{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,8,20]],"date-time":"2026-08-20T14:40:09Z","timestamp":1787236809338,"version":"build-2736575974"},"reference-count":44,"publisher":"MDPI AG","issue":"12","license":[{"start":{"date-parts":[[2022,12,11]],"date-time":"2022-12-11T00:00:00Z","timestamp":1670716800000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"name":"European Regional Development Fund of the European Union and Greek national funds","award":["T2EDK-00028\/MIS 5067540"],"award-info":[{"award-number":["T2EDK-00028\/MIS 5067540"]}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Biosensors"],"abstract":"<jats:p>In this work, a 3D printed sensor modified with a water-stable complex of Fe(III) basic benzoate is presented for the voltammetric detection of glucose (GLU) in acidic epidermal skin conditions. The GLU sensor was produced by the drop-casting of Fe(III)-cluster ethanolic mixture on the surface of a 3D printed electrode fabricated by a carbon black loaded polylactic acid filament. The oxidation of GLU was electrocatalyzed by Fe(III), which was electrochemically generated in-situ by the Fe(III)-cluster precursor. The GLU determination was carried out by differential pulse voltammetry without the interference from common electroactive metabolites presented in sweat (such as urea, uric acid, and lactic acid), offering a limit of detection of 4.3 \u03bcmol L\u22121. The exceptional electrochemical performance of [Fe3O(PhCO2)6(H2O)3]\u2219PhCO2 combined with 3D printing technology forms an innovative and low-cost enzyme-free sensor suitable for noninvasive applications, opening the way for integrated 3D printed wearable biodevices.<\/jats:p>","DOI":"10.3390\/bios12121156","type":"journal-article","created":{"date-parts":[[2022,12,12]],"date-time":"2022-12-12T01:42:27Z","timestamp":1670809347000},"page":"1156","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":15,"title":["3D Printed Voltammetric Sensor Modified with an Fe(III)-Cluster for the Enzyme-Free Determination of Glucose in Sweat"],"prefix":"10.3390","volume":"12","author":[{"given":"Eleni","family":"Koukouviti","sequence":"first","affiliation":[{"name":"Laboratory of Analytical Chemistry, Department of Chemistry, National and Kapodistrian University of Athens, 15771 Athens, Greece"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3284-3451","authenticated-orcid":false,"given":"Alexios K.","family":"Plessas","sequence":"additional","affiliation":[{"name":"Laboratory of Inorganic Chemistry, Department of Chemistry, National and Kapodistrian University of Athens, 15771 Athens, Greece"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-4590-9261","authenticated-orcid":false,"given":"Anastasios","family":"Economou","sequence":"additional","affiliation":[{"name":"Laboratory of Analytical Chemistry, Department of Chemistry, National and Kapodistrian University of Athens, 15771 Athens, Greece"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-4624-4735","authenticated-orcid":false,"given":"Nikolaos","family":"Thomaidis","sequence":"additional","affiliation":[{"name":"Laboratory of Analytical Chemistry, Department of Chemistry, National and Kapodistrian University of Athens, 15771 Athens, Greece"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5514-6371","authenticated-orcid":false,"given":"Giannis S.","family":"Papaefstathiou","sequence":"additional","affiliation":[{"name":"Laboratory of Inorganic Chemistry, Department of Chemistry, National and Kapodistrian University of Athens, 15771 Athens, Greece"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-4696-0245","authenticated-orcid":false,"given":"Christos","family":"Kokkinos","sequence":"additional","affiliation":[{"name":"Laboratory of Analytical Chemistry, Department of Chemistry, National and Kapodistrian University of Athens, 15771 Athens, Greece"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"1968","published-online":{"date-parts":[[2022,12,11]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"311","DOI":"10.1016\/j.diabres.2011.10.029","article-title":"IDF Diabetes Atlas: Global estimates of the prevalence of diabetes for 2011 and 2030","volume":"94","author":"Whiting","year":"2011","journal-title":"Diabetes Res. Clin. Pract."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"16","DOI":"10.1016\/j.coelec.2020.02.018","article-title":"Noninvasive monitoring of diabetes and hypoxia by wearable flow-through biosensors","volume":"23","author":"Karpova","year":"2020","journal-title":"Curr. Opin. Electrochem."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"389","DOI":"10.1038\/s41587-019-0045-y","article-title":"Wearable biosensors for healthcare monitoring","volume":"37","author":"Kim","year":"2019","journal-title":"Nat. Biotechnol."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"120922","DOI":"10.1016\/j.talanta.2020.120922","article-title":"Wearable non-invasive monitors of diabetes and hypoxia through continuous analysis of sweat","volume":"215","author":"Karpova","year":"2020","journal-title":"Talanta"},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"1","DOI":"10.1146\/annurev-anchem-061318-114910","article-title":"Wearable Sensors for Biochemical Sweat Analysis","volume":"12","author":"Bandodkar","year":"2019","journal-title":"Annu. Rev. Anal. Chem."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"237","DOI":"10.1002\/elan.202100273","article-title":"An Overview of Wearable and Implantable Electrochemical Glucose Sensors","volume":"34","author":"Zhu","year":"2022","journal-title":"Electroanalysis"},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"2230003","DOI":"10.1142\/S1793545822300038","article-title":"Blood glucose sensors and recent advances: A review","volume":"15","author":"Peng","year":"2022","journal-title":"J. Innov. Opt. Health Sci."},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"5537","DOI":"10.1039\/D2TB00749E","article-title":"Recent advancements in noninvasive glucose monitoring and closed-loop management systems for diabetes","volume":"10","author":"Ma","year":"2022","journal-title":"J. Mater. Chem. B"},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"38","DOI":"10.1016\/j.electacta.2016.03.193","article-title":"Non-enzymataic Glucose electrochemical sensor made of porous NiO thin films prepared by reactive magnetron sputtering at oblique angles","volume":"201","author":"Salazar","year":"2016","journal-title":"Electrochim. Acta"},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"879","DOI":"10.1016\/j.elecom.2005.05.009","article-title":"Non-enzymatic glucose detection free of ascorbic acid interference using nickel powder and nafion sol-gel dispersed renewable carbon ceramic electrode","volume":"7","author":"Salimi","year":"2005","journal-title":"Electrochem. Commun."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"1135","DOI":"10.1021\/acssensors.8b00168","article-title":"Nonenzymatic wearable sensor for electrochemical analysis of perspiration glucose","volume":"3","author":"Zhu","year":"2018","journal-title":"ACS Sens."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"3331","DOI":"10.1021\/acs.analchem.0c05057","article-title":"Smartphone-Addressable 3D-Printed Electrochemical Ring for Nonenzymatic Self-Monitoring of Glucose in Human Sweat","volume":"93","author":"Katseli","year":"2021","journal-title":"Anal. Chem."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"748957","DOI":"10.3389\/fchem.2021.748957","article-title":"Recent Advances in Non-Enzymatic Glucose Sensors Based on Metal and Metal Oxide Nanostructures for Diabetes Management\u2014A Review","volume":"9","author":"Naikoo","year":"2021","journal-title":"Front. Chem."},{"key":"ref_14","doi-asserted-by":"crossref","unstructured":"Thatikayala, D., Ponnamma, D., Sadasivuni, K.K., Cabibihan, J.J., Al-Ali, A.K., Malik, R.A., and Min, B. (2020). Progress of Advanced Nanomaterials in the Non-Enzymatic Electrochemical Sensing of Glucose and H2O2. Biosensors, 10.","DOI":"10.3390\/bios10110151"},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"1800","DOI":"10.1002\/elan.202100029","article-title":"Copper Nanoflowers on Carbon Cloth as a Flexible Electrode toward Both Enzymeless Electrocatalytic Glucose and H2O2","volume":"33","author":"Yuan","year":"2021","journal-title":"Electroanalysis"},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"786970","DOI":"10.3389\/fchem.2021.786970","article-title":"Cu-Based Conductive MOF Grown in situ on Cu Foam as a Highly Selective and Stable Non-Enzymatic Glucose Sensor","volume":"9","author":"Hu","year":"2021","journal-title":"Front. Chem."},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"835","DOI":"10.1002\/elan.202100519","article-title":"Heterostructural NiCo2O4 Nanocomposites for Nonenzymatic Electrochemical Glucose Sensing","volume":"34","author":"Yang","year":"2022","journal-title":"Electroanalysis"},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"1755","DOI":"10.1002\/elan.201700025","article-title":"Highly Sensitive Nonenzymatic Glucose Sensor Based on 3D Ultrathin NiFe Layered Double Hydroxide Nanosheets","volume":"29","author":"Lu","year":"2017","journal-title":"Electroanalysis"},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"115558","DOI":"10.1016\/j.jelechem.2021.115558","article-title":"min A Cu2O\/PEDOT\/graphene-modified electrode for the enzyme-free detection and quantification of glucose","volume":"897","author":"Liu","year":"2021","journal-title":"J. Electroanal. Chem."},{"key":"ref_20","doi-asserted-by":"crossref","unstructured":"Guati, C., Gomez-Coma, L., Fallanza, M., and Ortiz, I. (2021). Non-enzymatic amperometric glucose screen-printed sensors based on copper and copper oxide particles. Appl. Sci., 11.","DOI":"10.3390\/app112210830"},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"114888","DOI":"10.1016\/j.jelechem.2020.114888","article-title":"A highly sensitive nonenzymatic glucose sensor based on Cu\/Cu2O composite nanoparticles decorated single carbon fiber","volume":"880","author":"Fang","year":"2021","journal-title":"J. Electroanal. Chem."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"4790","DOI":"10.1021\/acsanm.1c00381","article-title":"Nonenzymatic Saliva-Range Glucose Sensing Using Electrodeposited Cuprous Oxide Nanocubes on a Graphene Strip","volume":"4","author":"Gao","year":"2021","journal-title":"ACS Appl. Nano Mater."},{"key":"ref_23","first-page":"829","article-title":"Cu2O ordered nanoarrays for non-enzymatic glucose detection","volume":"24","author":"Liu","year":"2021","journal-title":"J. Appl. Sci. Eng."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"113610","DOI":"10.1016\/j.bios.2021.113610","article-title":"Electrocatalytic CuBr@CuO nanoparticles based salivary glucose probes","volume":"194","author":"Lin","year":"2021","journal-title":"Biosens. Bioelectron."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"100453","DOI":"10.1016\/j.sbsr.2021.100453","article-title":"Nonenzymatic electrochemical sensors via Cu native oxides (CuNOx) for sweat glucose monitoring","volume":"34","author":"Alam","year":"2021","journal-title":"Sens. Bio-Sens. Res."},{"key":"ref_26","first-page":"100453","article-title":"Fully metallic copper 3D-printed electrodes via sintering for electrocatalytic biosensing","volume":"25","author":"Redondo","year":"2021","journal-title":"Appl. Mater. Today"},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"107852","DOI":"10.1016\/j.diamond.2020.107852","article-title":"Hybrid nanomaterial of ZnFe2O4\/\u03b1-Fe2O3 implanted graphene for electrochemical glucose sensing application","volume":"106","author":"Neravathu","year":"2020","journal-title":"Diam. Relat. Mater."},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"420","DOI":"10.1016\/j.msec.2013.11.030","article-title":"Construction of a non-enzymatic glucose sensor based on copolymer P4VP-co-PAN and Fe2O3 nanoparticles","volume":"35","author":"Chen","year":"2014","journal-title":"Mater. Sci. Eng. C"},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"4241","DOI":"10.1039\/c1an15367f","article-title":"A novel non-enzymatic glucose sensor modified with Fe2O3 nanowire arrays","volume":"136","author":"Cao","year":"2011","journal-title":"Analyst"},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"B19","DOI":"10.1149\/2.057401jes","article-title":"Highly Stable and Selective Non-Enzymatic Glucose Biosensor Using Carbon Nanotubes Decorated by Fe3O4 Nanoparticles","volume":"161","author":"Khodadadi","year":"2014","journal-title":"J. Electrochem. Soc."},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"1811","DOI":"10.1007\/s00604-015-1511-y","article-title":"Enzyme-free glucose sensing based on Fe3O4 nanorod arrays","volume":"182","author":"Zhang","year":"2015","journal-title":"Microchim. Acta"},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"1581","DOI":"10.1016\/j.elecom.2010.09.002","article-title":"A novel non-enzymatic electrochemical glucose sensor modified with FeOOH nanowire","volume":"12","author":"Xia","year":"2010","journal-title":"Electrochem. Commun."},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"116177","DOI":"10.1016\/j.trac.2020.116177","article-title":"The emerging role of 3D printing in the fabrication of detection systems","volume":"136","year":"2021","journal-title":"TrAC-Trends Anal. Chem."},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"78","DOI":"10.1016\/j.coelec.2020.04.009","article-title":"3D-printed electrochemical sensors: A new horizon for measurement of biomolecules","volume":"20","author":"Abdalla","year":"2020","journal-title":"Curr. Opin. Electrochem."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"16557","DOI":"10.1039\/D1RA01987B","article-title":"Recent progress of conductive 3D-printed electrodes based upon polymers\/carbon nanomaterials using a fused deposition modelling (FDM) method as emerging electrochemical sensing devices","volume":"11","author":"Omar","year":"2021","journal-title":"RSC Adv."},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"265","DOI":"10.1007\/s00604-021-04901-2","article-title":"How 3D printing can boost advances in analytical and bioanalytical chemistry","volume":"188","author":"Ambrosi","year":"2021","journal-title":"Microchim. Acta"},{"key":"ref_37","doi-asserted-by":"crossref","unstructured":"Earnshaw, A., Figgis, B.N., and Lewis, J. (1966). Chemistry of polynuclear compounds. Part VI. Magnetic properties of trimeric chromium and iron carboxylates. J. Chem. Soc. A Inorg. Phys. Theor., 1656\u20131663.","DOI":"10.1039\/j19660001656"},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"3710","DOI":"10.1002\/ejic.200600306","article-title":"Syntheses, Structural, and Physical Studies of Basic Cr III and Fe III Benzilates and Benzoates: Evidence of Antisymmetric Exchange and Distributions of Isotropic and Antisymmetric Exchange Parameters","volume":"2006","author":"Psycharis","year":"2006","journal-title":"Eur. J. Inorg. Chem."},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"229","DOI":"10.1007\/s10751-010-0179-2","article-title":"M\u00f6ssbauer spectra of two extended series of basic iron(III) carboxylates [Fe3O(O2CR)6(H2O)6]A (A\u2212 = ClO4\u2212, NO3\u2212)","volume":"198","author":"Georgopoulou","year":"2010","journal-title":"Hyperfine Interact."},{"key":"ref_40","first-page":"501","article-title":"Crystal and molecular structure of [Fe3O(C6H5COO)6(H2O)3] 3-Cl-PyH\u00b7(CH3C6H4SO3)2\u00b72H2O","volume":"71","author":"Cadelnic","year":"1997","journal-title":"Pol. J. Chem."},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"1231","DOI":"10.1107\/S0021889813013113","article-title":"EXPO2013: A kit of tools for phasing crystal structures from powder data","volume":"46","author":"Altomare","year":"2013","journal-title":"J. Appl. Crystallogr."},{"key":"ref_42","doi-asserted-by":"crossref","first-page":"17","DOI":"10.1186\/1758-2946-4-17","article-title":"Avogadro: An advanced semantic chemical editor, visualization, and analysis platform","volume":"4","author":"Hanwell","year":"2012","journal-title":"J. Cheminform."},{"key":"ref_43","doi-asserted-by":"crossref","first-page":"116393","DOI":"10.1016\/j.jelechem.2022.116393","article-title":"Graphite paste sensor modified with a Cu(II)-complex for the enzyme-free simultaneous voltammetric determination of glucose and uric acid in sweat","volume":"917","author":"Vasiliou","year":"2022","journal-title":"J. Electroanal. Chem."},{"key":"ref_44","doi-asserted-by":"crossref","first-page":"671","DOI":"10.1038\/nmeth.2089","article-title":"NIH Image to ImageJ: 25 years of image analysis","volume":"9","author":"Schneider","year":"2012","journal-title":"Nat. Methods"}],"container-title":["Biosensors"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/2079-6374\/12\/12\/1156\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,11]],"date-time":"2025-10-11T01:38:04Z","timestamp":1760146684000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/2079-6374\/12\/12\/1156"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2022,12,11]]},"references-count":44,"journal-issue":{"issue":"12","published-online":{"date-parts":[[2022,12]]}},"alternative-id":["bios12121156"],"URL":"https:\/\/doi.org\/10.3390\/bios12121156","relation":{},"ISSN":["2079-6374"],"issn-type":[{"value":"2079-6374","type":"electronic"}],"subject":[],"published":{"date-parts":[[2022,12,11]]}}}