Pub Date : 2026-01-24DOI: 10.1016/j.bioelechem.2026.109233
Arash Rasti , Muhamad Afiq Aziz , Zaira Zaman Chowdhury , Sook Mei Khor
Early detection of hydrocarbon pollution in saline ecosystems faces challenges due to their complexity and the limitations of current detection methods. Salinity, temperature variations, the presence of other organic matter, and weathering processes hinder the effectiveness of traditional techniques, while the cost and complexity of some advanced detection technologies limit their widespread application. In this study, a gold screen-printed electrode (Au-SPE) modified with d-luciferin was developed to monitor the metabolic response of Photobacterium leiognathi to hexane and aromatic hydrocarbons in saline water and seawater. The sensor works by capturing adenosine triphosphate (ATP)-dependent electron release associated with bacterial bioluminescence, which varies according to the type of hydrocarbon. D-luciferin was immobilized on the Au-SPE via a self-assembled monolayer using ethylenediamine and EDC/NHS coupling to create a biocompatible interface. CV analysis revealed time-dependent shifts of anodic and cathodic peaks from −0.5 V to +0.5 V. The presence of aromatic hydrocarbons increased both bioluminescence light emission and current, indicating metabolic stimulation. In contrast, hexane suppressed bioluminescence and decreased current, indicating metabolic inhibition. These distinct responses enable rapid and selective differentiation between different types of hydrocarbons. The developed biosensor exhibits strong potential for real-time monitoring of oil contamination and assessing water quality in saline ecosystems.
{"title":"Bioluminescence-based electrochemical sensor for dual-mode direct hydrocarbon detection in saline water utilizing Photobacterium leiognathi and d-luciferin-modified au-SPE","authors":"Arash Rasti , Muhamad Afiq Aziz , Zaira Zaman Chowdhury , Sook Mei Khor","doi":"10.1016/j.bioelechem.2026.109233","DOIUrl":"10.1016/j.bioelechem.2026.109233","url":null,"abstract":"<div><div>Early detection of hydrocarbon pollution in saline ecosystems faces challenges due to their complexity and the limitations of current detection methods. Salinity, temperature variations, the presence of other organic matter, and weathering processes hinder the effectiveness of traditional techniques, while the cost and complexity of some advanced detection technologies limit their widespread application. In this study, a gold screen-printed electrode (Au-SPE) modified with d-luciferin was developed to monitor the metabolic response of <em>Photobacterium leiognathi</em> to hexane and aromatic hydrocarbons in saline water and seawater. The sensor works by capturing adenosine triphosphate (ATP)-dependent electron release associated with bacterial bioluminescence, which varies according to the type of hydrocarbon. D-luciferin was immobilized on the Au-SPE via a self-assembled monolayer using ethylenediamine and EDC/NHS coupling to create a biocompatible interface. CV analysis revealed time-dependent shifts of anodic and cathodic peaks from −0.5 V to +0.5 V. The presence of aromatic hydrocarbons increased both bioluminescence light emission and current, indicating metabolic stimulation. In contrast, hexane suppressed bioluminescence and decreased current, indicating metabolic inhibition. These distinct responses enable rapid and selective differentiation between different types of hydrocarbons. The developed biosensor exhibits strong potential for real-time monitoring of oil contamination and assessing water quality in saline ecosystems.</div></div>","PeriodicalId":252,"journal":{"name":"Bioelectrochemistry","volume":"170 ","pages":"Article 109233"},"PeriodicalIF":4.5,"publicationDate":"2026-01-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146073977","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-23DOI: 10.1016/j.bioelechem.2026.109232
Zihao Wang , Xiaobao Zhou , Zuchuan Zhang , Lin Liu , Cong Li , Boxin Wei , Tangqing Wu
Microbiologically influenced corrosion (MIC) critically compromises the integrity of metal structures. This study investigates the effect of copper on the MIC behavior of CoNiV–Cux medium-entropy alloys (MEAs) in Desulfovibrio vulgaris environments. In sterile medium, increasing Cu reduced the combined film and charge transfer resistance, whereas in inoculated medium, the trend reversed. After 360 h, CoNiV–Cu10 MEA formed a protective oxide layer (δeff = 0.912 nm), three times thicker than CoNiV MEA. The corrosion current and passivation current were significantly lower in Cu-rich alloys under MIC. The apparently adverse effect of Cu in sterile conditions was associated with modifications in passive film defect chemistry and charge-transfer processes, whereas under MIC conditions, Cu addition enhanced passive film stability, suppressed microbial adhesion, and improved MIC resistance. These findings provide insight for designing Cu-alloyed MEAs with superior performance in MIC environments.
{"title":"Cu-enhanced microbiological corrosion resistance of CoNiV medium-entropy alloy","authors":"Zihao Wang , Xiaobao Zhou , Zuchuan Zhang , Lin Liu , Cong Li , Boxin Wei , Tangqing Wu","doi":"10.1016/j.bioelechem.2026.109232","DOIUrl":"10.1016/j.bioelechem.2026.109232","url":null,"abstract":"<div><div>Microbiologically influenced corrosion (MIC) critically compromises the integrity of metal structures. This study investigates the effect of copper on the MIC behavior of CoNiV–Cu<sub><em>x</em></sub> medium-entropy alloys (MEAs) in <em>Desulfovibrio vulgaris</em> environments. In sterile medium, increasing Cu reduced the combined film and charge transfer resistance, whereas in inoculated medium, the trend reversed. After 360 h, CoNiV–Cu<sub>10</sub> MEA formed a protective oxide layer (<em>δ</em><sub>eff</sub> = 0.912 nm), three times thicker than CoNiV MEA. The corrosion current and passivation current were significantly lower in Cu-rich alloys under MIC. The apparently adverse effect of Cu in sterile conditions was associated with modifications in passive film defect chemistry and charge-transfer processes, whereas under MIC conditions, Cu addition enhanced passive film stability, suppressed microbial adhesion, and improved MIC resistance. These findings provide insight for designing Cu-alloyed MEAs with superior performance in MIC environments.</div></div>","PeriodicalId":252,"journal":{"name":"Bioelectrochemistry","volume":"170 ","pages":"Article 109232"},"PeriodicalIF":4.5,"publicationDate":"2026-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146058377","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-22DOI: 10.1016/j.bioelechem.2026.109235
Vasumathi K. , Chin-Tsan Wang
Microbial fuel cells (MFCs) enable simultaneous wastewater treatment and bioelectricity generation, but their performance is often constrained by poor bacterial adhesion and slow anode electron transfer. Hydroxyapatite (HA) can address these limitations; however, most studies rely on commercial HA and rarely examine biowaste-derived sources or synthesis-route effects. In this study, eggshell-derived HA was synthesized via room-temperature precipitation (CHP) and hydrothermal treatment at 250 °C for 3 h (CHH), then blended with carbon to fabricate composite anodes. Dual-chamber MFCs inoculated with Shewanella putrefaciens were evaluated using electrochemical analyses (CV, EIS, polarization) and biofilm characterization (CFU counts, crystal violet staining, SEM). CHH achieved a peak power density of 0.164 W m−2, approximately 167% higher than bare carbon and 23–33% higher than carbon and CHP. CHP exhibited slightly lower peak power but superior sustained output over a wider current-density range, attributed to its low-crystallinity structure and rapid early colonization. The results demonstrate that HA nanostructure, governed by synthesis route, directly influences biofilm formation and electron transfer. Overall, eggshell-derived HA anodes significantly enhance MFC performance, establishing a clear synthesis–nanostructure–biofilm–performance relationship.
微生物燃料电池(mfc)能够同时进行废水处理和生物发电,但其性能往往受到细菌粘附性差和阳极电子转移缓慢的限制。羟基磷灰石(HA)可以解决这些限制;然而,大多数研究依赖于商业透明质酸,很少检查生物废物来源或合成途径的影响。在本研究中,通过室温沉淀(CHP)和250°C水热处理(CHH)合成蛋壳源HA,然后与碳混合制备复合阳极。采用电化学分析(CV、EIS、极化)和生物膜表征(CFU计数、结晶紫染色、扫描电镜)对接种了腐坏希瓦氏菌的双室mfc进行评价。CHH的峰值功率密度为0.164 W m−2,比裸碳高167%,比碳和CHP高23-33%。CHP的峰值功率略低,但由于其低结晶度结构和快速的早期定植,在较宽的电流密度范围内具有较好的持续输出。结果表明,透明质酸的纳米结构受合成路线的支配,直接影响生物膜的形成和电子的传递。总之,蛋壳衍生的HA阳极显著提高了MFC性能,建立了清晰的合成-纳米结构-生物膜-性能关系。
{"title":"Influence of synthesis temperature of eggshell-derived hydroxyapatite on biofilm formation and microbial fuel cell performance","authors":"Vasumathi K. , Chin-Tsan Wang","doi":"10.1016/j.bioelechem.2026.109235","DOIUrl":"10.1016/j.bioelechem.2026.109235","url":null,"abstract":"<div><div>Microbial fuel cells (MFCs) enable simultaneous wastewater treatment and bioelectricity generation, but their performance is often constrained by poor bacterial adhesion and slow anode electron transfer. Hydroxyapatite (HA) can address these limitations; however, most studies rely on commercial HA and rarely examine biowaste-derived sources or synthesis-route effects. In this study, eggshell-derived HA was synthesized via room-temperature precipitation (CHP) and hydrothermal treatment at 250 °C for 3 h (CHH), then blended with carbon to fabricate composite anodes. Dual-chamber MFCs inoculated with <em>Shewanella putrefaciens</em> were evaluated using electrochemical analyses (CV, EIS, polarization) and biofilm characterization (CFU counts, crystal violet staining, SEM). CHH achieved a peak power density of 0.164 W m<sup>−2</sup>, approximately 167% higher than bare carbon and 23–33% higher than carbon and CHP. CHP exhibited slightly lower peak power but superior sustained output over a wider current-density range, attributed to its low-crystallinity structure and rapid early colonization. The results demonstrate that HA nanostructure, governed by synthesis route, directly influences biofilm formation and electron transfer. Overall, eggshell-derived HA anodes significantly enhance MFC performance, establishing a clear synthesis–nanostructure–biofilm–performance relationship.</div></div>","PeriodicalId":252,"journal":{"name":"Bioelectrochemistry","volume":"170 ","pages":"Article 109235"},"PeriodicalIF":4.5,"publicationDate":"2026-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146073979","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-22DOI: 10.1016/j.bioelechem.2026.109236
Anh L. Duong , Keito Kaida , Kaito Goto , Iori Kojima , Bernard Delalande , Hirohisa Tamagawa
The Goldman–Hodgkin–Katz (GHK) equation provides a quantitative description of the membrane potential, a quantity commonly ascribed to passive and active ion movements through channels and pumps in the plasma membrane. Consequently, the membrane potential is frequently viewed as a hallmark of living cells. In physiology, the Nernst equation is often treated as a simplified version of the GHK equation. The factor (: ion valency; : membrane potential), termed the Nernst slope, serves as a key marker of the Nernst equation’s applicability and of cellular viability. Yet, nonliving systems can also develop potentials that exhibit the same characteristic slope, indicating that the Nernst slope is not necessarily a product of biological activity. An older, largely disregarded physiological model, the Association–Induction Hypothesis (AIH), explains membrane potential generation purely in terms of ion adsorption–desorption phenomena. Within the AIH framework, membrane potentials do not arise from ionic fluxes across the membrane but from equilibria that obey the law of mass action. In this study, we derive the Nernst slope using the AIH framework. This result suggests that the membrane potential may primarily reflect mass-action-determined equilibria rather than active physiological mechanisms.
{"title":"The Nernst slope within the Association–Induction Hypothesis framework","authors":"Anh L. Duong , Keito Kaida , Kaito Goto , Iori Kojima , Bernard Delalande , Hirohisa Tamagawa","doi":"10.1016/j.bioelechem.2026.109236","DOIUrl":"10.1016/j.bioelechem.2026.109236","url":null,"abstract":"<div><div>The Goldman–Hodgkin–Katz (GHK) equation provides a quantitative description of the membrane potential, a quantity commonly ascribed to passive and active ion movements through channels and pumps in the plasma membrane. Consequently, the membrane potential is frequently viewed as a hallmark of living cells. In physiology, the Nernst equation is often treated as a simplified version of the GHK equation. The factor <span><math><mrow><mo>−</mo><mi>e</mi><mi>ψ</mi><mo>/</mo><mi>z</mi><mi>k</mi><mi>T</mi></mrow></math></span> (<span><math><mi>z</mi></math></span>: ion valency; <span><math><mi>ψ</mi></math></span>: membrane potential), termed the Nernst slope, serves as a key marker of the Nernst equation’s applicability and of cellular viability. Yet, nonliving systems can also develop potentials that exhibit the same characteristic slope, indicating that the Nernst slope is not necessarily a product of biological activity. An older, largely disregarded physiological model, the Association–Induction Hypothesis (AIH), explains membrane potential generation purely in terms of ion adsorption–desorption phenomena. Within the AIH framework, membrane potentials do not arise from ionic fluxes across the membrane but from equilibria that obey the law of mass action. In this study, we derive the Nernst slope using the AIH framework. This result suggests that the membrane potential may primarily reflect mass-action-determined equilibria rather than active physiological mechanisms.</div></div>","PeriodicalId":252,"journal":{"name":"Bioelectrochemistry","volume":"170 ","pages":"Article 109236"},"PeriodicalIF":4.5,"publicationDate":"2026-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146073980","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-22DOI: 10.1016/j.bioelechem.2026.109234
Bal-Ram Adhikari, Reem Elmahdy, Carlos A Ramirez, Jacek Lipkowski, Aicheng Chen
We report on a novel nature-inspired electrochemical platform for the sensitive detection of thyroglobulin (Tg), a critical biomarker for monitoring treatment efficacy in patients with differentiated thyroid cancer following thyroidectomy. Current Tg diagnostic strategies typically require multiple complex reactions that require various washing steps and stringent experimental protocols. For this study, we have successfully developed a lactoperoxidase (LPO) based Ag nanoparticles (AgNP) and reduced graphene oxide (rGO) nanohybrid platform, on which LPO was immobilized through the creation of a self-assembled monolayer (SAM) of mercaptopropionic acid (MPA) followed by EDC/NHS activation. Cyclic voltammetry (CV) was employed to characterize the electrochemical behaviours of the rGO-AgNP nanohybrid, prior to and following the formation of the self-assembled monolayer (SAM). Electrochemical impedance spectroscopy (EIS) was used to further investigate the behaviour of the rGO-AgNP nanohybrid, following the immobilization of LPO. Our study has shown that the developed biosensor demonstrated rapid, sensitive, and selective Tg detection over a broad linear range of 4.0-90.0 ng/mL with a low limit of detection of 0.75 ng/mL, highlighting its strong potential for biological and clinical applications.
{"title":"Electrochemical detection of thyroglobulin based upon biomimetic thyroid chemistry.","authors":"Bal-Ram Adhikari, Reem Elmahdy, Carlos A Ramirez, Jacek Lipkowski, Aicheng Chen","doi":"10.1016/j.bioelechem.2026.109234","DOIUrl":"https://doi.org/10.1016/j.bioelechem.2026.109234","url":null,"abstract":"<p><p>We report on a novel nature-inspired electrochemical platform for the sensitive detection of thyroglobulin (Tg), a critical biomarker for monitoring treatment efficacy in patients with differentiated thyroid cancer following thyroidectomy. Current Tg diagnostic strategies typically require multiple complex reactions that require various washing steps and stringent experimental protocols. For this study, we have successfully developed a lactoperoxidase (LPO) based Ag nanoparticles (AgNP) and reduced graphene oxide (rGO) nanohybrid platform, on which LPO was immobilized through the creation of a self-assembled monolayer (SAM) of mercaptopropionic acid (MPA) followed by EDC/NHS activation. Cyclic voltammetry (CV) was employed to characterize the electrochemical behaviours of the rGO-AgNP nanohybrid, prior to and following the formation of the self-assembled monolayer (SAM). Electrochemical impedance spectroscopy (EIS) was used to further investigate the behaviour of the rGO-AgNP nanohybrid, following the immobilization of LPO. Our study has shown that the developed biosensor demonstrated rapid, sensitive, and selective Tg detection over a broad linear range of 4.0-90.0 ng/mL with a low limit of detection of 0.75 ng/mL, highlighting its strong potential for biological and clinical applications.</p>","PeriodicalId":252,"journal":{"name":"Bioelectrochemistry","volume":"170 ","pages":"109234"},"PeriodicalIF":4.5,"publicationDate":"2026-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111806","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-20DOI: 10.1016/j.bioelechem.2026.109230
Xiaolin Zhang, Zhicheng Li, Fangfang Yang, Jieyu Zhang, Jing Yu, Li Wang, Shufeng Liu
Nucleic acid probe design and immobilization are fundamental to the high performance of biosensors. However, the dependence on elaborate fabrication processes or meticulous optimization of probe immobilization poses challenges to achieving reliable bioanalysis and high sensing efficiency. Herein, we report an effective strategy for constructing electrochemical DNA biosensor that leverages a catalytic DNA reaction on a uniquely designed three-stranded duplex (TSD) probe. The TSD probe is engineered with an internally positioned thiol group to adopt a favorable flat-lying immobilization orientation. Compared to conventional upright TSD probe, the flat-lying design facilitates a more accessible interface and more stable assembly density with reduced dependence on immobilization concentration. This flat-lying system demonstrated superior sensing performance, including a faster reaction rate (completed within 1.5 h vs. 2.5 h for upright probes) and a lower detection limit of 244 fM for target, which is about 40-fold better than the upright configuration. The sensor also demonstrated excellent selectivity against mismatched sequences, better reproducibility and was successfully applied for target detection in diluted serum. This work presents a novel and facile probe design and immobilization paradigm that eliminates the traditional need for complex density optimization, offering a robust sensing platform for highly sensitive and efficient DNA detection.
{"title":"Engineering a flat-lying three-stranded duplex probe for catalytic DNA circuit toward enhanced electrochemical biosensing","authors":"Xiaolin Zhang, Zhicheng Li, Fangfang Yang, Jieyu Zhang, Jing Yu, Li Wang, Shufeng Liu","doi":"10.1016/j.bioelechem.2026.109230","DOIUrl":"10.1016/j.bioelechem.2026.109230","url":null,"abstract":"<div><div>Nucleic acid probe design and immobilization are fundamental to the high performance of biosensors. However, the dependence on elaborate fabrication processes or meticulous optimization of probe immobilization poses challenges to achieving reliable bioanalysis and high sensing efficiency. Herein, we report an effective strategy for constructing electrochemical DNA biosensor that leverages a catalytic DNA reaction on a uniquely designed three-stranded duplex (TSD) probe. The TSD probe is engineered with an internally positioned thiol group to adopt a favorable flat-lying immobilization orientation. Compared to conventional upright TSD probe, the flat-lying design facilitates a more accessible interface and more stable assembly density with reduced dependence on immobilization concentration. This flat-lying system demonstrated superior sensing performance, including a faster reaction rate (completed within 1.5 h vs. 2.5 h for upright probes) and a lower detection limit of 244 fM for target, which is about 40-fold better than the upright configuration. The sensor also demonstrated excellent selectivity against mismatched sequences, better reproducibility and was successfully applied for target detection in diluted serum. This work presents a novel and facile probe design and immobilization paradigm that eliminates the traditional need for complex density optimization, offering a robust sensing platform for highly sensitive and efficient DNA detection.</div></div>","PeriodicalId":252,"journal":{"name":"Bioelectrochemistry","volume":"170 ","pages":"Article 109230"},"PeriodicalIF":4.5,"publicationDate":"2026-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146023968","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-20DOI: 10.1016/j.bioelechem.2026.109231
Lucie Žaloudková , Vojtěch Hamala , Peter Šebest , Marek Zelinka , Hana Černocká , Jindřich Karban , Veronika Ostatná
Protein-ligand interactions are crucial for understanding biochemical reactions and pathways, as well as for the design of new therapeutics. In this work, we compare the electrochemical behavior of four neutral organoferrocene ligands that differ in the number of monosaccharide and ferrocene units. The presence of a carbohydrate moiety results in increased hydrophilicity, while ferrocene units increase hydrophobicity, which significantly influences interactions with the surface, as well as with serum albumin. The adsorption of di-ferrocene ligands on the electrode surface and to serum albumin is more pronounced than that of mono-ferrocenes. Additionally, di-ferrocene ligands require dissolution in organic solvents, such as dimethyl sulfoxide, which also influences ligand-electrode and ligand-protein affinities. The conclusions of our work highlight the importance of ligand nature in determining the dissociation constant and mutual interactions with proteins, including those where ligands bind non-specifically. Electrochemical methods are suitable for studying the interactions of hydrophobic ligands with proteins because the ligands are typically present at micromolar concentrations to ensure their solubility in water. In addition, these methods exhibit high sensitivity to subtle structural changes of the protein.
{"title":"Electrochemical sensing of organoferrocene ligand interaction with serum albumin in dimethyl sulfoxide media","authors":"Lucie Žaloudková , Vojtěch Hamala , Peter Šebest , Marek Zelinka , Hana Černocká , Jindřich Karban , Veronika Ostatná","doi":"10.1016/j.bioelechem.2026.109231","DOIUrl":"10.1016/j.bioelechem.2026.109231","url":null,"abstract":"<div><div>Protein-ligand interactions are crucial for understanding biochemical reactions and pathways, as well as for the design of new therapeutics. In this work, we compare the electrochemical behavior of four neutral organoferrocene ligands that differ in the number of monosaccharide and ferrocene units. The presence of a carbohydrate moiety results in increased hydrophilicity, while ferrocene units increase hydrophobicity, which significantly influences interactions with the surface, as well as with serum albumin. The adsorption of di-ferrocene ligands on the electrode surface and to serum albumin is more pronounced than that of mono-ferrocenes. Additionally, di-ferrocene ligands require dissolution in organic solvents, such as dimethyl sulfoxide, which also influences ligand-electrode and ligand-protein affinities. The conclusions of our work highlight the importance of ligand nature in determining the dissociation constant and mutual interactions with proteins, including those where ligands bind non-specifically. Electrochemical methods are suitable for studying the interactions of hydrophobic ligands with proteins because the ligands are typically present at micromolar concentrations to ensure their solubility in water. In addition, these methods exhibit high sensitivity to subtle structural changes of the protein.</div></div>","PeriodicalId":252,"journal":{"name":"Bioelectrochemistry","volume":"170 ","pages":"Article 109231"},"PeriodicalIF":4.5,"publicationDate":"2026-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146023967","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-19DOI: 10.1016/j.bioelechem.2026.109229
Hou-Yun Yang , Xiang Geng , Zhi-Dao Quan , Li Yu , Xian-Huai Huang , Wei-Hua Li , Tong-Zhan Xue , Yang Mu
Azo dyes, containing one or more azo bonds (–N=N–), are widely used but pose environmental and health risks due to their toxicity and resistance to degradation. Bioelectrochemical systems (BESs) offer a potential approach for their reductive degradation, yet the role of molecular structure in degradation remains unclear. In this study, nine representative azo dyes were examined to access how substituent type and position affect degradation kinetics and electron transfer under controlled cathodic potentials in BESs. Electron-withdrawing substituents (e.g., –SO3−, –NO2) and o−/m- substitution enhanced azo bond cleavage, while p-substitution or steric hindered degradation. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) revealed that higher reduction currents and lower charge-transfer resistance correlated with faster degradation. Quantitative structure-activity relationship (QSAR) analysis identified that the –N=N– group and other molecular features such as atom count, are key determinants of azo dyes removal. Experimental and theoretical calculations showed that molecular structure regulates the electron transfer efficiency from electrode to dye by affecting the electron density and steric hindrance of the azo bond, thereby determining degradation kinetics. This study deepened the influence of the molecular structure on azo dyes bioelectrochemical removal, and provided optimized guidance for the treatment of wastewater containing azo dyes by BESs.
{"title":"Molecular structure-dependent bioelectrochemical decolorization of azo dyes","authors":"Hou-Yun Yang , Xiang Geng , Zhi-Dao Quan , Li Yu , Xian-Huai Huang , Wei-Hua Li , Tong-Zhan Xue , Yang Mu","doi":"10.1016/j.bioelechem.2026.109229","DOIUrl":"10.1016/j.bioelechem.2026.109229","url":null,"abstract":"<div><div>Azo dyes, containing one or more azo bonds (–N=N–), are widely used but pose environmental and health risks due to their toxicity and resistance to degradation. Bioelectrochemical systems (BESs) offer a potential approach for their reductive degradation, yet the role of molecular structure in degradation remains unclear. In this study, nine representative azo dyes were examined to access how substituent type and position affect degradation kinetics and electron transfer under controlled cathodic potentials in BESs. Electron-withdrawing substituents (e.g., –SO<sub>3</sub><sup>−</sup>, –NO<sub>2</sub>) and o−/m- substitution enhanced azo bond cleavage, while p-substitution or steric hindered degradation. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) revealed that higher reduction currents and lower charge-transfer resistance correlated with faster degradation. Quantitative structure-activity relationship (QSAR) analysis identified that the –N=N– group and other molecular features such as atom count, are key determinants of azo dyes removal. Experimental and theoretical calculations showed that molecular structure regulates the electron transfer efficiency from electrode to dye by affecting the electron density and steric hindrance of the azo bond, thereby determining degradation kinetics. This study deepened the influence of the molecular structure on azo dyes bioelectrochemical removal, and provided optimized guidance for the treatment of wastewater containing azo dyes by BESs.</div></div>","PeriodicalId":252,"journal":{"name":"Bioelectrochemistry","volume":"170 ","pages":"Article 109229"},"PeriodicalIF":4.5,"publicationDate":"2026-01-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146023969","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-14DOI: 10.1016/j.bioelechem.2026.109226
Cam Abdullaeva , Daniel Coughlin , Nadiah Alyamni , Alexander G. Zestos
Endorphins are three proteins that belong to a family of neuropeptides that regulate pain perception, mood, and immune function by targeting opioid receptors. The biological role of ꞵ-endorphin is well studied, but α- and γ-endorphins are less understood. By creating more fast and reliable methods of detection, we can progress towards determining the physiological role of each endorphin. Carbon fiber microelectrodes (CFMEs) are promising sensors for biomolecule detection as they are small, cheap sensors that can target specific brain regions. Fast-scan cyclic voltammetry (FSCV) is an electroanalytical technique, often coupled with CFMEs, that has been used to measure a variety of neurotransmitters (NTs) and neuropeptides. This method is of interest due to its exceptionally high temporal resolution, but it is also relatively affordable, minimally invasive, and biocompatible. Because the endorphins contain tyrosine, they can be easily measured with FSCV using a modified sawhorse waveform (MSW). Endorphins were detected at as low as nanomolar concentrations with high stability, exhibiting a mixed adsorption- and diffusion-controlled mechanism, and can be co-detected with small molecule NTs such as dopamine (DA). ꞵ-Endorphins saturated the electrode quicker due to its bulkier size, and the CFME was found to be significantly more sensitive to α-endorphin than γ-endorphin. Finally, we detected endorphins in brain samples for proof of principle analysis of the assay.
{"title":"Characterizing human endorphins with fast-scan cyclic voltammetry and carbon fiber microelectrodes","authors":"Cam Abdullaeva , Daniel Coughlin , Nadiah Alyamni , Alexander G. Zestos","doi":"10.1016/j.bioelechem.2026.109226","DOIUrl":"10.1016/j.bioelechem.2026.109226","url":null,"abstract":"<div><div>Endorphins are three proteins that belong to a family of neuropeptides that regulate pain perception, mood, and immune function by targeting opioid receptors. The biological role of ꞵ-endorphin is well studied, but α- and γ-endorphins are less understood. By creating more fast and reliable methods of detection, we can progress towards determining the physiological role of each endorphin. Carbon fiber microelectrodes (CFMEs) are promising sensors for biomolecule detection as they are small, cheap sensors that can target specific brain regions. Fast-scan cyclic voltammetry (FSCV) is an electroanalytical technique, often coupled with CFMEs, that has been used to measure a variety of neurotransmitters (NTs) and neuropeptides. This method is of interest due to its exceptionally high temporal resolution, but it is also relatively affordable, minimally invasive, and biocompatible. Because the endorphins contain tyrosine, they can be easily measured with FSCV using a modified sawhorse waveform (MSW). Endorphins were detected at as low as nanomolar concentrations with high stability, exhibiting a mixed adsorption- and diffusion-controlled mechanism, and can be co-detected with small molecule NTs such as dopamine (DA). ꞵ-Endorphins saturated the electrode quicker due to its bulkier size, and the CFME was found to be significantly more sensitive to α-endorphin than γ-endorphin. Finally, we detected endorphins in brain samples for proof of principle analysis of the assay.</div></div>","PeriodicalId":252,"journal":{"name":"Bioelectrochemistry","volume":"170 ","pages":"Article 109226"},"PeriodicalIF":4.5,"publicationDate":"2026-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146008077","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-14DOI: 10.1016/j.bioelechem.2026.109225
Christian Meinert Bache , Michael E.J. López Mujica , Stepan Shipovskov , Andrew Ewing , Elena E. Ferapontova
Specific electroanalysis of neurotransmitters in the brain, bloodstream, cerebrospinal fluid (CSF), or at the cellular level critically depends on the availability of miniaturized electrodes for aptasensing. Yet, with electrode miniaturization, sensitivity of analysis and limits of detection (LOD) can be compromised. Here, we adapted the RNA-aptamer-based macroelectrode assay for dopamine to the microelectrode format, by using gold-plated carbon fiber microelectrodes (CFE), modified via thiol chemistry with cysteamine and an RNA aptamer, for specific dopamine detection. The sensitivity of analysis with gold-plated cylindrical microelectrodes improved 90-fold, to 9.75 μA μM−1 cm−2 (at +0.100 V) vs. 108 nA μM−1 cm−2 (at optimal +0.185 V) shown with gold disk macroelectrodes, with LOD being 60 and 100 nM, in PBS and in artificial CSF, respectively. Yet, epinephrine interfered at 0.1 V. At 0.05 V, the sensitivity dropped to 4.62 μA μM−1 cm−2 but the RNA-aptamer/cysteamine-modified CFEs demonstrated excellent selectivity for dopamine over epinephrine, norepinephrine, L-DOPA, DOPAC, and uric and ascorbic acids. These findings suggest a straightforward strategy for constructing biospecific aptamer-based microelectrodes. However, in matrices more complex than CSF, such as serum, dopamine oxidation was inhibited. Therefore, effective monitoring of dopamine levels in blood using aptamer microelectrodes will likely require the use of protective membranes.
{"title":"RNA aptamer-modified gold-plated carbon fiber microelectrodes for selective dopamine sensing","authors":"Christian Meinert Bache , Michael E.J. López Mujica , Stepan Shipovskov , Andrew Ewing , Elena E. Ferapontova","doi":"10.1016/j.bioelechem.2026.109225","DOIUrl":"10.1016/j.bioelechem.2026.109225","url":null,"abstract":"<div><div>Specific electroanalysis of neurotransmitters in the brain, bloodstream, cerebrospinal fluid (CSF), or at the cellular level critically depends on the availability of miniaturized electrodes for aptasensing. Yet, with electrode miniaturization, sensitivity of analysis and limits of detection (LOD) can be compromised. Here, we adapted the RNA-aptamer-based macroelectrode assay for dopamine to the microelectrode format, by using gold-plated carbon fiber microelectrodes (CFE), modified via thiol chemistry with cysteamine and an RNA aptamer, for specific dopamine detection. The sensitivity of analysis with gold-plated cylindrical microelectrodes improved 90-fold, to 9.75 μA μM<sup>−1</sup> cm<sup>−2</sup> (at +0.100 V) vs. 108 nA μM<sup>−1</sup> cm<sup>−2</sup> (at optimal +0.185 V) shown with gold disk macroelectrodes, with LOD being 60 and 100 nM, in PBS and in artificial CSF, respectively. Yet, epinephrine interfered at 0.1 V. At 0.05 V, the sensitivity dropped to 4.62 μA μM<sup>−1</sup> cm<sup>−2</sup> but the RNA-aptamer/cysteamine-modified CFEs demonstrated excellent selectivity for dopamine over epinephrine, norepinephrine, L-DOPA, DOPAC, and uric and ascorbic acids. These findings suggest a straightforward strategy for constructing biospecific aptamer-based microelectrodes. However, in matrices more complex than CSF, such as serum, dopamine oxidation was inhibited. Therefore, effective monitoring of dopamine levels in blood using aptamer microelectrodes will likely require the use of protective membranes.</div></div>","PeriodicalId":252,"journal":{"name":"Bioelectrochemistry","volume":"170 ","pages":"Article 109225"},"PeriodicalIF":4.5,"publicationDate":"2026-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146008106","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}