodeposition on single-walled carbon nanotubes electrodes have been established to obtain the best SERS response. Using this substrate and analyzing the changes of in situ Raman spectra obtained at different potentials, we have been able to explain simultaneously the oxidation mechanism of purine bases, differentiating the oxidation intermediates and their orientation during the different oxidation steps. Adenine orientation hardly changes during the whole oxidation; the molecule maintains a parallel configuration and only shows a slightly tilted orientation after the first oxidation step. On the other hand, guanine orientation changes completely during its oxidation. Initially, guanine is perpendicular respect to gold nanoparticles, changing its orientation after the first oxidation process when the molecule shows a slightly tilted orientation, and it finishes parallel respect to the electrode surface after the second oxidation step

Janus Electrochemistry: Asymmetric Functionalization in One Step

Janus structures represent an overwhelming member of materials with adaptable chemical and physical properties. Development of new synthesis routes has allowed the fabrication of Janus architectures with specific characteristics depending on the final applications. In the case of the membranes, the improvement of wet routes has been limited to the capillary effect, in which the solution can gradually penetrate through the membrane, avoiding a double modification different at each face of the membrane. In this work, we propose a new electrochemical methodology to circumvent the capillary limitation and obtain a double electrochemical functionalization in only one step in a controlled way. This innovative methodology has been validated using a tridirectional spectroelectrochemistry setup. Moreover, the information provided by this optical arrangement should be especially useful for the study of the different processes (ion transfer, assisted ion transfer, and electron transfer) that can take place at liquid/liquid interfaces. Janus electrochemistry allows us to modify the two faces of a free-standing single-walled carbon nanotube electrode in a single experiment. As proof of concept, the free-standing films have been functionalized with two different conducting polymers, polyaniline and poly­(3-hexylthiophene), in one electrochemical experiment. According to the obtained results, this new electrochemical methodology will open new gates for the design and functionalization of Janus materials

In-situ Evidence of the Redox-State Dependence of Photoluminescence in Graphene Quantum Dots

Changes in the optical properties of graphene quantum dots (GQD) during electrochemical reduction and oxidation were investigated by photoluminescence (PL) spectroelectrochemistry, which provided direct in situ evidence of the dependence of GQD luminescence on their redox state. We demonstrated that GQD PL intensity was enhanced upon reduction (quantum yield increased from 0.44 to 0.55) and substantially bleached during oxidation (quantum yield ∼0.12). Moreover, PL emission blue/red-shifted upon GQD reduction/oxidation, rendering information about electronic transitions involved in the redox processes, namely, the π → π* and the <i>n</i> → π* transitions between energy levels of the aromatic sp² domains and the functional groups, respectively. PL intensity changes during GQD reduction/oxidation resulted from a variation in structural changes in GQD as a result of charge injection, as corroborated by in situ Raman spectroelectrochemistry

Silver hexacyanoferrate (II) nanocrystals as a new material to improve Raman scattering enhancement during silver surface oxidation

Raman spectroscopy is a powerful analysis technique that shows its full potential when a high amplification of the Raman signal is achieved. In this sense, Surface-Enhanced Raman scattering (SERS) has been the most widely used phenomenon for analysis. SERS provides the amplification of the Raman intensity due to the interaction of molecules with a plasmonic nanostructured surface. The enhancement of the Raman signal can be also obtained during the electrochemical oxidation of a metal electrode; this phenomenon was denoted as Electrochemical-Surface Oxidation Enhanced Raman Scattering (EC-SOERS) and yields a good Raman signal enhancement with high reproducibility. Until now, only chloride and bromide have been employed in EC-SOERS, using a silver electrode to generate silver chloride and silver bromide nanocrystals. In this work, a new EC-SOERS substrate based on the electrogeneration of silver hexacyanoferrate (II) nanocrystals is presented which provides a very sensitive Raman response. The electrogeneration of this new material can be easily followed using spectroelectrochemistry since the characteristic Raman bands of the nanocrystals lie outside of the fingerprint region used for the analysis where the detection of most of the target molecules is performed. Indigo Carmine has been selected as target molecule, obtaining a very good response at nanomolar level under Raman resonance and non-resonance conditions.</p

Raman, UV−Vis absorption, and fluorescence spectroelectrochemistry for studying the enhancement of the Raman scattering using nanocrystals activated by metal cations

Raman signal enhancement is fundamental to develop different analytical tools for chemical analysis, interface reaction studies, or new materials characterization, among others. Thus, phenomena such as surface-enhanced Raman scattering (SERS) have been used for decades to increase the sensitivity of Raman spectroscopy, leading to a huge development of this field. Recently, an alternative method to SERS for the amplification of Raman signals has been reported. This method, known as electrochemical surface oxidation-enhanced Raman scattering (EC-SOERS), has been experimentally described. However, to date, it has not yet been fully understood. In this work, new experimental data that clarify the origin of the Raman enhancement in SOERS are provided. The use of a complete and unique set of combined spectroelectrochemistry techniques, including time-resolved operando UV−vis absorption, fluorescence, and Raman spectroelectrochemistry, reveals that such enhancement is related to the generation of dielectric or semiconductor nanocrystals on the surface of the electrode and that the interaction between the target molecule and the dielectric substrate is mediated by metal cations. According to these results, the interaction metal electrode−nanocrystal−metal cation−molecule is proposed as being responsible for the Raman enhancement in Ag and Cu substrates. Elucidation of the origin of the Raman enhancement will help to promote the rational design of SOERS substrates as an attractive alternative to the well-known SERS phenomenon.</p