Electrochemistry and Spectroscopy-Based Biosensors

A special issue of Biosensors (ISSN 2079-6374). This special issue belongs to the section "Optical and Photonic Biosensors".

Deadline for manuscript submissions: closed (31 October 2022) | Viewed by 23665

Special Issue Editor

Group of Supramolecular Analysis at Institute of Biochemistry, Life Sciences Centre, Vilnius University, LT-10257 Vilnius, Lithuania
Department of Functional Materials and Electronics at Center for Physical Sciences and Technology, Saulėtekio av. 3, Vilnius, LT-10257, Lithuania
Interests: supramolecular chemistry; self-assembled monolayers-based sensors; molecular imprinted polymers; DET-based biosensors; enzymes for non-natural chemistry; theoretical chemistry
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleague,

We invite the submission of research articles and reviews to a Special Issue of the open access Biosensors journal (Q1 in the categories of Analytical Chemistry and Instruments & Instrumentation). Your recent discoveries and improvements to biosensors in the topics of electrochemistry and spectroscopy are welcome. This Special Issue of Biosensors provides the most recent progress and unique advantages in these areas.

Many electrochemistry and spectroscopy methods have been widely employed to analyze and detect glucose, urea, neuromediators, RNA, and other bioanalytes and biomarkers for industrial and food process control, or analysis of biological and medical samples. These methods of bioanalysis are also important in the fight against the COVID-19 pandemic. Therefore, this issue welcomes contributions utilizing the ultraviolet, visible, infrared, THz wavelength regions sensing via direct absorption or reflection, as well as Raman, total internal reflection ellipsometry, fluorescence, Plasmon-enhanced, or other spectroscopic processes. Furthermore, the application of electrochemical impedance spectroscopy and amperometry or potentiometry for biosensors, studies of a direct electron transfer through enzymes, mediator-based processes, and analyses of biological structures at strong magnetic and electric fields are welcome.

Dr. Gintautas Bagdziunas
Guest Editor

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Keywords

  • Optical/infrared/terahertz biosensors
  • Raman spectroscopy-based
  • Fluorescence-based
  • Electrochemical impedance spectroscopy
  • Direct electron transfer
  • Mediator-based
  • DNR-based
  • Molecular imprinted polymers
  • Total internal reflection ellipsometry
  • Amperometric/potentiometric biosensors
  • Plasmon-enhanced spectroscopy-based

Published Papers (11 papers)

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Editorial

Jump to: Research, Review

2 pages, 180 KiB  
Editorial
Electrochemistry and Spectroscopy-Based Biosensors
by Gintautas Bagdžiūnas
Biosensors 2023, 13(1), 9; https://doi.org/10.3390/bios13010009 - 22 Dec 2022
Viewed by 983
Abstract
During and after the COVID-19 pandemic, the development of low-cost detection and analysis methods of bioanalytes as well as infection biomarkers became an increasingly important challenge in order to improve public and personal health [...] Full article
(This article belongs to the Special Issue Electrochemistry and Spectroscopy-Based Biosensors)

Research

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13 pages, 1308 KiB  
Article
Selective Sensing of Darolutamide and Thalidomide in Pharmaceutical Preparations and in Spiked Biofluids
by Wael Talaat, Abdelbasset A. Farahat and Reda Mohammed Keshk
Biosensors 2022, 12(11), 1005; https://doi.org/10.3390/bios12111005 - 11 Nov 2022
Cited by 5 | Viewed by 1362
Abstract
Selective spectrofluorometric sensing is introduced for the analysis of non-steroidal anti-androgens, darolutamide, and thalidomide in pharmaceutical preparations and biofluids. An organic fluorophore, 2,4,8,10-tetramethylpyrido[2′,3′:3,4]pyrazolo[1,5-a]pyrimidine 2 was synthesized in our laboratories by new simple methods to act as a fluorescent reagent for the analysis of [...] Read more.
Selective spectrofluorometric sensing is introduced for the analysis of non-steroidal anti-androgens, darolutamide, and thalidomide in pharmaceutical preparations and biofluids. An organic fluorophore, 2,4,8,10-tetramethylpyrido[2′,3′:3,4]pyrazolo[1,5-a]pyrimidine 2 was synthesized in our laboratories by new simple methods to act as a fluorescent reagent for the analysis of the studied drugs. Elemental and spectral analyses were performed to approve the fluorophore structure. The fluorophore possesses a fluorescence at λem 422 nm when excited at 328 nm. The interaction between the studied drugs and the fluorophore was found to be quenching. The quenching mechanisms were studied and interpreted through the Stern–Volmer relationship. Moreover, the Stern–Volmer constants were calculated for the quenching interactions of both drugs. The introduced method was validated for the estimation of darolutamide and thalidomide in dosage forms, plasma, and urine, offering good percentage recoveries. Full article
(This article belongs to the Special Issue Electrochemistry and Spectroscopy-Based Biosensors)
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12 pages, 1463 KiB  
Article
Threonine Phosphorylation of an Electrochemical Peptide-Based Sensor to Achieve Improved Uranyl Ion Binding Affinity
by Channing C. Thompson and Rebecca Y. Lai
Biosensors 2022, 12(11), 961; https://doi.org/10.3390/bios12110961 - 02 Nov 2022
Cited by 3 | Viewed by 1480
Abstract
We have successfully designed a uranyl ion (U(VI)-specific peptide and used it in the fabrication of an electrochemical sensor. The 12-amino acid peptide sequence, (n) DKDGDGYIpTAAE (c), originates from calmodulin, a Ca(II)-binding protein, and contains a phosphothreonine that enhances the sequence’s affinity for [...] Read more.
We have successfully designed a uranyl ion (U(VI)-specific peptide and used it in the fabrication of an electrochemical sensor. The 12-amino acid peptide sequence, (n) DKDGDGYIpTAAE (c), originates from calmodulin, a Ca(II)-binding protein, and contains a phosphothreonine that enhances the sequence’s affinity for U(VI) over Ca(II). The sensing mechanism of this U(VI) sensor is similar to other electrochemical peptide-based sensors, which relies on the change in the flexibility of the peptide probe upon interacting with the target. The sensor was systematically characterized using alternating current voltammetry (ACV) and cyclic voltammetry. Its limit of detection was 50 nM, which is lower than the United States Environmental Protection Agency maximum contaminant level for uranium. The signal saturation time was ~40 min. In addition, it showed minimal cross-reactivity when tested against nine different metal ions, including Ca(II), Mg(II), Pb(II), Hg(II), Cu(II), Fe(II), Zn(II), Cd(II), and Cr(VI). Its reusability and ability to function in diluted aquifer and drinking water samples were further confirmed and validated. The response of the sensor fabricated with the same peptide sequence but with a nonphosphorylated threonine was also analyzed, substantiating the positive effects of threonine phosphorylation on U(VI) binding. This study places emphasis on strategic utilization of non-standard amino acids in the design of metal ion-chelating peptides, which will further diversify the types of peptide recognition elements available for metal ion sensing applications. Full article
(This article belongs to the Special Issue Electrochemistry and Spectroscopy-Based Biosensors)
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10 pages, 1792 KiB  
Communication
Disposable Electrochemical Biosensor Based on the Inhibition of Alkaline Phosphatase Encapsulated in Acrylamide Hydrogels
by Yolanda Alacid, Andrés F. Quintero Jaime, María José Martínez-Tomé, C. Reyes Mateo and Francisco Montilla
Biosensors 2022, 12(9), 698; https://doi.org/10.3390/bios12090698 - 29 Aug 2022
Cited by 3 | Viewed by 1734
Abstract
The present work describes the development of an easy-to-use portable electrochemical biosensor based on alkaline phosphatase (ALP) as a recognition element, which has been immobilized in acrylamide-based hydrogels prepared through a green protocol over disposable screen-printed electrodes. To carry out the electrochemical transduction, [...] Read more.
The present work describes the development of an easy-to-use portable electrochemical biosensor based on alkaline phosphatase (ALP) as a recognition element, which has been immobilized in acrylamide-based hydrogels prepared through a green protocol over disposable screen-printed electrodes. To carry out the electrochemical transduction, an electroinactive substrate (hydroquinone diphosphate) was used in the presence of the enzyme and then it was hydrolyzed to an electroactive species (hydroquinone). The activity of the protein within the matrix was determined voltammetrically. Due to the adhesive properties of the hydrogel, this was easily deposited on the surface of the electrodes, greatly increasing the sensitivity of the biosensor. The device was optimized to allow the determination of phosphate ion, a competitive inhibitor of ALP, in aqueous media. Our study provides a proof-of-concept demonstrating the potential use of the developed biosensor for in situ, real-time measurement of water pollutants that act as ALP inhibitors. Full article
(This article belongs to the Special Issue Electrochemistry and Spectroscopy-Based Biosensors)
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14 pages, 2833 KiB  
Article
Ratiometric Fluorescence Detection of Colorectal Cancer-Associated Exosomal miR-92a-3p with DSN-Assisted Signal Amplification by a MWCNTs@Au NCs Nanoplatform
by Zhiwei Sun, Juan Li, Yao Tong, Li Zhao, Xiaoyu Zhou, Hui Li, Chuanxin Wang, Lutao Du and Yanyan Jiang
Biosensors 2022, 12(7), 533; https://doi.org/10.3390/bios12070533 - 17 Jul 2022
Cited by 6 | Viewed by 2283
Abstract
The detection of miRNA shows great promise in disease diagnosis. In this work, a ratiometric fluorescent biosensor based on multi-walled carbon nanotubes@gold nanoclusters (MWCNTs@Au NCs) and duplex-specific nuclease (DSN)-assisted signal amplification was fabricated for miRNA detection. Colorectal cancer (CRC)-associated miR-92a-3p extracted from exosomes [...] Read more.
The detection of miRNA shows great promise in disease diagnosis. In this work, a ratiometric fluorescent biosensor based on multi-walled carbon nanotubes@gold nanoclusters (MWCNTs@Au NCs) and duplex-specific nuclease (DSN)-assisted signal amplification was fabricated for miRNA detection. Colorectal cancer (CRC)-associated miR-92a-3p extracted from exosomes was selected as the target. MWCNTs@Au NCs performs the dual functions of fluorescence quencher and internal fluorescence reference. In the absence of miR-92a-3p, an Atto-425-modified single-stranded DNA probe is adsorbed on MWCNTs@Au NCs, resulting in the quenching of Atto-425. In the presence of miR-92a-3p, the duplex is formed by hybridization of the probe and miR-92a-3p and leaves the MWCNTs@Au NCs, resulting in the fluorescence recovery of Atto-425. DSN can cleave the probe and result in the release of miR-92a-3p. The released miR-92a-3p can hybridize with other probes to form a signal amplification cycle. The fluorescence of MWCNTs@Au NCs remains stable and constitutes a ratiometric fluorescence system with that of Atto-425. A detection concentration interval of 0.1–10 pM and a limit of detection of 31 fM was obtained under optimized measurement conditions. In addition, the accuracy of the biosensor was validated by detecting the concentration of miR-92a-3p extracted from clinical exosome samples. Full article
(This article belongs to the Special Issue Electrochemistry and Spectroscopy-Based Biosensors)
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14 pages, 3077 KiB  
Article
Potentiometric Performance of Ion-Selective Electrodes Based on Polyaniline and Chelating Agents: Detection of Fe2+ or Fe3+ Ions
by Rimeh Ismail, Ivana Šeděnková, Zulfiya Černochová, Iryna Romanenko, Ognen Pop-Georgievski, Martin Hrubý and Elena Tomšík
Biosensors 2022, 12(7), 446; https://doi.org/10.3390/bios12070446 - 23 Jun 2022
Cited by 7 | Viewed by 2026
Abstract
We constructed a sensor for the determination of Fe2+ and/or Fe3+ ions that consists of a polyaniline layer as an ion-to-electron transducer; on top of it, chelating molecules are deposited (which can selectively chelate specific ions) and protected with a non-biofouling [...] Read more.
We constructed a sensor for the determination of Fe2+ and/or Fe3+ ions that consists of a polyaniline layer as an ion-to-electron transducer; on top of it, chelating molecules are deposited (which can selectively chelate specific ions) and protected with a non-biofouling poly(2-methyl-2-oxazoline)s layer. We have shown that our potentiometric sensing layers show a rapid response to the presence of Fe2+ or Fe3+ ions, do not experience interference with other ions (such as Cu2+), and work in a biological environment in the presence of bovine serum albumin (as a model serum protein). The sensing layers detect iron ions in the concentration range from 5 nM to 50 µM. Full article
(This article belongs to the Special Issue Electrochemistry and Spectroscopy-Based Biosensors)
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12 pages, 3433 KiB  
Article
Prefab Hollow Glass Microsphere-Based Immunosensor with Liquid Crystal Sensitization for Acute Myocardial Infarction Biomarker Detection
by Panpan Niu, Junfeng Jiang, Kun Liu, Shuang Wang, Tianhua Xu, Ziyihui Wang, Tong Wang, Xuezhi Zhang, Zhenyang Ding, Yize Liu and Tiegen Liu
Biosensors 2022, 12(7), 439; https://doi.org/10.3390/bios12070439 - 22 Jun 2022
Cited by 2 | Viewed by 1765
Abstract
Quantitative detection of cardiac troponin biomarkers in blood is an important method for clinical diagnosis of acute myocardial infarction (AMI). In this work, a whispering gallery mode (WGM) microcavity immunosensor based on a prefab hollow glass microsphere (HGMS) with liquid crystal (LC) sensitization [...] Read more.
Quantitative detection of cardiac troponin biomarkers in blood is an important method for clinical diagnosis of acute myocardial infarction (AMI). In this work, a whispering gallery mode (WGM) microcavity immunosensor based on a prefab hollow glass microsphere (HGMS) with liquid crystal (LC) sensitization was proposed and experimentally demonstrated for label-free cardiac troponin I-C (cTnI-C) complex detection. The proposed fiber-optic immunosensor has a simple structure; the tiny modified HGMS serves as the key sensing element and the microsample reservoir simultaneously. A sensitive LC layer with cTnI-C recognition ability was deposited on the inner wall of the HGMS microcavity. The arrangement of LC molecules is affected by the cTnI-C antigen—antibody binding in the HGMS, and the small change of the surface refractive index caused by the binding can be amplified owing to the birefringence property of LC. Using the annular waveguide of the HGMS, the WGMs were easily excited by the coupling scanning laser with a microfiber, and an all-fiber cTnI-C immunosensor can be achieved by measuring the resonant wavelength shift of the WGM spectrum. Moreover, the dynamic processes of the cTnI-C antigen—antibody binding and unbinding was revealed by monitoring the wavelength shift continuously. The proposed immunosensor with a spherical microcavity can be a cost-effective tool for AMI diagnosis. Full article
(This article belongs to the Special Issue Electrochemistry and Spectroscopy-Based Biosensors)
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12 pages, 2107 KiB  
Article
Functionalization of Glucose Oxidase in Organic Solvent: Towards Direct Electrical Communication across Enzyme-Electrode Interface
by Vygailė Dudkaitė and Gintautas Bagdžiūnas
Biosensors 2022, 12(5), 335; https://doi.org/10.3390/bios12050335 - 13 May 2022
Cited by 6 | Viewed by 2395
Abstract
Enzymatic biosensors based on glucose oxidase has been proven to be one of the effective strategies for the detection of glucose and contributed to health improvements. Therefore, research and debates to date are ongoing in an attempt to find the most effective way [...] Read more.
Enzymatic biosensors based on glucose oxidase has been proven to be one of the effective strategies for the detection of glucose and contributed to health improvements. Therefore, research and debates to date are ongoing in an attempt to find the most effective way to detect this analyte using this enzyme as the recognition center. The 3rd generation biosensors using direct electron transfer (DET) type enzymes are a great way towards practical devices. In this work, we developed a simple method for the functionalization of glucose oxidase with redoxable ferrocene groups in chloroform. The enzyme retained its activity after storage in this organic solvent and after the functionalization procedures. This enzyme functionalization strategy was employed to develop the biosensing monolayer-based platforms for the detection of glucose utilizing the quasi-DET mechanism. As a result of an electrochemical regeneration of the catalytic center, the formation of harmful H2O2 is minimized during enzymatic electrocatalysis. Full article
(This article belongs to the Special Issue Electrochemistry and Spectroscopy-Based Biosensors)
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13 pages, 9315 KiB  
Article
Effect of Al2O3 Passive Layer on Stability and Doping of MoS2 Field-Effect Transistor (FET) Biosensors
by Tung Pham, Ying Chen, Jhoann Lopez, Mei Yang, Thien-Toan Tran and Ashok Mulchandani
Biosensors 2021, 11(12), 514; https://doi.org/10.3390/bios11120514 - 13 Dec 2021
Cited by 6 | Viewed by 3160
Abstract
Molybdenum disulfide (MoS2) features a band gap of 1.3 eV (indirect) to 1.9 eV (direct). This tunable band gap renders MoS2 a suitable conducting channel for field-effect transistors (FETs). In addition, the highly sensitive surface potential in MoS2 layers [...] Read more.
Molybdenum disulfide (MoS2) features a band gap of 1.3 eV (indirect) to 1.9 eV (direct). This tunable band gap renders MoS2 a suitable conducting channel for field-effect transistors (FETs). In addition, the highly sensitive surface potential in MoS2 layers allows the feasibility of FET applications in biosensors, where direct immobilization and detection of biological molecules are conducted in wet conditions. In this work, we report, for the first time, the degradation of chemical vapor deposition (CVD) grown MoS2 FET-based sensors in the presence of phosphate buffer and water, which caused false positive response in detection. We conclude the degradation was originated by physical delamination of MoS2 thin films from the SiO2 substrate. The problem was alleviated by coating the sensors with a 30 nm thick aluminum oxide (Al2O3) layer using atomic layer deposition technique (ALD). This passive oxide thin film not only acted as a protecting layer against the device degradation but also induced a strong n-doping onto MoS2, which permitted a facile method of detection in MoS2 FET-based sensors using a low-power mode chemiresistive I-V measurement at zero gate voltage (Vgate = 0 V). Additionally, the oxide layer provided available sites for facile functionalization with bioreceptors. As immunoreaction plays a key role in clinical diagnosis and environmental analysis, our work presented a promising application using such enhanced Al2O3-coated MoS2 chemiresistive biosensors for detection of HIgG with high sensitivity and selectivity. The biosensor was successfully applied to detect HIgG in artificial urine, a complex matrix containing organics and salts. Full article
(This article belongs to the Special Issue Electrochemistry and Spectroscopy-Based Biosensors)
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15 pages, 2715 KiB  
Article
Reagentless D-Tagatose Biosensors Based on the Oriented Immobilization of Fructose Dehydrogenase onto Coated Gold Nanoparticles- or Reduced Graphene Oxide-Modified Surfaces: Application in a Prototype Bioreactor
by Ieva Šakinytė, Marius Butkevičius, Vidutė Gurevičienė, Jonita Stankevičiūtė, Rolandas Meškys and Julija Razumienė
Biosensors 2021, 11(11), 466; https://doi.org/10.3390/bios11110466 - 19 Nov 2021
Cited by 2 | Viewed by 1792
Abstract
As electrode nanomaterials, thermally reduced graphene oxide (TRGO) and modified gold nanoparticles (AuNPs) were used to design bioelectrocatalytic systems for reliable D-tagatose monitoring in a long-acting bioreactor where the valuable sweetener D-tagatose was enzymatically produced from a dairy by-product D-galactose. For this goal [...] Read more.
As electrode nanomaterials, thermally reduced graphene oxide (TRGO) and modified gold nanoparticles (AuNPs) were used to design bioelectrocatalytic systems for reliable D-tagatose monitoring in a long-acting bioreactor where the valuable sweetener D-tagatose was enzymatically produced from a dairy by-product D-galactose. For this goal D-fructose dehydrogenase (FDH) from Gluconobacter industrius immobilized on these electrode nanomaterials by forming three amperometric biosensors: AuNPs coated with 4-mercaptobenzoic acid (AuNP/4-MBA/FDH) or AuNPs coated with 4-aminothiophenol (AuNP/PATP/FDH) monolayer, and a layer of TRGO on graphite (TRGO/FDH) were created. The immobilized FDH due to changes in conformation and spatial orientation onto proposed electrode surfaces catalyzes a direct D-tagatose oxidation reaction. The highest sensitivity for D-tagatose of 0.03 ± 0.002 μA mM−1cm−2 was achieved using TRGO/FDH. The TRGO/FDH was applied in a prototype bioreactor for the quantitative evaluation of bioconversion of D-galactose into D-tagatose by L-arabinose isomerase. The correlation coefficient between two independent analyses of the bioconversion mixture: spectrophotometric and by the biosensor was 0.9974. The investigation of selectivity showed that the biosensor was not active towards D-galactose as a substrate. Operational stability of the biosensor indicated that detection of D-tagatose could be performed during six hours without loss of sensitivity. Full article
(This article belongs to the Special Issue Electrochemistry and Spectroscopy-Based Biosensors)
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Review

Jump to: Editorial, Research

18 pages, 4627 KiB  
Review
Recent Advances in Inflammatory Diagnosis with Graphene Quantum Dots Enhanced SERS Detection
by Seyyed Mojtaba Mousavi, Seyyed Alireza Hashemi, Masoomeh Yari Kalashgrani, Darwin Kurniawan, Ahmad Gholami, Vahid Rahmanian, Navid Omidifar and Wei-Hung Chiang
Biosensors 2022, 12(7), 461; https://doi.org/10.3390/bios12070461 - 27 Jun 2022
Cited by 18 | Viewed by 3367
Abstract
Inflammatory diseases are some of the most common diseases in different parts of the world. So far, most attention has been paid to the role of environmental factors in the inflammatory process. The diagnosis of inflammatory changes is an important goal for the [...] Read more.
Inflammatory diseases are some of the most common diseases in different parts of the world. So far, most attention has been paid to the role of environmental factors in the inflammatory process. The diagnosis of inflammatory changes is an important goal for the timely diagnosis and treatment of various metastatic, autoimmune, and infectious diseases. Graphene quantum dots (GQDs) can be used for the diagnosis of inflammation due to their excellent properties, such as high biocompatibility, low toxicity, high stability, and specific surface area. Additionally, surface-enhanced Raman spectroscopy (SERS) allows the very sensitive structural detection of analytes at low concentrations by amplifying electromagnetic fields generated by the excitation of localized surface plasmons. In recent years, the use of graphene quantum dots amplified by SERS has increased for the diagnosis of inflammation. The known advantages of graphene quantum dots SERS include non-destructive analysis methods, sensitivity and specificity, and the generation of narrow spectral bands characteristic of the molecular components present, which have led to their increased application. In this article, we review recent advances in the diagnosis of inflammation using graphene quantum dots and their improved detection of SERS. In this review study, the graphene quantum dots synthesis method, bioactivation method, inflammatory biomarkers, plasma synthesis of GQDs and SERS GQD are investigated. Finally, the detection mechanisms of SERS and the detection of inflammation are presented. Full article
(This article belongs to the Special Issue Electrochemistry and Spectroscopy-Based Biosensors)
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