This study explores a carbon-based electrode alternative of conventional gold-thiolate monolayers for high-throughput biosensor development. We investigate the functionalization of glassy carbon electrodes (GCEs) with aptamers to create biosensing interfaces. The modification process of carbon involves three main steps: (1) electrografting of 4-aminobenzoic acid (ABA) onto the electrode surface to introduce carboxyl (–COOH) groups, (2) –COOH groups activation using EDC/NHS chemistry, and (3) coupling 5′-amine-terminated aptamers for tobramycin (apt-TOB). Surface modification of the resulting GCE/ABA/aptamer was characterized rigorously using cyclic voltammetry (CV), water contact angle, electrochemical impedance spectroscopy (EIS), and attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy. The obtained interface exhibits an exceptional surface coverage of ≈170 pmol cm−2, exceeding that of conventional gold-thiolate monolayers. As a proof of concept, we demonstrate the impedimetric detection of tobramycin using the GCE/ABA/aptamer-modified electrodes. The range of detection achieved was 1 nM–10 μM and a LOD of 1 nM. This work aims to evaluate the feasibility of using ABA (via carbodiimide chemistry) as a linker for aptamer immobilization on GCE, like a practical alternative to gold for high-performance aptamer-based sensors in clinical, ambiental, and alimentary analyses.
{"title":"Surface Functionalization of Glassy Carbon Electrodes via Electrografting of Aminobenzoic Acid: A Proof-of-Concept Study for Aptasensor Design","authors":"Cristina Corona-Elizarrarás, Cyrine Slim, Netzahualcóyotl Arroyo-Currás, Sophie Griveau, Silvia Gutiérrez Granados","doi":"10.1002/elan.70082","DOIUrl":"https://doi.org/10.1002/elan.70082","url":null,"abstract":"<p>This study explores a carbon-based electrode alternative of conventional gold-thiolate monolayers for high-throughput biosensor development. We investigate the functionalization of glassy carbon electrodes (GCEs) with aptamers to create biosensing interfaces. The modification process of carbon involves three main steps: (1) electrografting of 4-aminobenzoic acid (ABA) onto the electrode surface to introduce carboxyl (–COOH) groups, (2) –COOH groups activation using EDC/NHS chemistry, and (3) coupling 5<sup>′</sup>-amine-terminated aptamers for tobramycin (apt-TOB). Surface modification of the resulting GCE/ABA/aptamer was characterized rigorously using cyclic voltammetry (CV), water contact angle, electrochemical impedance spectroscopy (EIS), and attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy. The obtained interface exhibits an exceptional surface coverage of ≈170 pmol cm<sup>−2</sup>, exceeding that of conventional gold-thiolate monolayers. As a proof of concept, we demonstrate the impedimetric detection of tobramycin using the GCE/ABA/aptamer-modified electrodes. The range of detection achieved was 1 nM–10 μM and a LOD of 1 nM. This work aims to evaluate the feasibility of using ABA (via carbodiimide chemistry) as a linker for aptamer immobilization on GCE, like a practical alternative to gold for high-performance aptamer-based sensors in clinical, ambiental, and alimentary analyses.</p>","PeriodicalId":162,"journal":{"name":"Electroanalysis","volume":"37 12","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145686217","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
This study explores a carbon-based electrode alternative of conventional gold-thiolate monolayers for high-throughput biosensor development. We investigate the functionalization of glassy carbon electrodes (GCEs) with aptamers to create biosensing interfaces. The modification process of carbon involves three main steps: (1) electrografting of 4-aminobenzoic acid (ABA) onto the electrode surface to introduce carboxyl (–COOH) groups, (2) –COOH groups activation using EDC/NHS chemistry, and (3) coupling 5′-amine-terminated aptamers for tobramycin (apt-TOB). Surface modification of the resulting GCE/ABA/aptamer was characterized rigorously using cyclic voltammetry (CV), water contact angle, electrochemical impedance spectroscopy (EIS), and attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy. The obtained interface exhibits an exceptional surface coverage of ≈170 pmol cm−2, exceeding that of conventional gold-thiolate monolayers. As a proof of concept, we demonstrate the impedimetric detection of tobramycin using the GCE/ABA/aptamer-modified electrodes. The range of detection achieved was 1 nM–10 μM and a LOD of 1 nM. This work aims to evaluate the feasibility of using ABA (via carbodiimide chemistry) as a linker for aptamer immobilization on GCE, like a practical alternative to gold for high-performance aptamer-based sensors in clinical, ambiental, and alimentary analyses.
{"title":"Surface Functionalization of Glassy Carbon Electrodes via Electrografting of Aminobenzoic Acid: A Proof-of-Concept Study for Aptasensor Design","authors":"Cristina Corona-Elizarrarás, Cyrine Slim, Netzahualcóyotl Arroyo-Currás, Sophie Griveau, Silvia Gutiérrez Granados","doi":"10.1002/elan.70082","DOIUrl":"https://doi.org/10.1002/elan.70082","url":null,"abstract":"<p>This study explores a carbon-based electrode alternative of conventional gold-thiolate monolayers for high-throughput biosensor development. We investigate the functionalization of glassy carbon electrodes (GCEs) with aptamers to create biosensing interfaces. The modification process of carbon involves three main steps: (1) electrografting of 4-aminobenzoic acid (ABA) onto the electrode surface to introduce carboxyl (–COOH) groups, (2) –COOH groups activation using EDC/NHS chemistry, and (3) coupling 5<sup>′</sup>-amine-terminated aptamers for tobramycin (apt-TOB). Surface modification of the resulting GCE/ABA/aptamer was characterized rigorously using cyclic voltammetry (CV), water contact angle, electrochemical impedance spectroscopy (EIS), and attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy. The obtained interface exhibits an exceptional surface coverage of ≈170 pmol cm<sup>−2</sup>, exceeding that of conventional gold-thiolate monolayers. As a proof of concept, we demonstrate the impedimetric detection of tobramycin using the GCE/ABA/aptamer-modified electrodes. The range of detection achieved was 1 nM–10 μM and a LOD of 1 nM. This work aims to evaluate the feasibility of using ABA (via carbodiimide chemistry) as a linker for aptamer immobilization on GCE, like a practical alternative to gold for high-performance aptamer-based sensors in clinical, ambiental, and alimentary analyses.</p>","PeriodicalId":162,"journal":{"name":"Electroanalysis","volume":"37 12","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145686222","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The application of electrochemical impedance spectroscopy (EIS) for electrode characterization and biosensor development has become challenging due to the overlapping or superimposed semicircles and features on the Nyquist plot and numerous possible equivalent circuits. This study aimed to apply an EIS analysis workflow consisting of data validation using the Kramers–Kronig Model, distribution of relaxation times (DRT) analysis, and equivalent circuit model (ECM) parameterization using the recently available pyDRTtools and the Python package “impedance.py”. The effect of modifying the electrode with a metal organic framework – Cu-BTC, graphite, and gold nanoparticles (AuNP) was studied by calculating the effective capacitance (Ceff) and electrochemically active surface area (ECSA) from the ECM parameters. 60% Cu-BTC mixed with graphite (v/v) showed the highest increase in the Ceff and therefore the ECSA from 0.18 to 12.72 cm2. Electrodeposition of AuNP reduced this value to 0.31 cm2 due to in-between particle agglomeration. The final hybrid nanomaterial was composed of DNA tagged with ferrocene and thiol, AuNP, and a 60% Cu-BTC and graphite mixture assembled on a glassy carbon electrode. DRT analysis was used to propose the data-driven ECMs. Based on the root mean square error of each model circuit and the percent standard error for each parameter, the transmission line model has the best fit mathematically. However, a Randles circuit with a constant phase element and a custom circuit composed of two RC in series between a resistor and a Warburg element are practical to use for further biosensor development using this electrode assembly.
{"title":"Application of Distribution of Relaxation Times and Equivalent Circuit Modeling for Biosensor Electrode Development","authors":"Resmond L. Reaño","doi":"10.1002/elan.70084","DOIUrl":"https://doi.org/10.1002/elan.70084","url":null,"abstract":"<p>The application of electrochemical impedance spectroscopy (EIS) for electrode characterization and biosensor development has become challenging due to the overlapping or superimposed semicircles and features on the Nyquist plot and numerous possible equivalent circuits. This study aimed to apply an EIS analysis workflow consisting of data validation using the Kramers–Kronig Model, distribution of relaxation times (DRT) analysis, and equivalent circuit model (ECM) parameterization using the recently available pyDRTtools and the Python package “impedance.py”. The effect of modifying the electrode with a metal organic framework – Cu-BTC, graphite, and gold nanoparticles (AuNP) was studied by calculating the effective capacitance (<i>C</i><sub><i>eff</i></sub>) and electrochemically active surface area (ECSA) from the ECM parameters. 60% Cu-BTC mixed with graphite (v/v) showed the highest increase in the <i>C</i><sub><i>eff</i></sub> and therefore the ECSA from 0.18 to 12.72 cm<sup>2</sup>. Electrodeposition of AuNP reduced this value to 0.31 cm<sup>2</sup> due to in-between particle agglomeration. The final hybrid nanomaterial was composed of DNA tagged with ferrocene and thiol, AuNP, and a 60% Cu-BTC and graphite mixture assembled on a glassy carbon electrode. DRT analysis was used to propose the data-driven ECMs. Based on the root mean square error of each model circuit and the percent standard error for each parameter, the transmission line model has the best fit mathematically. However, a Randles circuit with a constant phase element and a custom circuit composed of two RC in series between a resistor and a Warburg element are practical to use for further biosensor development using this electrode assembly.</p>","PeriodicalId":162,"journal":{"name":"Electroanalysis","volume":"37 12","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-11-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145686434","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The application of electrochemical impedance spectroscopy (EIS) for electrode characterization and biosensor development has become challenging due to the overlapping or superimposed semicircles and features on the Nyquist plot and numerous possible equivalent circuits. This study aimed to apply an EIS analysis workflow consisting of data validation using the Kramers–Kronig Model, distribution of relaxation times (DRT) analysis, and equivalent circuit model (ECM) parameterization using the recently available pyDRTtools and the Python package “impedance.py”. The effect of modifying the electrode with a metal organic framework – Cu-BTC, graphite, and gold nanoparticles (AuNP) was studied by calculating the effective capacitance (Ceff) and electrochemically active surface area (ECSA) from the ECM parameters. 60% Cu-BTC mixed with graphite (v/v) showed the highest increase in the Ceff and therefore the ECSA from 0.18 to 12.72 cm2. Electrodeposition of AuNP reduced this value to 0.31 cm2 due to in-between particle agglomeration. The final hybrid nanomaterial was composed of DNA tagged with ferrocene and thiol, AuNP, and a 60% Cu-BTC and graphite mixture assembled on a glassy carbon electrode. DRT analysis was used to propose the data-driven ECMs. Based on the root mean square error of each model circuit and the percent standard error for each parameter, the transmission line model has the best fit mathematically. However, a Randles circuit with a constant phase element and a custom circuit composed of two RC in series between a resistor and a Warburg element are practical to use for further biosensor development using this electrode assembly.
{"title":"Application of Distribution of Relaxation Times and Equivalent Circuit Modeling for Biosensor Electrode Development","authors":"Resmond L. Reaño","doi":"10.1002/elan.70084","DOIUrl":"https://doi.org/10.1002/elan.70084","url":null,"abstract":"<p>The application of electrochemical impedance spectroscopy (EIS) for electrode characterization and biosensor development has become challenging due to the overlapping or superimposed semicircles and features on the Nyquist plot and numerous possible equivalent circuits. This study aimed to apply an EIS analysis workflow consisting of data validation using the Kramers–Kronig Model, distribution of relaxation times (DRT) analysis, and equivalent circuit model (ECM) parameterization using the recently available pyDRTtools and the Python package “impedance.py”. The effect of modifying the electrode with a metal organic framework – Cu-BTC, graphite, and gold nanoparticles (AuNP) was studied by calculating the effective capacitance (<i>C</i><sub><i>eff</i></sub>) and electrochemically active surface area (ECSA) from the ECM parameters. 60% Cu-BTC mixed with graphite (v/v) showed the highest increase in the <i>C</i><sub><i>eff</i></sub> and therefore the ECSA from 0.18 to 12.72 cm<sup>2</sup>. Electrodeposition of AuNP reduced this value to 0.31 cm<sup>2</sup> due to in-between particle agglomeration. The final hybrid nanomaterial was composed of DNA tagged with ferrocene and thiol, AuNP, and a 60% Cu-BTC and graphite mixture assembled on a glassy carbon electrode. DRT analysis was used to propose the data-driven ECMs. Based on the root mean square error of each model circuit and the percent standard error for each parameter, the transmission line model has the best fit mathematically. However, a Randles circuit with a constant phase element and a custom circuit composed of two RC in series between a resistor and a Warburg element are practical to use for further biosensor development using this electrode assembly.</p>","PeriodicalId":162,"journal":{"name":"Electroanalysis","volume":"37 12","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-11-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145686462","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Cover picture provided by Dr. Elena Benito-Peña and Dr. Susana Campuzano. Electroanalysis covers all branches of electroanalytical chemistry, including both fundamental and application papers as well as reviews dealing with analytical voltammetry, potentiometry, new electrochemical sensors and detection schemes, nanoscale electrochemistry, advanced electromaterials, nanobioelectronics, point-of-care diagnostics, wearable sensors, and practical applications.