Electrochemical Biosensing and Voltammetry Based on Modified Electrodes

A special issue of Biosensors (ISSN 2079-6374). This special issue belongs to the section "Biosensor and Bioelectronic Devices".

Deadline for manuscript submissions: closed (29 April 2024) | Viewed by 12794

Special Issue Editors


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Analytical Chemistry Laboratory, Chemistry Department, Aristotle University of Thessaloniki, 54124 Thessaloniki, Greece
Interests: analytical chemistry; electroanalysis; electrochemical biosensors; chemical metrology
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Guest Editor
Chemistry Department, Analytical Chemistry Laboratory, Aristotle University of Thessaloniki, 54124 Thessaloniki, Greece
Interests: electroanalysis; electrochemical biosensors; bioanalysis nanocomposites conductive polymers, molecularly imprinted polymers

Special Issue Information

Dear Colleagues,

Chemically modified electrodes consist of electroactive monolayers as well as thicker films deposited on conductive substrates. Chemically modified electrodes possess unique properties compared to the non-modified ones. The application of chemically modified electrode surfaces with electroanalytical methods, especially voltammetry, offer the advantages of fast, portable, low-cost, sensitive, simple, and accurate alternatives in chemical analysis.

This Special Issue aims to report the development of the types as well as the basic principles and the way of making the electroactive monolayer layers, as well as the thicker films deposited on substrate conductors, which are commonly referred to as chemically modified electrodes, and their successful application in chemical analysis and problem solving in complex analytical problems.

This field of electroanalysis has been very active in recent years, and there are many review articles dealing with the construction, characterization, and electrochemical behavior of chemically modified electrodes.

Usually, to improve sensitivity and selectivity, electrodes are modified with carbon-based nanomaterials, such as multiwalled carbon nanotubes (MWCNTs), or metal nanoparticles (NPs), such as AuNPs, PtNPs, and AgNPs.

Meanwhile, conducting polymers (CP) are also of interest for their use as sensitive electrode surface coatings on electrochemical sensors and biosensors (electrode surface modifiers). They exhibit large electrical conductivity and satisfying electrochemical reversibility and can therefore be applied in sensor transducer signaling. Furthermore, CPs can be chemically acquired functional groups, which act as "tags" because of their ability to identify biological or chemical items. Recent trends in chemically modifying electrodes are building high-specific CP recognition points, which will strengthen selectivity and advance the sensitivity of the nidification procedure. In connection with the specificity of the process, molecularly imprinted polymers (MIPs) can be administered in the synthesis of polymers with predetermined molecular recognition features and can be used in constructing sensors and biosensors. Molecular imprinting is the innovation of these designs, as they enjoy plentiful improved traits: they are sensible, fast, simple, and can be portable.

The main goal of this Special Issue is to attract the attention of distinguished scholars carrying out intensive research in the field of electrochemical biosensing and voltammetry based on modified electrodes.

Dr. Stella Girousi
Dr. Sophia Karastogianni
Guest Editors

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Keywords

  • voltammetry
  • biosensing
  • electrodes
  • chemical modification
  • electroanalysis
  • conductive polymers
  • molecular imprinting

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Published Papers (5 papers)

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Research

13 pages, 1614 KiB  
Article
Bismuth Film along with dsDNA-Modified Electrode Surfaces as Promising (bio)Sensors in the Analysis of Heavy Metals in Soils
by Vasiliki Keramari, Sotiria G. Papadimou, Evangelia E. Golia and Stella Girousi
Biosensors 2024, 14(6), 310; https://doi.org/10.3390/bios14060310 - 18 Jun 2024
Cited by 1 | Viewed by 1300
Abstract
Heavy metals constitute pollutants that are particularly common in air, water, and soil. They are present in both urban and rural environments, on land, and in marine ecosystems, where they cause serious environmental problems since they do not degrade easily, remain almost unchanged [...] Read more.
Heavy metals constitute pollutants that are particularly common in air, water, and soil. They are present in both urban and rural environments, on land, and in marine ecosystems, where they cause serious environmental problems since they do not degrade easily, remain almost unchanged for long periods, and bioaccumulate. The detection and especially the quantification of metals require a systematic process. Regular monitoring is necessary because of seasonal variations in metal levels. Consequently, there is a significant need for rapid and low-cost metal determination methods. In this study, we compare and analytically validate absorption spectrometry with a sensitive voltammetric method, which uses a bismuth film-plated electrode surface and applies stripping voltammetry. Atomic absorption spectroscopy (AAS) represents a well-established analytical technique, while the applicability of anodic stripping voltammetry (ASV) in complicated sample matrices such as soil samples is currently unknown. This sample-handling challenge is investigated in the present study. The results show that the AAS and ASV methods were satisfactorily correlated and showed that the metal concentration in soils was lower than the limit values but with an increasing trend. Therefore, continuous monitoring of metal levels in the urban complex of a city is necessary and a matter of great importance. The limits of detection of cadmium (Cd) were lower when using the stripping voltammetry (SWASV) graphite furnace technique compared with those obtained with AAS when using the graphite furnace. However, when using flame atomic absorption spectroscopy (flame-AAS), the measurements tended to overestimate the concentration of Cd compared with the values found using SWASV. This highlights the differences in sensitivity and accuracy between these analytical methods for detecting Cd. The SWASV method has the advantage of being cheaper and faster, enabling the simultaneous determination of heavy elements across the range of concentrations that these elements can occur in Mediterranean soils. Additionally, a dsDNA biosensor is suggested for the discrimination of Cu(I) along with Cu(II) based on the oxidation peak of guanine, and adenine residues can be applied in the redox speciation analysis of copper in soil, which represents an issue of great importance. Full article
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10 pages, 2392 KiB  
Article
Detection of Interleukin-6 Protein Using Graphene Field-Effect Transistor
by Manoharan Arun Kumar, Ramasamy Jayavel, Shanmugam Mahalingam, Junghwan Kim and Raji Atchudan
Biosensors 2023, 13(9), 834; https://doi.org/10.3390/bios13090834 - 22 Aug 2023
Cited by 3 | Viewed by 1879
Abstract
Universal platforms to analyze biomolecules using sensor devices can address critical diagnostic challenges. Sensor devices like electrical-based field-effect transistors play an essential role in sensing biomolecules by charge probing. Graphene-based devices are more suitable for these applications. It has been previously reported that [...] Read more.
Universal platforms to analyze biomolecules using sensor devices can address critical diagnostic challenges. Sensor devices like electrical-based field-effect transistors play an essential role in sensing biomolecules by charge probing. Graphene-based devices are more suitable for these applications. It has been previously reported that Graphene Field-Effect Transistor (GFET) devices detect DNA hybridization, pH sensors, and protein molecules. Graphene became a promising material for electrical-based field-effect transistor devices in sensing biomarkers, including biomolecules and proteins. In the last decade, FET devices have detected biomolecules such as DNA molecules, pH, glucose, and protein. These studies have suggested that the reference electrode is placed externally and measures the transfer characteristics. However, the external probing method damages the samples, requiring safety measurements and a substantial amount of time. To control this problem, the graphene field-effect transistor (GFET) device is fabricated with an inbuilt gate that acts as a reference electrode to measure the biomolecules. Herein, the monolayer graphene is exfoliated, and the GFET is designed with an in-built gate to detect the Interleukin-6 (IL-6) protein. IL-6 is a multifunctional cytokine which plays a significant role in immune regulation and metabolism. Additionally, IL-6 subsidizes a variability of disease states, including many types of cancer development, and metastasis, progression, and increased levels of IL-6 are associated with a higher risk of cancer and can also serve as a prognostic marker for cancer. Here, the protein is desiccated on the GFET device and measured, and Dirac point shifting in the transfer characteristics systematically evaluates the device’s performance. Our work yielded a conductive and electrical response with the IL-6 protein. This graphene-based transducer with an inbuilt gate gives a promising platform to enable low-cost, compact, facile, real-time, and sensitive amperometric sensors to detect IL-6. Targeting this pathway may help develop treatments for several other symptoms, such as neuromyelitis optica, uveitis, and, more recently, COVID-19 pneumonia. Full article
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15 pages, 3069 KiB  
Article
Direct Identification of Label-Free Gram-Negative Bacteria with Bioreceptor-Free Concentric Interdigitated Electrodes
by Mazin Zamzami, Samer Alamoudi, Abrar Ahmad, Hani Choudhry, Mohammad Imran Khan, Salman Hosawi, Gulam Rabbani, El-Sayed Shalaan and Bassim Arkook
Biosensors 2023, 13(2), 179; https://doi.org/10.3390/bios13020179 - 23 Jan 2023
Cited by 5 | Viewed by 2634
Abstract
This investigation demonstrates an electrochemical method for directly identifying unlabeled Gram-negative bacteria without other additives or labeling agents. After incubation, the bacterial cell surface is linked to the interdigitated electrode through electroadsorption. Next, these cells are exposed to a potential difference between the [...] Read more.
This investigation demonstrates an electrochemical method for directly identifying unlabeled Gram-negative bacteria without other additives or labeling agents. After incubation, the bacterial cell surface is linked to the interdigitated electrode through electroadsorption. Next, these cells are exposed to a potential difference between the two electrodes. The design geometry of an electrode has a significant effect on the electrochemical detection of Gram-negative bacteria. Therefore, electrode design geometry is a crucial factor that needs to be considered when designing electrodes for electrochemical sensing. They provide the area for the reaction and are responsible for transferring electrons from one electrode to another. This work aims to study the available design in the commercial market to determine the most suitable electrode geometry with a high detection sensitivity that can be used to identify and quantify bacterial cells in normal saline solutions. To work on detecting bacterial cells without the biorecognition element, we have to consider the microelectrode’s design, which makes it very susceptible to bacteria size. The concentration–dilution technique measures the effect of the concentration on label-free Gram-negative bacteria in a normal saline solution without needing bio-recognized elements for a fast screening evaluation. This method’s limit of detection (LOD) cannot measure concentrations less than 102 CFU/mL and cannot distinguish between live and dead cells. Nevertheless, this approach exhibited excellent detection performance under optimal experimental conditions and took only a few hours. Full article
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14 pages, 3708 KiB  
Article
Zip Nucleic Acid-Based Genomagnetic Assay for Electrochemical Detection of microRNA-34a
by Arzum Erdem and Ece Eksin
Biosensors 2023, 13(1), 144; https://doi.org/10.3390/bios13010144 - 15 Jan 2023
Cited by 7 | Viewed by 2988
Abstract
Zip nucleic acid (ZNA)-based genomagnetic assay was developed herein for the electrochemical detection of microRNA-34a (miR-34a), which is related to neurological disorders and cancer. The hybridization between the ZNA probe and miR-34a target was performed in the solution phase; then, the resultant hybrids [...] Read more.
Zip nucleic acid (ZNA)-based genomagnetic assay was developed herein for the electrochemical detection of microRNA-34a (miR-34a), which is related to neurological disorders and cancer. The hybridization between the ZNA probe and miR-34a target was performed in the solution phase; then, the resultant hybrids were immobilized onto the surface of magnetic beads (MBs). After magnetic separation, the hybrids were separated from the surface of MBs and then immobilized on the surface of pencil graphite electrodes (PGEs). In the case of a full-match hybridization, the guanine oxidation signal was measured via the differential pulse voltammetry (DPV) technique. All the experimental parameters that influenced the hybridization efficiency (i.e., hybridization strategy, probe concentration, hybridization temperature, etc.) were optimized. The cross-selectivity of the genomagnetic assay was tested against two different miRNAs, miR-155 and miR-181b, individually as well as in mixture samples. To show the applicability of the ZNA-based genomagnetic assay for miR-34a detection in real samples, a batch of experiments was carried out in this study by using the total RNA samples isolated from the human hepatocellular carcinoma cell line (HUH-7). Full article
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10 pages, 2250 KiB  
Article
Voltammetry Peak Tracking for Longer-Lasting and Reference-Electrode-Free Electrochemical Biosensors
by Adam McHenry, Mark Friedel and Jason Heikenfeld
Biosensors 2022, 12(10), 782; https://doi.org/10.3390/bios12100782 - 22 Sep 2022
Cited by 7 | Viewed by 2859
Abstract
Electrochemical aptamer-based sensors offer reagent-free and continuous analyte measurement but often suffer from poor longevity and potential drift even with a robust 3-electrode system. Presented here is a simple, software-enabled approach that tracks the redox-reporter peak in an electrochemical aptamer-based sensor and uses [...] Read more.
Electrochemical aptamer-based sensors offer reagent-free and continuous analyte measurement but often suffer from poor longevity and potential drift even with a robust 3-electrode system. Presented here is a simple, software-enabled approach that tracks the redox-reporter peak in an electrochemical aptamer-based sensor and uses the measurement of redox peak potential to reduce the scanning window to a partial measure of redox-peak-height vs. baseline (~10X reduction in voltage range). This same measurement further creates a virtual reference standard in buffered biofluids such as blood and interstitial fluid, thereby eliminating the effects of potential drift and the need for a reference electrode. The software intelligently tracks voltammogram peak potential via the inflection points of the rising and falling slopes of the measured redox peak. Peak-tracking-derived partial scanning was validated over several days and minimized electrochemically induced signal loss to <5%. Furthermore, the peak-tracking approach was shown to be robust against confounding effects such as fouling. From an applied perspective in creating wearable biosensors, the peak-tracking approach further enables use of a single implanted working electrode, while the counter/reference-electrode may utilize a simple gel-pad electrode on the surface of the skin, compared to implanting working, counter, and reference electrodes conventionally used for stability and reliability but is also costly and invasive. Cumulatively, peak-tracking provides multiple leaps forward required for practical molecular monitoring by extending sensor longevity, eliminating potential drift, simplifying biosensor device construction, and in vivo placement for any redox-mediated sensor that forms parabolic-like data. Full article
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