Pub Date : 2026-01-31DOI: 10.1016/j.electacta.2026.148348
Filipe C.D.A. Lima, Frank N. Crespilho
Electron transport in proteins has traditionally been described within Marcus theory, where localized hopping events between redox centers are modulated by nuclear reorganization. Recent advances in scanning tunneling microscopy (STM) and single-protein junction measurements, however, reveal measurable conductance values and resonant tunneling features that suggest delocalized quantum contributions. In this work, we present a unified theoretical model that combines Landauer transmission with Marcus heterogeneous kinetics to rationalize enzymatic electron transport. Within the Landauer–Büttiker formalism, STM conductance maps provide access to local transmission probabilities and electrode–protein couplings, which can be recast into effective electronic coupling parameters. These couplings, when introduced into Marcus theory, yield spatially resolved heterogeneous rate constants (<span><span style=""></span><span data-mathml='<math xmlns="http://www.w3.org/1998/Math/MathML"><msub is="true"><mi is="true">k</mi><mtext is="true">het</mtext></msub></math>' role="presentation" style="font-size: 90%; display: inline-block; position: relative;" tabindex="0"><svg aria-hidden="true" focusable="false" height="2.317ex" role="img" style="vertical-align: -0.582ex;" viewbox="0 -747.2 1604.7 997.6" width="3.727ex" xmlns:xlink="http://www.w3.org/1999/xlink"><g fill="currentColor" stroke="currentColor" stroke-width="0" transform="matrix(1 0 0 -1 0 0)"><g is="true"><g is="true"><use xlink:href="#MJMATHI-6B"></use></g><g is="true" transform="translate(521,-150)"><use transform="scale(0.707)" xlink:href="#MJMAIN-68"></use><use transform="scale(0.707)" x="556" xlink:href="#MJMAIN-65" y="0"></use><use transform="scale(0.707)" x="1001" xlink:href="#MJMAIN-74" y="0"></use></g></g></g></svg><span role="presentation"><math xmlns="http://www.w3.org/1998/Math/MathML"><msub is="true"><mi is="true">k</mi><mtext is="true">het</mtext></msub></math></span></span><script type="math/mml"><math><msub is="true"><mi is="true">k</mi><mtext is="true">het</mtext></msub></math></script></span>), bridging quantum conductance channels with classical ET kinetics. We illustrate this connection with model calculations, including Breit–Wigner transmission functions, Marcus parabolas across conductance ranges of 1–100 nS, and simulated STM conductance maps for enzymes with multiple hotspots. The results demonstrate that nanoscale conductance variations translate into orders-of-magnitude differences in <span><span style=""></span><span data-mathml='<math xmlns="http://www.w3.org/1998/Math/MathML"><msub is="true"><mi is="true">k</mi><mtext is="true">het</mtext></msub></math>' role="presentation" style="font-size: 90%; display: inline-block; position: relative;" tabindex="0"><svg aria-hidden="true" focusable="false" height="2.317ex" role="img" style="vertical-align: -0.582ex;" viewbox="0 -747.2 1604.7 99
{"title":"Protein Local Conductance in Quantum Bioelectrochemistry via Landauer–Marcus Kinetics","authors":"Filipe C.D.A. Lima, Frank N. Crespilho","doi":"10.1016/j.electacta.2026.148348","DOIUrl":"https://doi.org/10.1016/j.electacta.2026.148348","url":null,"abstract":"Electron transport in proteins has traditionally been described within Marcus theory, where localized hopping events between redox centers are modulated by nuclear reorganization. Recent advances in scanning tunneling microscopy (STM) and single-protein junction measurements, however, reveal measurable conductance values and resonant tunneling features that suggest delocalized quantum contributions. In this work, we present a unified theoretical model that combines Landauer transmission with Marcus heterogeneous kinetics to rationalize enzymatic electron transport. Within the Landauer–Büttiker formalism, STM conductance maps provide access to local transmission probabilities and electrode–protein couplings, which can be recast into effective electronic coupling parameters. These couplings, when introduced into Marcus theory, yield spatially resolved heterogeneous rate constants (<span><span style=\"\"></span><span data-mathml='<math xmlns=\"http://www.w3.org/1998/Math/MathML\"><msub is=\"true\"><mi is=\"true\">k</mi><mtext is=\"true\">het</mtext></msub></math>' role=\"presentation\" style=\"font-size: 90%; display: inline-block; position: relative;\" tabindex=\"0\"><svg aria-hidden=\"true\" focusable=\"false\" height=\"2.317ex\" role=\"img\" style=\"vertical-align: -0.582ex;\" viewbox=\"0 -747.2 1604.7 997.6\" width=\"3.727ex\" xmlns:xlink=\"http://www.w3.org/1999/xlink\"><g fill=\"currentColor\" stroke=\"currentColor\" stroke-width=\"0\" transform=\"matrix(1 0 0 -1 0 0)\"><g is=\"true\"><g is=\"true\"><use xlink:href=\"#MJMATHI-6B\"></use></g><g is=\"true\" transform=\"translate(521,-150)\"><use transform=\"scale(0.707)\" xlink:href=\"#MJMAIN-68\"></use><use transform=\"scale(0.707)\" x=\"556\" xlink:href=\"#MJMAIN-65\" y=\"0\"></use><use transform=\"scale(0.707)\" x=\"1001\" xlink:href=\"#MJMAIN-74\" y=\"0\"></use></g></g></g></svg><span role=\"presentation\"><math xmlns=\"http://www.w3.org/1998/Math/MathML\"><msub is=\"true\"><mi is=\"true\">k</mi><mtext is=\"true\">het</mtext></msub></math></span></span><script type=\"math/mml\"><math><msub is=\"true\"><mi is=\"true\">k</mi><mtext is=\"true\">het</mtext></msub></math></script></span>), bridging quantum conductance channels with classical ET kinetics. We illustrate this connection with model calculations, including Breit–Wigner transmission functions, Marcus parabolas across conductance ranges of 1–100 nS, and simulated STM conductance maps for enzymes with multiple hotspots. The results demonstrate that nanoscale conductance variations translate into orders-of-magnitude differences in <span><span style=\"\"></span><span data-mathml='<math xmlns=\"http://www.w3.org/1998/Math/MathML\"><msub is=\"true\"><mi is=\"true\">k</mi><mtext is=\"true\">het</mtext></msub></math>' role=\"presentation\" style=\"font-size: 90%; display: inline-block; position: relative;\" tabindex=\"0\"><svg aria-hidden=\"true\" focusable=\"false\" height=\"2.317ex\" role=\"img\" style=\"vertical-align: -0.582ex;\" viewbox=\"0 -747.2 1604.7 99","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"58 1","pages":""},"PeriodicalIF":6.6,"publicationDate":"2026-01-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146095522","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-30DOI: 10.1016/j.electacta.2026.148335
Adane Y. Heram, Ephriem T. Mengesha, Abi T. Mengesha, Zewdu Bezu, Yiheyis Bogale, Endale T. Bedada, Tadele T. Megerssa
{"title":"E. coli Imprinted CdS/ZnO/Ag2CO3 Nanocomposites for Rapid, Sensitive and Selective Electrochemical E. Coli Sensing","authors":"Adane Y. Heram, Ephriem T. Mengesha, Abi T. Mengesha, Zewdu Bezu, Yiheyis Bogale, Endale T. Bedada, Tadele T. Megerssa","doi":"10.1016/j.electacta.2026.148335","DOIUrl":"https://doi.org/10.1016/j.electacta.2026.148335","url":null,"abstract":"","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"8 1","pages":"148335"},"PeriodicalIF":6.6,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146072737","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-30DOI: 10.1016/j.electacta.2026.148341
Dijana Jadreško, Robert Vianello, Ivana Novak Jovanović
{"title":"Electrochemical oxidation and voltammetric determination of γ-carbolinone-derived synthetic cannabinoid 5F-Cumyl-PEGACLONE","authors":"Dijana Jadreško, Robert Vianello, Ivana Novak Jovanović","doi":"10.1016/j.electacta.2026.148341","DOIUrl":"https://doi.org/10.1016/j.electacta.2026.148341","url":null,"abstract":"","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"7 1","pages":""},"PeriodicalIF":6.6,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146089405","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Polysulfides are poorly retained within porous cathodes and readily diffuse into the electrolyte over time, leading to the well-known shuttle effect that undermines the reversibility of Li–S batteries. Here, we demonstrate that catalytic disproportionation of polysulfides provides an effective pathway to suppress this process by rapidly converting dissolved species into solid sulfur and sulfides, thereby preventing their migration into the electrolyte. Fundamentally, the sluggish kinetics of sulfur redox reactions are responsible for the accumulation and redistribution of soluble polysulfides in the bulk electrolyte. By accelerating these kinetics, catalyzed disproportionation not only confines sulfur within the conductive cathode matrix but also promotes the homogeneous precipitation of Li₂S₂/Li₂S, which enhances electrochemical reversibility and cycling stability. Using nitrogen-doped carbon (NC800) as a model catalyst, we reveal its ability to drive a pseudo-16-electron reduction pathway, leading to a single dominant Li₂S product and uniform deposition within the porous framework. In contrast, a non-catalytic carbon (KB) yields multiple polysulfide intermediates and heterogeneous deposition. The mechanistic insights provided here highlight the pivotal role of catalytic disproportionation in reshaping sulfur redox pathways and offer a rational strategy for mitigating polysulfide shuttling in practical Li–S pouch cells.
{"title":"Mitigation of polysulfide shuttle effect in Li-S batteries through catalytic disproportionation reaction","authors":"Huainan Qu , Dantong Qiu , Xiaoxiao Zhang , Dong Zheng , Xiao-Qing Yang , Deyang Qu","doi":"10.1016/j.electacta.2026.148334","DOIUrl":"10.1016/j.electacta.2026.148334","url":null,"abstract":"<div><div>Polysulfides are poorly retained within porous cathodes and readily diffuse into the electrolyte over time, leading to the well-known shuttle effect that undermines the reversibility of Li–S batteries. Here, we demonstrate that catalytic disproportionation of polysulfides provides an effective pathway to suppress this process by rapidly converting dissolved species into solid sulfur and sulfides, thereby preventing their migration into the electrolyte. Fundamentally, the sluggish kinetics of sulfur redox reactions are responsible for the accumulation and redistribution of soluble polysulfides in the bulk electrolyte. By accelerating these kinetics, catalyzed disproportionation not only confines sulfur within the conductive cathode matrix but also promotes the homogeneous precipitation of Li₂S₂/Li₂S, which enhances electrochemical reversibility and cycling stability. Using nitrogen-doped carbon (NC800) as a model catalyst, we reveal its ability to drive a pseudo-16-electron reduction pathway, leading to a single dominant Li₂S product and uniform deposition within the porous framework. In contrast, a non-catalytic carbon (KB) yields multiple polysulfide intermediates and heterogeneous deposition. The mechanistic insights provided here highlight the pivotal role of catalytic disproportionation in reshaping sulfur redox pathways and offer a rational strategy for mitigating polysulfide shuttling in practical Li–S pouch cells.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"554 ","pages":"Article 148334"},"PeriodicalIF":5.6,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146072750","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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