Electroassisted Incorporation of Ferrocene Within Sol–Gel Silica Films to Enhance Electron Transfer—Part II: Boosting Protein Sensing with Polyelectrolyte-Modified Silica

Silica-modified electrodes possess physicochemical properties that make them valuable in electrochemical sensing and energy-related applications. Although intrinsically insulating, silica thin films can selectively interact with redox species, producing sieving effects that enhance electrochemical r...

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Main Authors: Rayane-Ichrak Loughlani, Alonso Gamero-Quijano, Francisco Montilla
Format: Article
Language:English
Published: MDPI AG 2025-08-01
Series:Molecules
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Online Access:https://www.mdpi.com/1420-3049/30/15/3246
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author Rayane-Ichrak Loughlani
Alonso Gamero-Quijano
Francisco Montilla
author_facet Rayane-Ichrak Loughlani
Alonso Gamero-Quijano
Francisco Montilla
author_sort Rayane-Ichrak Loughlani
collection DOAJ
description Silica-modified electrodes possess physicochemical properties that make them valuable in electrochemical sensing and energy-related applications. Although intrinsically insulating, silica thin films can selectively interact with redox species, producing sieving effects that enhance electrochemical responses. We synthesized Class I hybrid silica matrices incorporating either negatively charged poly(4-styrene sulfonic acid) or positively charged poly(diallyl dimethylammonium chloride). These hybrid films were deposited onto ITO electrodes and evaluated via cyclic voltammetry in aqueous ferrocenium solutions. The polyelectrolyte charge played a key role in the electroassisted incorporation of ferrocene: silica-PSS films promoted accumulation, while silica-PDADMAC films hindered it due to electrostatic repulsion. In situ UV-vis spectroscopy confirmed that only a fraction of the embedded ferrocene was electroactive. Nevertheless, this fraction enabled effective mediated detection of cytochrome c in solution. These findings highlight the crucial role of ionic interactions and hybrid composition in electron transfer to redox proteins, providing valuable insights for the development of advanced bioelectronic sensors.
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institution Kabale University
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series Molecules
spelling doaj-art-80d65bcb70594c4cb6e9120aa60cc3c32025-08-20T03:36:32ZengMDPI AGMolecules1420-30492025-08-013015324610.3390/molecules30153246Electroassisted Incorporation of Ferrocene Within Sol–Gel Silica Films to Enhance Electron Transfer—Part II: Boosting Protein Sensing with Polyelectrolyte-Modified SilicaRayane-Ichrak Loughlani0Alonso Gamero-Quijano1Francisco Montilla2Departamento de Química Física, Instituto Universitario de Materiales de Alicante (IUMA), Universidad de Alicante, Carretera San Vicente s/n, 03690 Alicante, SpainDepartamento de Química Física, Instituto Universitario de Materiales de Alicante (IUMA), Universidad de Alicante, Carretera San Vicente s/n, 03690 Alicante, SpainDepartamento de Química Física, Instituto Universitario de Materiales de Alicante (IUMA), Universidad de Alicante, Carretera San Vicente s/n, 03690 Alicante, SpainSilica-modified electrodes possess physicochemical properties that make them valuable in electrochemical sensing and energy-related applications. Although intrinsically insulating, silica thin films can selectively interact with redox species, producing sieving effects that enhance electrochemical responses. We synthesized Class I hybrid silica matrices incorporating either negatively charged poly(4-styrene sulfonic acid) or positively charged poly(diallyl dimethylammonium chloride). These hybrid films were deposited onto ITO electrodes and evaluated via cyclic voltammetry in aqueous ferrocenium solutions. The polyelectrolyte charge played a key role in the electroassisted incorporation of ferrocene: silica-PSS films promoted accumulation, while silica-PDADMAC films hindered it due to electrostatic repulsion. In situ UV-vis spectroscopy confirmed that only a fraction of the embedded ferrocene was electroactive. Nevertheless, this fraction enabled effective mediated detection of cytochrome c in solution. These findings highlight the crucial role of ionic interactions and hybrid composition in electron transfer to redox proteins, providing valuable insights for the development of advanced bioelectronic sensors.https://www.mdpi.com/1420-3049/30/15/3246hybrid silica functionalizationferroceneelectroassisted accumulation mediated electron transfercytochrome c
spellingShingle Rayane-Ichrak Loughlani
Alonso Gamero-Quijano
Francisco Montilla
Electroassisted Incorporation of Ferrocene Within Sol–Gel Silica Films to Enhance Electron Transfer—Part II: Boosting Protein Sensing with Polyelectrolyte-Modified Silica
Molecules
hybrid silica functionalization
ferrocene
electroassisted accumulation mediated electron transfer
cytochrome c
title Electroassisted Incorporation of Ferrocene Within Sol–Gel Silica Films to Enhance Electron Transfer—Part II: Boosting Protein Sensing with Polyelectrolyte-Modified Silica
title_full Electroassisted Incorporation of Ferrocene Within Sol–Gel Silica Films to Enhance Electron Transfer—Part II: Boosting Protein Sensing with Polyelectrolyte-Modified Silica
title_fullStr Electroassisted Incorporation of Ferrocene Within Sol–Gel Silica Films to Enhance Electron Transfer—Part II: Boosting Protein Sensing with Polyelectrolyte-Modified Silica
title_full_unstemmed Electroassisted Incorporation of Ferrocene Within Sol–Gel Silica Films to Enhance Electron Transfer—Part II: Boosting Protein Sensing with Polyelectrolyte-Modified Silica
title_short Electroassisted Incorporation of Ferrocene Within Sol–Gel Silica Films to Enhance Electron Transfer—Part II: Boosting Protein Sensing with Polyelectrolyte-Modified Silica
title_sort electroassisted incorporation of ferrocene within sol gel silica films to enhance electron transfer part ii boosting protein sensing with polyelectrolyte modified silica
topic hybrid silica functionalization
ferrocene
electroassisted accumulation mediated electron transfer
cytochrome c
url https://www.mdpi.com/1420-3049/30/15/3246
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