{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,8,4]],"date-time":"2026-08-04T13:51:40Z","timestamp":1785851500538,"version":"3.56.0"},"reference-count":46,"publisher":"American Chemical Society (ACS)","issue":"30","license":[{"start":{"date-parts":[[2026,6,25]],"date-time":"2026-06-25T00:00:00Z","timestamp":1782345600000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/100010663","name":"H2020 European Research Council","doi-asserted-by":"publisher","award":["851957"],"award-info":[{"award-number":["851957"]}],"id":[{"id":"10.13039\/100010663","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/100014440","name":"Ministerio de Ciencia, Innovaci?n y Universidades","doi-asserted-by":"publisher","award":["JDC2023-051694-I"],"award-info":[{"award-number":["JDC2023-051694-I"]}],"id":[{"id":"10.13039\/100014440","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/100014440","name":"Ministerio de Ciencia, Innovaci?n y Universidades","doi-asserted-by":"publisher","award":["PID2022-140418NA-I00"],"award-info":[{"award-number":["PID2022-140418NA-I00"]}],"id":[{"id":"10.13039\/100014440","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100004895","name":"European Social Fund Plus","doi-asserted-by":"publisher","award":["NA"],"award-info":[{"award-number":["NA"]}],"id":[{"id":"10.13039\/501100004895","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":[],"published-print":{"date-parts":[[2026,8,4]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>Carbon nanopipettes (CNPs) have emerged as powerful tools to track intracellular redox processes with high spatial resolution. Their implementation for robust H2O2 sensing, however, is still limited by stability and mechanistic constraints largely attributed to the surface chemistry of the electrode under nanoconfinement. To address this challenge, we report for the first time a combination of Prussian Blue\u2013Nickel hexacyanoferrate (PB-NiHCF) modified carbon nanopipettes for the electrochemical detection of H2O2 under nanoconfined conditions. Electrodeposition strategies and stabilization protocols for the growth of PB-NiHCF thin films are thoroughly inspected. Cyclic voltammetry and double-potential step chronoamperometry (DPSC) are used to rationalize the thin-layer regime established within the nanometric inner tip of the CNPs. Attention is devoted to the nature and catalytic properties of the electrodeposited materials, which are key factors governing the sensing performance. Notably, both the open-circuit potential of the modified nanopipette and the management of the applied potential at the working electrode prove crucial for the detection mechanism. The analytical performance of the system is evaluated by DPSC, demonstrating stable sensing and a linear response up to 500 \u03bcM H2O2 (R2 = 0.996), with a limit of detection of 28.9 \u03bcM at physiological pH, supporting further in vivo single-cell analysis. Overall, this work provides an analytical framework for H2O2 detection in thin-layer electrochemical cells, opening new perspectives for nanoscale electroanalysis in confined environments and coulometric sensor development.<\/jats:p>","DOI":"10.1021\/acs.analchem.6c02551","type":"journal-article","created":{"date-parts":[[2026,6,25]],"date-time":"2026-06-25T13:41:37Z","timestamp":1782394897000},"page":"22348-22358","source":"Crossref","is-referenced-by-count":0,"title":["Nanoelectroanalysis\nwith Carbon Nanopipettes Based\non Prussian Blue-NiHCF for Hydrogen Peroxide Sensing"],"prefix":"10.1021","volume":"98","author":[{"given":"Antonino Biagio","family":"Carbonaro","sequence":"first","affiliation":[{"name":"UCAM-SENS, Universidad Cato\u0301lica San Antonio de Murcia, UCAM HiTech , Avda. Andre\u0301s Herna\u0301ndez Ros, 1 , ,","place":["Murcia, Spain, 30107"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Gregorio","family":"Laucirica","sequence":"additional","affiliation":[{"name":"UCAM-SENS, Universidad Cato\u0301lica San Antonio de Murcia, UCAM HiTech , Avda. Andre\u0301s Herna\u0301ndez Ros, 1 , ,","place":["Murcia, Spain, 30107"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1221-3906","authenticated-orcid":true,"given":"Gasto\u0301n A.","family":"Crespo","sequence":"additional","affiliation":[{"name":"UCAM-SENS, Universidad Cato\u0301lica San Antonio de Murcia, UCAM HiTech , Avda. Andre\u0301s Herna\u0301ndez Ros, 1 , ,","place":["Murcia, Spain, 30107"]},{"name":"KTH Royal Institute of Technology , , Teknikringen 30 , ,","place":["Stockholm, Sweden, SE-114 28"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-3858-8466","authenticated-orcid":true,"given":"Mari\u0301a","family":"Cuartero","sequence":"additional","affiliation":[{"name":"UCAM-SENS, Universidad Cato\u0301lica San Antonio de Murcia, UCAM HiTech , Avda. Andre\u0301s Herna\u0301ndez Ros, 1 , ,","place":["Murcia, Spain, 30107"]},{"name":"KTH Royal Institute of Technology , , Teknikringen 30 , ,","place":["Stockholm, Sweden, SE-114 28"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,6,25]]},"reference":[{"key":"2026080409204864700_cit1","doi-asserted-by":"publisher","first-page":"46","DOI":"10.1016\/j.trac.2016.01.018","article-title":"Nanoelectrodes: Applications in Electrocatalysis, Single-Cell\nAnalysis and High-Resolution Electrochemical Imaging","volume":"79","author":"Clausmeyer","year":"2016","journal-title":"TrAC, Trends Anal. Chem."},{"key":"2026080409204864700_cit2","doi-asserted-by":"publisher","DOI":"10.1002\/admt.202500684","article-title":"Electrochemical Nanosensors: Fabrication,\nFunctionalization, and\nIntracellular Measurement","volume":"10","author":"Wu","year":"2025","journal-title":"Adv. Mater. Technol."},{"issue":"1","key":"2026080409204864700_cit3","doi-asserted-by":"publisher","first-page":"265","DOI":"10.1146\/annurev-anchem-061417-125840","article-title":"Fabrication\nand Use of Nanopipettes\nin Chemical Analysis","volume":"11","author":"Zhang","year":"2018","journal-title":"Annu. Rev. Anal Chem."},{"issue":"1","key":"2026080409204864700_cit4","doi-asserted-by":"publisher","first-page":"015304","DOI":"10.1088\/0957-4484\/21\/1\/015304","article-title":"Small Diameter Carbon Nanopipettes","volume":"21","author":"Singhal","year":"2010","journal-title":"Nanotechnology"},{"issue":"34","key":"2026080409204864700_cit5","doi-asserted-by":"publisher","first-page":"11654","DOI":"10.1021\/jacs.7b05058","article-title":"Electron-Transfer Gated Ion Transport\nin Carbon Nanopipets","volume":"139","author":"Wang","year":"2017","journal-title":"J. Am. Chem. Soc."},{"issue":"44","key":"2026080409204864700_cit6","doi-asserted-by":"publisher","first-page":"14752","DOI":"10.1039\/D1SC04282C","article-title":"Quantification of the Charge Transport\nProcesses inside Carbon Nanopipettes","volume":"12","author":"Liu","year":"2021","journal-title":"Chem.\nSci."},{"issue":"34","key":"2026080409204864700_cit7","doi-asserted-by":"publisher","first-page":"9056","DOI":"10.1039\/D0SC02807J","article-title":"The Double Life of Conductive Nanopipette: A Nanopore\nand an Electrochemical Nanosensor","volume":"11","author":"Jia","year":"2020","journal-title":"Chem. Sci."},{"key":"2026080409204864700_cit8","doi-asserted-by":"publisher","first-page":"137116","DOI":"10.1016\/j.snb.2024.137116","article-title":"Single\nCell Sensing\nand Degradation of H2O2 via Cyt C@ZIF-8 Confined Nanoreactor","volume":"426","author":"Lv","year":"2025","journal-title":"Sensors Actuators B Chem."},{"issue":"25","key":"2026080409204864700_cit9","doi-asserted-by":"publisher","first-page":"10228","DOI":"10.1021\/acs.analchem.4c00680","article-title":"An Ultramicroelectrode\nElectrochemistry and Surface Plasmon Resonance\nCoupling Method for Cell Exocytosis Study","volume":"96","author":"Zhao","year":"2024","journal-title":"Anal.\nChem."},{"issue":"47","key":"2026080409204864700_cit10","doi-asserted-by":"publisher","first-page":"15744","DOI":"10.1021\/acs.analchem.1c03874","article-title":"Potentiometric\nPH Nanosensor for Intracellular Measurements: Real-Time and Continuous\nAssessment of Local Gradients","volume":"93","author":"Aref","year":"2021","journal-title":"Anal. Chem."},{"issue":"7","key":"2026080409204864700_cit11","doi-asserted-by":"publisher","first-page":"4618","DOI":"10.1021\/acs.analchem.8b05885","article-title":"Cavity Carbon-Nanopipette Electrodes\nfor Dopamine Detection","volume":"91","author":"Yang","year":"2019","journal-title":"Anal. Chem."},{"issue":"7","key":"2026080409204864700_cit12","doi-asserted-by":"publisher","first-page":"3365","DOI":"10.1021\/ac403547b","article-title":"Carbon Pipette-Based Electrochemical\nNanosampler","volume":"86","author":"Yu","year":"2014","journal-title":"Anal. Chem."},{"issue":"32","key":"2026080409204864700_cit13","doi-asserted-by":"publisher","first-page":"17659","DOI":"10.1021\/acs.analchem.5c02834","article-title":"Thin-Layer\nBehavior in Carbon Nanopipettes.\nUnderstanding the Iontronic-Electronic Contributions","volume":"97","author":"Laucirica","year":"2025","journal-title":"Anal. Chem."},{"issue":"6","key":"2026080409204864700_cit14","doi-asserted-by":"publisher","first-page":"5054","DOI":"10.1021\/acs.analchem.5c07422","article-title":"Fundamental Insights\ninto Nanoconfined Devices by Using Electrochemical Impedance Spectroscopy","volume":"98","author":"Laucirica","year":"2026","journal-title":"Anal. Chem."},{"issue":"22","key":"2026080409204864700_cit15","doi-asserted-by":"publisher","first-page":"11462","DOI":"10.1021\/acs.analchem.4c06914","article-title":"Quantification of Tryptophan Enantiomers in a Single Cell by \u03b2-Cyclodextrin-Modified\nCarbon Nanopipettes","volume":"97","author":"Li","year":"2025","journal-title":"Anal. Chem."},{"key":"2026080409204864700_cit16","doi-asserted-by":"publisher","first-page":"138983","DOI":"10.1016\/j.snb.2025.138983","article-title":"Electrochemical\nQuantification of Intracellular Hydrogen Peroxide Using Cobalt Phthalocyanine\nModified Carbon Nanopipettes","volume":"448","author":"Yu","year":"2026","journal-title":"Sensors Actuators\nB Chem."},{"key":"2026080409204864700_cit17","doi-asserted-by":"publisher","DOI":"10.1002\/celc.202200373","article-title":"Metal-Organic-Framework-Based\nElectrochemical Nanosensor\nfor Hydrogen Peroxide","volume":"9","author":"Hesari","year":"2022","journal-title":"ChemElectroChem"},{"issue":"49","key":"2026080409204864700_cit18","doi-asserted-by":"publisher","first-page":"16987","DOI":"10.1021\/acs.analchem.2c04449","article-title":"Electrodeposition of\nMetal Nanoparticles inside Carbon Nanopipettes for Sensing Applications","volume":"94","author":"Wang","year":"2022","journal-title":"Anal. Chem."},{"issue":"3","key":"2026080409204864700_cit19","doi-asserted-by":"publisher","first-page":"389","DOI":"10.1016\/j.bios.2004.12.001","article-title":"Sensor and\nBiosensor Preparation, Optimisation and\nApplications of Prussian Blue Modified Electrodes","volume":"21","author":"Ricci","year":"2005","journal-title":"Biosens. Bioelectron."},{"issue":"105","key":"2026080409204864700_cit20","doi-asserted-by":"publisher","first-page":"103328","DOI":"10.1039\/C6RA24128J","article-title":"Iron\u2013Nickel Hexacyanoferrate\nBilayer as an Advanced Electrocatalyst for H 2 O 2 Reduction","volume":"6","author":"Karpova","year":"2016","journal-title":"RSC Adv."},{"issue":"6","key":"2026080409204864700_cit21","doi-asserted-by":"publisher","first-page":"2359","DOI":"10.1021\/ac1033352","article-title":"Superstable Advanced\nHydrogen Peroxide Transducer Based on Transition Metal Hexacyanoferrates","volume":"83","author":"Sitnikova","year":"2011","journal-title":"Anal. Chem."},{"key":"2026080409204864700_cit22","doi-asserted-by":"publisher","first-page":"535","DOI":"10.1016\/j.redox.2014.02.006","article-title":"Hydrogen Peroxide\nSensing, Signaling and Regulation of Transcription Factors","volume":"2","author":"Marinho","year":"2014","journal-title":"Redox Biol."},{"key":"2026080409204864700_cit23","doi-asserted-by":"publisher","first-page":"613","DOI":"10.1016\/j.redox.2016.12.035","article-title":"Hydrogen Peroxide\nas a Central Redox Signaling Molecule in Physiological Oxidative Stress:\nOxidative Eustress","volume":"11","author":"Sies","year":"2017","journal-title":"Redox Biol."},{"issue":"18","key":"2026080409204864700_cit24","doi-asserted-by":"publisher","first-page":"3691","DOI":"10.1016\/j.molcel.2021.08.018","article-title":"Redox Metabolism:\nROS as Specific Molecular Regulators\nof Cell Signaling and Function","volume":"81","author":"Lennicke","year":"2021","journal-title":"Mol. Cell"},{"issue":"12","key":"2026080409204864700_cit25","doi-asserted-by":"publisher","first-page":"1129","DOI":"10.1038\/ni1202-1129","article-title":"Hydrogen Peroxide\nas Second Messenger in Lymphocyte Activation","volume":"3","author":"Reth","year":"2002","journal-title":"Nat. Immunol."},{"issue":"4","key":"2026080409204864700_cit26","doi-asserted-by":"publisher","first-page":"281","DOI":"10.1038\/nmeth866","article-title":"Genetically Encoded\nFluorescent Indicator for Intracellular Hydrogen Peroxide","volume":"3","author":"Belousov","year":"2006","journal-title":"Nat. Methods"},{"key":"2026080409204864700_cit27","doi-asserted-by":"publisher","first-page":"127203","DOI":"10.1016\/j.cej.2020.127203","article-title":"Real-Time\nPhotoelectrochemical Quantification of Hydrogen Peroxide Produced\nby Living Cells","volume":"407","author":"Hu","year":"2021","journal-title":"Chem. Eng. J."},{"issue":"19","key":"2026080409204864700_cit28","doi-asserted-by":"publisher","first-page":"9970","DOI":"10.1021\/ac502909c","article-title":"A Highly Sensitive\nRatiometric Fluorescent\nProbe for the Detection of Cytoplasmic and Nuclear Hydrogen Peroxide","volume":"86","author":"Wen","year":"2014","journal-title":"Anal. Chem."},{"key":"2026080409204864700_cit29","doi-asserted-by":"publisher","first-page":"28","DOI":"10.1016\/j.elecom.2013.12.015","article-title":"Nanosensors\nfor the Detection of\nHydrogen Peroxide","volume":"40","author":"Clausmeyer","year":"2014","journal-title":"Electrochem. Commun."},{"issue":"12","key":"2026080409204864700_cit30","doi-asserted-by":"publisher","first-page":"2125","DOI":"10.1002\/celc.201600390","article-title":"Intracellular\nHydrogen Peroxide Detection with Functionalised Nanoelectrodes","volume":"3","author":"Marquitan","year":"2016","journal-title":"ChemElectroChem"},{"issue":"7","key":"2026080409204864700_cit31","doi-asserted-by":"publisher","first-page":"838","DOI":"10.1021\/acssensors.6b00247","article-title":"Can Calibration-Free\nSensors Be Realized?","volume":"1","author":"Bakker","year":"2016","journal-title":"ACS Sens."},{"issue":"5","key":"2026080409204864700_cit32","doi-asserted-by":"publisher","first-page":"6326","DOI":"10.1007\/s12274-023-5692-0","article-title":"Pillar Effect\nBoosting the Electrochemical\nStability of Prussian Blue-Polypyrrole for Potassium Ion Batteries","volume":"16","author":"Zhou","year":"2023","journal-title":"Nano Res."},{"issue":"1","key":"2026080409204864700_cit33","doi-asserted-by":"publisher","first-page":"3","DOI":"10.1016\/j.talanta.2003.11.044","article-title":"Prussian Blue\nModified Glassy Carbon Electrodes?Study on Operational Stability and\nIts Application as a Sucrose Biosensor","volume":"64","author":"Haghighi","year":"2004","journal-title":"Talanta"},{"issue":"10","key":"2026080409204864700_cit34","doi-asserted-by":"publisher","first-page":"813","DOI":"10.1002\/1521-4109(200106)13:10&lt;813::AID-ELAN813&gt;3.0.CO;2-Z","article-title":"Prussian\nBlue and Its Analogues: Electrochemistry and Analytical Applications","volume":"13","author":"Karyakin","year":"2001","journal-title":"Electroanalysis"},{"key":"2026080409204864700_cit35","doi-asserted-by":"publisher","first-page":"410","DOI":"10.1016\/j.talanta.2015.08.072","article-title":"Application\nof Prussian Blue Electrodes for Amperometric Detection of Free Chlorine\nin Water Samples Using Flow Injection Analysis","volume":"146","author":"Salazar","year":"2016","journal-title":"Talanta"},{"issue":"15","key":"2026080409204864700_cit36","doi-asserted-by":"publisher","first-page":"7135","DOI":"10.1021\/acs.jpcc.5c00877","article-title":"Degradation Mechanisms of Prussian\nBlue Analogues and State-of-the-Art Approaches for Stability Optimization:\nA Review","volume":"129","author":"Sterzinger","year":"2025","journal-title":"J. Phys. Chem. C"},{"issue":"2","key":"2026080409204864700_cit37","doi-asserted-by":"publisher","first-page":"78","DOI":"10.1016\/S1388-2481(99)00010-7","article-title":"On the Mechanism\nof H2O2 Reduction at Prussian Blue Modified Electrodes","volume":"1","author":"Karyakin","year":"1999","journal-title":"Electrochem. Commun."},{"key":"2026080409204864700_cit38","doi-asserted-by":"publisher","first-page":"180","DOI":"10.1016\/j.jmst.2021.11.020","article-title":"One-Step Synthesis\nof Novel Core-Shell Bimetallic Hexacyanoferrate for High Performance\nSodium-Storage Cathode","volume":"114","author":"Zuo","year":"2022","journal-title":"J. Mater. Sci. Technol."},{"key":"2026080409204864700_cit39","doi-asserted-by":"publisher","first-page":"173","DOI":"10.1016\/j.electacta.2013.10.020","article-title":"Iron Triad-Mate Hexacyanoferrates\nas Prussian Blue Stabilizers: Toward the Advanced Hydrogen Peroxide\nTransducer","volume":"122","author":"Sitnikova","year":"2014","journal-title":"Electrochim. Acta"},{"issue":"28","key":"2026080409204864700_cit40","doi-asserted-by":"publisher","first-page":"4261","DOI":"10.1016\/j.electacta.2003.08.001","article-title":"Influence of Experimental\nConditions on Electrochemical Behavior of Prussian Blue Type Nickel\nHexacyanoferrate Film","volume":"48","author":"Zamponi","year":"2003","journal-title":"Electrochim. Acta"},{"issue":"9","key":"2026080409204864700_cit41","doi-asserted-by":"publisher","first-page":"4131","DOI":"10.1021\/ac500595v","article-title":"Transition Metal Hexacyanoferrates in Electrocatalysis\nof H 2 O 2 Reduction: An Exclusive Property of Prussian Blue","volume":"86","author":"Sitnikova","year":"2014","journal-title":"Anal. Chem."},{"key":"2026080409204864700_cit42","doi-asserted-by":"publisher","first-page":"107838","DOI":"10.1016\/j.bioelechem.2021.107838","article-title":"A Feasible Electrochemical Biosensor\nfor Determination of Glucose\nBased on Prussian Blue \u2013 Enzyme Aggregates Cascade Catalytic\nSystem","volume":"141","author":"Yan","year":"2021","journal-title":"Bioelectrochemistry"},{"key":"2026080409204864700_cit43","doi-asserted-by":"publisher","first-page":"119314","DOI":"10.1016\/j.ica.2019.119314","article-title":"H2O2-Sensing Abilities\nof Mixed-Metal (Fe-Ni) Prussian Blue Analogs in a Wide PH Range","volume":"502","author":"Ishizaki","year":"2020","journal-title":"Inorg. Chim. Acta"},{"key":"2026080409204864700_cit44","doi-asserted-by":"publisher","first-page":"113","DOI":"10.1016\/j.snb.2016.06.094","article-title":"PH-Dependent\nResponse of a Hydrogen Peroxide Sensing Probe","volume":"237","author":"Akbari Khorami","year":"2016","journal-title":"Sensors Actuators B Chem."},{"issue":"18","key":"2026080409204864700_cit45","doi-asserted-by":"publisher","first-page":"8897","DOI":"10.1021\/ac5022908","article-title":"Open Carbon Nanopipettes as Resistive-Pulse\nSensors, Rectification Sensors, and Electrochemical Nanoprobes","volume":"86","author":"Hu","year":"2014","journal-title":"Anal. Chem."},{"issue":"18","key":"2026080409204864700_cit46","doi-asserted-by":"publisher","first-page":"13197","DOI":"10.1021\/acs.analchem.6c00702","article-title":"Scan-Rate-Induced\nTransition from Redox to Ion Current Rectification in Carbon Nanopipettes","volume":"98","author":"Laucirica","year":"2026","journal-title":"Anal. Chem."}],"container-title":["Analytical Chemistry"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/pubs.acs.org\/doi\/pdf\/10.1021\/acs.analchem.6c02551","content-type":"application\/pdf","content-version":"vor","intended-application":"unspecified"},{"URL":"https:\/\/pubs.acs.org\/ancham\/article-pdf\/98\/30\/22348\/66381807\/acs.analchem.6c02551.pdf","content-type":"application\/pdf","content-version":"vor","intended-application":"syndication"},{"URL":"https:\/\/pubs.acs.org\/ancham\/article-pdf\/98\/30\/22348\/66381807\/acs.analchem.6c02551.pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,8,4]],"date-time":"2026-08-04T13:23:44Z","timestamp":1785849824000},"score":1,"resource":{"primary":{"URL":"https:\/\/pubs.acs.org\/ancham\/article\/98\/30\/22348\/5242482\/Nanoelectroanalysis-with-Carbon-Nanopipettes-Based"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2026,6,25]]},"references-count":46,"journal-issue":{"issue":"30","published-online":{"date-parts":[[2026,6,25]]},"published-print":{"date-parts":[[2026,8,4]]}},"URL":"https:\/\/doi.org\/10.1021\/acs.analchem.6c02551","relation":{},"ISSN":["0003-2700","1520-6882"],"issn-type":[{"value":"0003-2700","type":"print"},{"value":"1520-6882","type":"electronic"}],"subject":[],"published":{"date-parts":[[2026,6,25]]}}}