{"title":"Mini Review on Revisiting Marcus Theory and Novel Understanding Heterogeneous Electron Transfer by Programing Tools","authors":"Xuanze Wang, Jie Deng, Kulika Pithaksinsakul, Yachao Zhu, Jiaxin Ren, Jiangfeng Qian, Olivier Fontaine","doi":"10.1002/elan.12045","DOIUrl":"https://doi.org/10.1002/elan.12045","url":null,"abstract":"<p>Electron transfer is always the spotlight in electrochemistry, especially electrochemical energy storage. However, the current understanding of electron transfer, particularly in heterogeneous systems as explained by Marcus theory, faces challenges in accurately accounting for surface effects, solvent reorganization, and quantum tunneling, which are critical to real-world applications. Here, this review presents a comprehensive analysis of the heterogeneous electron transfer processes within the framework of Marcus theory, focusing on computing approaches using Python and Wolfram Language. The introduction outlines the significance of Marcus theory in explaining electron transfer reactions and sets the stage for the subsequent discussions. In the results and discussions section, the electron distribution in heterogeneous systems is explored, comparing the effects of different formalisms on electron transfer. A detailed comparison of the computational approaches using Python and Mathematica underscores the essential role of programing in tackling complex electron transfer models. These tools offer powerful, complementary capabilities for simulating the nuanced behavior of heterogeneous electron transfer processes, providing researchers with the flexibility and precision necessary to address the limitations of traditional theoretical methods. Finally, the work delves into the law of conservation of energy within the context of Marcus theory, offering a nuanced discussion of its implications for electron transfer studies. This review aims to equip researchers with practical insights and computing tools to enhance their understanding and application of Marcus theory in heterogeneous systems.</p>","PeriodicalId":162,"journal":{"name":"Electroanalysis","volume":"37 4","pages":""},"PeriodicalIF":2.7,"publicationDate":"2025-04-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143793570","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}
{"title":"Mini Review on Revisiting Marcus Theory and Novel Understanding Heterogeneous Electron Transfer by Programing Tools","authors":"Xuanze Wang, Jie Deng, Kulika Pithaksinsakul, Yachao Zhu, Jiaxin Ren, Jiangfeng Qian, Olivier Fontaine","doi":"10.1002/elan.12045","DOIUrl":"https://doi.org/10.1002/elan.12045","url":null,"abstract":"<p>Electron transfer is always the spotlight in electrochemistry, especially electrochemical energy storage. However, the current understanding of electron transfer, particularly in heterogeneous systems as explained by Marcus theory, faces challenges in accurately accounting for surface effects, solvent reorganization, and quantum tunneling, which are critical to real-world applications. Here, this review presents a comprehensive analysis of the heterogeneous electron transfer processes within the framework of Marcus theory, focusing on computing approaches using Python and Wolfram Language. The introduction outlines the significance of Marcus theory in explaining electron transfer reactions and sets the stage for the subsequent discussions. In the results and discussions section, the electron distribution in heterogeneous systems is explored, comparing the effects of different formalisms on electron transfer. A detailed comparison of the computational approaches using Python and Mathematica underscores the essential role of programing in tackling complex electron transfer models. These tools offer powerful, complementary capabilities for simulating the nuanced behavior of heterogeneous electron transfer processes, providing researchers with the flexibility and precision necessary to address the limitations of traditional theoretical methods. Finally, the work delves into the law of conservation of energy within the context of Marcus theory, offering a nuanced discussion of its implications for electron transfer studies. This review aims to equip researchers with practical insights and computing tools to enhance their understanding and application of Marcus theory in heterogeneous systems.</p>","PeriodicalId":162,"journal":{"name":"Electroanalysis","volume":"37 4","pages":""},"PeriodicalIF":2.7,"publicationDate":"2025-04-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143793644","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}
Saptarshi Paul, John F. Koons, Michael L. Harrigan, Kingshuk Roy, Jeffrey E. Dick
{"title":"Tuning Nanoparticle Microstructure through Nanodroplet-Mediated Electrodeposition: Applications to PtCu Alloy Nanoparticle Synthesis and Electrocatalysis","authors":"Saptarshi Paul, John F. Koons, Michael L. Harrigan, Kingshuk Roy, Jeffrey E. Dick","doi":"10.1002/elan.12043","DOIUrl":"https://doi.org/10.1002/elan.12043","url":null,"abstract":"<p>Nanoparticles are an indispensable part of our lives. From electronic devices to drug delivery to catalysis and energy storage, nanoparticles have found various important applications. Out of the many synthetic strategies to generate nanoparticles, electrodeposition has stood out due to its cost effectiveness, low time consumption and simplicity. However, traditional electrodeposition techniques have suffered from controlling the size, shape, morphology and microstructure of nanoparticles. Here, we use a technique called nanodroplet-mediated electrodeposition, where nanodroplets carrying the metal salt precursor collide with a negatively-biased electrode. In this work, we use this nanodroplet-mediated electrodeposition technique along with transmission electron microscopy, selected-area electron diffraction and high-angle-annular dark-field scanning transmission electron microscopy to show control over the microstructure of single nanoparticles. Along with that, we use X-ray photoelectron spectroscopy to get mechanistic insights behind the alteration of microstructure observed. Having achieved a control over the microstructure, we show the application by synthesising polycrystalline alloys at room temperature and evaluating the electrocatalytic behavior of the different microstructures towards the hydrogen evolution reaction. This fundamental work of controlling microstructures of single nanoparticles and its applications in alloy synthesis and electrocatalysis opens a new avenue of tuning nanoparticles for various applications.</p>","PeriodicalId":162,"journal":{"name":"Electroanalysis","volume":"37 4","pages":""},"PeriodicalIF":2.7,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/elan.12043","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143769976","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Saptarshi Paul, John F. Koons, Michael L. Harrigan, Kingshuk Roy, Jeffrey E. Dick
{"title":"Tuning Nanoparticle Microstructure through Nanodroplet-Mediated Electrodeposition: Applications to PtCu Alloy Nanoparticle Synthesis and Electrocatalysis","authors":"Saptarshi Paul, John F. Koons, Michael L. Harrigan, Kingshuk Roy, Jeffrey E. Dick","doi":"10.1002/elan.12043","DOIUrl":"https://doi.org/10.1002/elan.12043","url":null,"abstract":"<p>Nanoparticles are an indispensable part of our lives. From electronic devices to drug delivery to catalysis and energy storage, nanoparticles have found various important applications. Out of the many synthetic strategies to generate nanoparticles, electrodeposition has stood out due to its cost effectiveness, low time consumption and simplicity. However, traditional electrodeposition techniques have suffered from controlling the size, shape, morphology and microstructure of nanoparticles. Here, we use a technique called nanodroplet-mediated electrodeposition, where nanodroplets carrying the metal salt precursor collide with a negatively-biased electrode. In this work, we use this nanodroplet-mediated electrodeposition technique along with transmission electron microscopy, selected-area electron diffraction and high-angle-annular dark-field scanning transmission electron microscopy to show control over the microstructure of single nanoparticles. Along with that, we use X-ray photoelectron spectroscopy to get mechanistic insights behind the alteration of microstructure observed. Having achieved a control over the microstructure, we show the application by synthesising polycrystalline alloys at room temperature and evaluating the electrocatalytic behavior of the different microstructures towards the hydrogen evolution reaction. This fundamental work of controlling microstructures of single nanoparticles and its applications in alloy synthesis and electrocatalysis opens a new avenue of tuning nanoparticles for various applications.</p>","PeriodicalId":162,"journal":{"name":"Electroanalysis","volume":"37 4","pages":""},"PeriodicalIF":2.7,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/elan.12043","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143769977","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ElectroanalysisPub Date : 2025-03-26DOI: 10.1002/elan.202580104
{"title":"Cover Picture: (Electroanalysis 4/2025)","authors":"","doi":"10.1002/elan.202580104","DOIUrl":"https://doi.org/10.1002/elan.202580104","url":null,"abstract":"<p>Cover picture provided by Dr. Elena Benito-Peña and Dr. Susana Campuzano. <i>Electroanalysis</i> 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.\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure></p>","PeriodicalId":162,"journal":{"name":"Electroanalysis","volume":"37 4","pages":""},"PeriodicalIF":2.7,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/elan.202580104","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143698948","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ElectroanalysisPub Date : 2025-03-26DOI: 10.1002/elan.202580104
{"title":"Cover Picture: (Electroanalysis 4/2025)","authors":"","doi":"10.1002/elan.202580104","DOIUrl":"https://doi.org/10.1002/elan.202580104","url":null,"abstract":"<p>Cover picture provided by Dr. Elena Benito-Peña and Dr. Susana Campuzano. <i>Electroanalysis</i> 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.\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure></p>","PeriodicalId":162,"journal":{"name":"Electroanalysis","volume":"37 4","pages":""},"PeriodicalIF":2.7,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/elan.202580104","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143698946","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Electrochemical Sensor for Carboxypeptidase Y Using a 4-Aminonaphthol-Conjugated Peptide Substrate Lacking a Free Carboxyl Group at the C-Terminus","authors":"Hyeryeong Lee, Seonhwa Park, Haesik Yang","doi":"10.1002/elan.12044","DOIUrl":"https://doi.org/10.1002/elan.12044","url":null,"abstract":"<p>Carboxypeptidase Y (CPY) is a serine carboxypeptidase crucial for understanding protein processing, degradation pathways, and intracellular transport, yet no electrochemical detection method has been reported. Here, we present the first electrochemical sensor for CPY, leveraging its ability to cleave 4-aminonaphthol (AN)-conjugated succinyl-Leu–Leu-Val-Tyr (Suc-LLVY-AN) even in the absence of a free carboxyl group at the C-terminus. Upon proteolysis, the electroactive species AN is released and detected using electrochemical–enzymatic redox cycling. We optimized pH, temperature, and incubation time to maximize the signal-to-background ratio. Under optimal conditions (pH 7.4, 37°C, 30 min), the sensor achieved a detection limit of 0.2 µg/mL in phosphate-buffered saline, outperforming a comparable fluorescence-based method (0.6 µg/mL). Even in artificial saliva, the sensor maintained favorable sensitivity (0.5 µg/mL), demonstrating its potential for complex sample analysis. Selectivity tests against other proteases confirmed high specificity, as only CPY effectively cleaved the Suc-LLVY-AN substrate. Overall, this novel electrochemical approach offers enhanced sensitivity and specificity for CPY detection, broadening the scope of electrochemical protease sensors and providing a valuable tool for diverse biochemical and diagnostic applications.</p>","PeriodicalId":162,"journal":{"name":"Electroanalysis","volume":"37 3","pages":""},"PeriodicalIF":2.7,"publicationDate":"2025-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143689113","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}
Fungai D. Chibaya, Usisipho Feleni, Thabo T. I. Nkambule, Ntuthuko W. Hlongwa
{"title":"Tungsten Selenide Quantum Dot-Based Electrocatalytic Detection of Lamivudine","authors":"Fungai D. Chibaya, Usisipho Feleni, Thabo T. I. Nkambule, Ntuthuko W. Hlongwa","doi":"10.1002/elan.12038","DOIUrl":"https://doi.org/10.1002/elan.12038","url":null,"abstract":"<p>\u0000Lamivudine (LAM) is an antiviral drug used against hepatitis, human immunodeficiency virus, and acquired immunodeficiency syndrome. Due to the increasing occurrence of antiviral drugs in wastewaters around the globe, and the health hazards and risks associated with the inherent human and ecosystem exposure, researchers have taken advantage of the reactivity of these antiviral drugs and their affinity to form various bonds with novel nanoparticles, to foster more convenient and environmentally friendly methods of wastewater monitoring of antivirals using nanomaterials in sensor fabrication. The deviation from the conventional methods of wastewater monitoring seeks to overcome the inefficiency, tediousness, and complexity of sample preparation of the conventional methods. In the current research work, a colloidal synthesis method was developed and used to synthesize L-cysteine-functionalized tungsten diselenide quantum dots (L-cyst-WSe<sub>2</sub>QDs) for the monitoring of LAM in water. Characterization of nanoparticles was done using different spectroscopy methods, transmission electron microscopy (TEM), and X-ray diffraction (XRD) patterns. Successful capping and functionalization of QDs was demonstrated by Fourier-transform infrared spectroscopy. Small-angle X-ray scattering and zetasizer analytical studies corroborated the formation of QDs of sizes less than 10 nm. High-resolution TEM, XRD, and small-angle electron diffraction confirmed the highly crystalline nature of the QDs. The L-cyst-WSe<sub>2</sub>QDs were bound by Nafion to a preactivated glassy carbon (GC) electrode, and the fabricated sensor exhibited excellent electrochemical sensing efficiency as compared to previously reported WSe<sub>2</sub> sensors and other various sensors used to detect LAM, presenting high sensitivity and good selectivity with the lowest reported limit of detection (LOD) of 0.1 nM using the square wave voltammetry (SWV) technique in wastewater effluents. This work provided a lower LOD than previous reports on electrochemical sensing of LAM using differential pulse voltammetry and SWV. Though the electrochemical behavior of LAM on L-cyst-WSe<sub>2</sub>QDs/GC was established for the first time through this current study, LAM was irreversibly reduced at negative potentials, validating a previously established characteristic response. The sensor exhibited high reproducibility with an excellent stability by retaining 87.2% sensor functionality and stability after 7 days. The reduction peak current of LAM presented a linear range of 2–10 pM with a correlation coefficient of 0.993. The application of the LAM sensor in the determination of LAM in real wastewater samples exhibited excellent recoveries ranging between 94.6% and 99.9%, thereby demonstrating the suitability of the sensor for application in real time.</p>","PeriodicalId":162,"journal":{"name":"Electroanalysis","volume":"37 3","pages":""},"PeriodicalIF":2.7,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/elan.12038","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143688952","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Nadiah Alyamni, Clarice Cook, Jandro L. Abot, Alexander G. Zestos
{"title":"Enzyme-Modified Microelectrodes for Measurement of Glutamate: Characterization and Applications","authors":"Nadiah Alyamni, Clarice Cook, Jandro L. Abot, Alexander G. Zestos","doi":"10.1002/elan.12041","DOIUrl":"https://doi.org/10.1002/elan.12041","url":null,"abstract":"<p>Glutamate is a critical neurotransmitter in the central nervous system that plays a key role in numerous physiological processes and neurological disorders. Traditional methods of glutamate detection have low spatiotemporal resolution, while electrochemical methods are limited due to glutamate not being readily redox active at unmodified carbon electrode surfaces. This study presents the development of a glutamate oxidase-modified microelectrode for the sensitive, real-time detection of glutamate using fast-scan cyclic voltammetry (FSCV) with a triangle waveform. Here, we employed a chitosan-hydrogel coating to immobilize glutamate oxidase onto carbon-fiber microelectrodes, enabling selective metabolism of glutamate to hydrogen peroxide. The metabolism to hydrogen peroxide facilitates indirect detection with high sensitivity across a concentration range relevant to physiological concentrations. We utilized FSCV for detection, which enhanced temporal resolution and chemical selectivity, allowing for the codetection of glutamate with other neurotransmitters such as dopamine and norepinephrine. We performed proof-of-concept validation and testing utilizing both biological fluids and complex food samples, demonstrating the enzyme-modified microelectrode's broad applicability in clinical diagnostics and food quality assessment. The sensor showed excellent stability, resistance to fouling, and retained over 90% of its initial response after multiple uses. This work highlights the potential of this biosensor as a versatile tool for minimally invasive, biocompatible, rapid, and accurate glutamate measurement in a wide variety of samples for a diverse set of applications.</p>","PeriodicalId":162,"journal":{"name":"Electroanalysis","volume":"37 3","pages":""},"PeriodicalIF":2.7,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143638653","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}
{"title":"Single Entity Electrochemistry in Motion","authors":"Emily Dominique, Christophe Renault","doi":"10.1002/elan.12040","DOIUrl":"https://doi.org/10.1002/elan.12040","url":null,"abstract":"<p>Single entity electrochemistry (SEE) finds exciting application in analytical chemistry. Multiple methodologies have been tailored to measure conventional quantities such as concentration and size for a large variety of particles. Intense effort is also dedicated to investigation of chemical dynamics in electro-catalysis. This mini-review will focus its attention to the analysis of motion of particles at the interface and near the interface. The velocity of particles and types of motion (lateral, transversal, and rotational) will be discussed for a wide range of particles including solid metal and polystyrene particles as well as soft liquid droplets and gas bubbles. A new perspective on motion in SEE will be given by discussing the motion of phase boundaries within solid particles as well as soft liquid droplets and gas bubbles.</p>","PeriodicalId":162,"journal":{"name":"Electroanalysis","volume":"37 3","pages":""},"PeriodicalIF":2.7,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143638654","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}