{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,2,5]],"date-time":"2026-02-05T10:16:45Z","timestamp":1770286605101,"version":"3.49.0"},"reference-count":45,"publisher":"MDPI AG","issue":"14","license":[{"start":{"date-parts":[[2023,7,11]],"date-time":"2023-07-11T00:00:00Z","timestamp":1689033600000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"name":"Regione Emilia-Romagna","award":["POR FSE 2014\/2020"],"award-info":[{"award-number":["POR FSE 2014\/2020"]}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Sensors"],"abstract":"<jats:p>R-(+)-limonene, one of the major constituents of citrus oils, is a monoterpene that is widely used as a fragrance additive in cosmetics, foods, and industrial solvents. Nowadays, its detection mainly relies on bulky and expensive analytical methods and only a few research works proved its revelation through affordable and portable sensors, such as electrochemical and quartz crystal microbalance sensors. In response to the demand for effective miniaturized sensing devices to be integrated into Internet of Things systems, this study represents a pioneering investigation of chemoresistive gas sensor capabilities addressed to R-(+)-limonene detection. An array of seven metal-oxide sensors was exploited to perform a complete electrical characterization of the target analyte. The experimental evidence allowed us to identify the WO3-based sensor as the most promising candidate for R-(+)-limonene detection. The material was highly sensitive already at sub-ppm concentrations (response of 2.5 at 100 ppb), consistent with applicative parameters, and it resulted in selective vs. different gases at a lower operating temperature (200 \u00b0C) than the other sensors tested. Furthermore, it exhibited a humidity-independent behavior under real-life conditions (relative humidity &gt; 20%). Finally, the WO3 sensor also demonstrated a remarkable cross-selectivity, thus enabling its exploitation in cutting-edge applications.<\/jats:p>","DOI":"10.3390\/s23146291","type":"journal-article","created":{"date-parts":[[2023,7,11]],"date-time":"2023-07-11T01:58:14Z","timestamp":1689040694000},"page":"6291","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":13,"title":["New Approach for the Detection of Sub-ppm Limonene: An Investigation through Chemoresistive Metal-Oxide Semiconductors"],"prefix":"10.3390","volume":"23","author":[{"given":"Arianna","family":"Rossi","sequence":"first","affiliation":[{"name":"Department of Physics and Earth Sciences, University of Ferrara, Via Saragat 1\/C, 44122 Ferrara, Italy"}]},{"given":"Elena","family":"Spagnoli","sequence":"additional","affiliation":[{"name":"Department of Physics and Earth Sciences, University of Ferrara, Via Saragat 1\/C, 44122 Ferrara, Italy"}]},{"given":"Francesco","family":"Tralli","sequence":"additional","affiliation":[{"name":"Department of Physics and Earth Sciences, University of Ferrara, Via Saragat 1\/C, 44122 Ferrara, Italy"}]},{"given":"Marco","family":"Marzocchi","sequence":"additional","affiliation":[{"name":"Sacmi Imola S.C., Olfactory Systems, Via Selice Prov.le, 17\/a, 40026 Imola, Italy"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9726-8481","authenticated-orcid":false,"given":"Vincenzo","family":"Guidi","sequence":"additional","affiliation":[{"name":"Department of Physics and Earth Sciences, University of Ferrara, Via Saragat 1\/C, 44122 Ferrara, Italy"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0188-2178","authenticated-orcid":false,"given":"Barbara","family":"Fabbri","sequence":"additional","affiliation":[{"name":"Department of Physics and Earth Sciences, University of Ferrara, Via Saragat 1\/C, 44122 Ferrara, Italy"}]}],"member":"1968","published-online":{"date-parts":[[2023,7,11]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"668","DOI":"10.1016\/j.fct.2018.07.052","article-title":"Review of Toxicological Assessment of D-Limonene, a Food and Cosmetics Additive","volume":"120","author":"Ravichandran","year":"2018","journal-title":"Food Chem. Toxicol."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"17","DOI":"10.1080\/10937404.2013.769418","article-title":"Safety Evaluation And Risk Assessment Of d-Limonene","volume":"16","author":"Kim","year":"2013","journal-title":"J. Toxicol. Environ. Health Part B"},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"132479","DOI":"10.1016\/j.foodchem.2022.132479","article-title":"Nanodelivery Systems for D-Limonene; Techniques and Applications","volume":"384","author":"Sadeghi","year":"2022","journal-title":"Food Chem."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"278","DOI":"10.1016\/j.atmosenv.2012.01.006","article-title":"Use of Electronic Nose and GC-MS in Detection and Monitoring Some VOC","volume":"51","author":"Giraldez","year":"2012","journal-title":"Atmos. Environ."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"97","DOI":"10.1016\/j.cbi.2018.02.007","article-title":"Limonene: Aroma of Innovation in Health and Disease","volume":"283","author":"Vieira","year":"2018","journal-title":"Chem. Biol. Interact."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"1811","DOI":"10.1021\/es026231i","article-title":"Ozone-Initiated Reactions with Mixtures of Volatile Organic Compounds under Simulated Indoor Conditions","volume":"37","author":"Fan","year":"2003","journal-title":"Environ. Sci. Technol."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"3851","DOI":"10.5194\/acp-9-3851-2009","article-title":"Photodegradation of Secondary Organic Aerosol Generated from Limonene Oxidation by Ozone Studied with Chemical Ionization Mass Spectrometry","volume":"9","author":"Pan","year":"2009","journal-title":"Atmos. Chem. Phys."},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"107556","DOI":"10.1016\/j.buildenv.2020.107556","article-title":"In-Situ-Desorption of Indoor Relevant VOC Toluene and Limonene on Activated Carbon Based Filter Media Using High Relative Humidity","volume":"191","author":"Ligotski","year":"2021","journal-title":"Build. Environ."},{"key":"ref_9","unstructured":"(2023, June 16). PubChem, Available online: https:\/\/Pubchem.Ncbi.Nlm.Nih.Gov\/Compound\/D-Limonene#section=Threshold-Limit-Values-%28TLV%29."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"115977","DOI":"10.1016\/j.jelechem.2021.115977","article-title":"Electrochemical Sensing of Limonene Using Thiol Capped Gold Nanoparticles and Its Detection in the Real Breath Sample of a Cirrhotic Patient","volume":"905","author":"Nazir","year":"2022","journal-title":"J. Electroanal. Chem."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"129048","DOI":"10.1016\/j.snb.2020.129048","article-title":"Rapid Detection of D-Limonene Emanating from Citrus Infestation by Bactrocera Dorsalis (Hendel) Using a Developed Gas-Sensing System Based on QCM Sensors Coated with Ethyl Cellulose","volume":"328","author":"Wen","year":"2021","journal-title":"Sens. Actuators B Chem."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"112183","DOI":"10.1016\/j.bios.2020.112183","article-title":"Reliable Chiral Recognition with an Optoelectronic Nose","volume":"159","author":"Maho","year":"2020","journal-title":"Biosens. Bioelectron."},{"key":"ref_13","doi-asserted-by":"crossref","unstructured":"Chai, X., Huang, X., Zhang, T., Wu, K., Duan, X., Yu, H., and Liu, X. (2023). Comparative Study of E-Nose, GC-MS, and GC-IMS to Distinguish Star Anise Essential Oil Extracted Using Different Extraction Methods. Separations, 10.","DOI":"10.3390\/separations10040256"},{"key":"ref_14","doi-asserted-by":"crossref","unstructured":"Song, S.-Y., Ahn, M.-S., Mekapogu, M., Jung, J.-A., Song, H.-Y., Lim, S.-H., Jin, J.-S., and Kwon, O.-K. (2023). Analysis of Floral Scent and Volatile Profiles of Different Aster Species by E-Nose and HS-SPME-GC-MS. Metabolites, 13.","DOI":"10.3390\/metabo13040503"},{"key":"ref_15","doi-asserted-by":"crossref","unstructured":"Niculae, A.-R., Stefan-van Staden, R.-I., van Staden, J.F., and Georgescu State, R. (2022). Sulfur-Doped Graphene-Based Electrochemical Sensors for Fast and Sensitive Determination of (R)-(+)-Limonene from Beverages. Sensors, 22.","DOI":"10.3390\/s22155851"},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"133687","DOI":"10.1016\/j.snb.2023.133687","article-title":"Discrimination of Citrus Infested with Bactrocera Dorsalis (Hendel) Using an Olfactory Detection System Based on MIPs-QCM Sensor Array and Bayesian Optimized Classification Algorithms","volume":"385","author":"Wen","year":"2023","journal-title":"Sens. Actuators B Chem."},{"key":"ref_17","doi-asserted-by":"crossref","unstructured":"N\u00fa\u00f1ez-Carmona, E., Abbatangelo, M., and Sberveglieri, V. (2021). Internet of Food (IoF), Tailor-Made Metal Oxide Gas Sensors to Support Tea Supply Chain. Sensors, 21.","DOI":"10.3390\/s21134266"},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"1550","DOI":"10.1149\/MA2021-01571550mtgabs","article-title":"Development of a Sensor Array Based on Pt, Pd, Ag and Au Nanocluster Decorated SnO2 for Precision Agriculture","volume":"MA2021-01","author":"Gaiardo","year":"2021","journal-title":"Meet. Abstr."},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"132426","DOI":"10.1016\/j.snb.2022.132426","article-title":"Design of a Metal-Oxide Solid Solution for Selective Detection of Ethanol with Marginal Influence by Humidity","volume":"370","author":"Spagnoli","year":"2022","journal-title":"Sens. Actuators B Chem."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"130593","DOI":"10.1016\/j.snb.2021.130593","article-title":"Development and Characterization of WO3 Nanoflakes for Selective Ethanol Sensing","volume":"347","author":"Spagnoli","year":"2021","journal-title":"Sens. Actuators B Chem."},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"89","DOI":"10.1016\/S0925-4005(01)00795-X","article-title":"Preparation and Characterization of SnO2 and WOx\u2013SnO2 Nanosized Powders and Thick Films for Gas Sensing","volume":"78","author":"Chiorino","year":"2001","journal-title":"Sens. Actuators B Chem."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"402","DOI":"10.1016\/j.snb.2012.08.016","article-title":"High-Sensitivity Detection of Acetaldehyde","volume":"174","author":"Giberti","year":"2012","journal-title":"Sens. Actuators B Chem."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"573","DOI":"10.1021\/acssensors.1c02481","article-title":"Design of a Metal-Oxide Solid Solution for Sub-Ppm H2 Detection","volume":"7","author":"Spagnoli","year":"2022","journal-title":"ACS Sens."},{"key":"ref_24","unstructured":"Guidi, V., Malag\u00f9, C., Carotta, M.C., and Vendemiati, B. (2012). Printed Films, Elsevier."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"127227","DOI":"10.1016\/j.snb.2019.127227","article-title":"Correlation of Gaseous Emissions to Water Stress in Tomato and Maize Crops: From Field to Laboratory and Back","volume":"303","author":"Fabbri","year":"2020","journal-title":"Sens. Actuators B Chem."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"44711","DOI":"10.1021\/acsami.1c10763","article-title":"Air Stable Nickel-Decorated Black Phosphorus and Its Room-Temperature Chemiresistive Gas Sensor Capabilities","volume":"13","author":"Valt","year":"2021","journal-title":"ACS Appl. Mater. Interfaces"},{"key":"ref_27","doi-asserted-by":"crossref","unstructured":"Rossi, A., Fabbri, B., Spagoli, E., Gaiardo, A., Valt, M., Ferroni, M., Ardit, M., Krik, S., Pedrielli, A., and Vanzetti, L. (2023). Functionalization of Indium Oxide for Empowered Detection of CO2 over an Extra-Wide Range of Concentrations. ACS Appl. Mater. Interfaces.","DOI":"10.22541\/au.167947762.24408959\/v1"},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"127768","DOI":"10.1016\/j.matchemphys.2023.127768","article-title":"Batch Fabrication of H2S Sensors Based on Evaporated Pd\/WO3 Film with Ppb-Level Detection Limit","volume":"302","author":"Guo","year":"2023","journal-title":"Mater. Chem. Phys."},{"key":"ref_29","doi-asserted-by":"crossref","unstructured":"Marikutsa, A., Rumyantseva, M., Konstantinova, E.A., and Gaskov, A. (2021). The Key Role of Active Sites in the Development of Selective Metal Oxide Sensor Materials. Sensors, 21.","DOI":"10.3390\/s21072554"},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"131","DOI":"10.1016\/j.chemphys.2018.10.015","article-title":"Adsorption of Probe Molecules to Investigate by EPR the Redox Properties of Silver Loaded on Ceria","volume":"517","author":"Skaf","year":"2019","journal-title":"Chem. Phys."},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"1875","DOI":"10.1039\/C6CS00914J","article-title":"IR Spectroscopic Investigations of Chemical and Photochemical Reactions on Metal Oxides: Bridging the Materials Gap","volume":"46","author":"Wang","year":"2017","journal-title":"Chem. Soc. Rev."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"131066","DOI":"10.1016\/j.snb.2021.131066","article-title":"Influence of Major Parameters on the Sensing Mechanism of Semiconductor Metal Oxide Based Chemiresistive Gas Sensors: A Review Focused on Personalized Healthcare","volume":"352","author":"Das","year":"2022","journal-title":"Sens. Actuators B Chem."},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"8411","DOI":"10.1039\/C6CE01587E","article-title":"Porous Tungsten Trioxide Nanolamellae with Uniform Structures for High-Performance Ethanol Sensing","volume":"18","author":"Liu","year":"2016","journal-title":"CrystEngComm"},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"480","DOI":"10.1016\/j.snb.2013.11.034","article-title":"Different Morphologies of ZnO and Their Ethanol Sensing Property","volume":"192","author":"Wei","year":"2014","journal-title":"Sens. Actuators B Chem."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"143","DOI":"10.1023\/A:1014405811371","article-title":"Conduction Model of Metal Oxide Gas Sensors","volume":"7","author":"Barsan","year":"2001","journal-title":"J. Electroceramics"},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"127279","DOI":"10.1016\/j.chemosphere.2020.127279","article-title":"Adsorption Isotherm Models: Classification, Physical Meaning, Application and Solving Method","volume":"258","author":"Wang","year":"2020","journal-title":"Chemosphere"},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"132495","DOI":"10.1016\/j.snb.2022.132495","article-title":"Operando DRIFT Measurements on Flame-Spray-Made Zn2SnO4 Nanoparticles Based Environmental Sensors","volume":"371","author":"Khamfoo","year":"2022","journal-title":"Sens. Actuators B Chem."},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"6561","DOI":"10.1002\/anie.202015856","article-title":"Surface Functionalized Sensors for Humidity-Independent Gas Detection","volume":"60","author":"Qu","year":"2021","journal-title":"Angew. Chemie Int. Ed."},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"20","DOI":"10.1016\/j.apcata.2011.08.018","article-title":"Study in Support Effect of In2O3\/MOx (M=Al, Si, Zr) Catalysts for Dehydrogenation of Propane in the Presence of CO2","volume":"407","author":"Chen","year":"2011","journal-title":"Appl. Catal. A Gen."},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"70","DOI":"10.1016\/j.progsolidstchem.2011.04.002","article-title":"Electronic Properties of Oxides: Chemical and Theoretical Approaches","volume":"39","author":"Matar","year":"2011","journal-title":"Prog. Solid State Chem."},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"1008","DOI":"10.1021\/acssensors.1c02463","article-title":"Nanoplasmonic NO2 Sensor with a Sub-10 Parts per Billion Limit of Detection in Urban Air","volume":"7","author":"Tanyeli","year":"2022","journal-title":"ACS Sens."},{"key":"ref_42","doi-asserted-by":"crossref","first-page":"36","DOI":"10.1007\/s11244-020-01355-3","article-title":"Selective Photo-Epoxidation of (R)-(+)- and (S)-(\u2212)-Limonene by Chiral and Non-Chiral Dioxo-Mo(VI) Complexes Anchored on TiO2-Nanotubes","volume":"64","year":"2021","journal-title":"Top. Catal."},{"key":"ref_43","doi-asserted-by":"crossref","first-page":"307","DOI":"10.1016\/j.cattod.2006.07.032","article-title":"Limonene Oxidation over V2O5\/TiO2 Catalysts","volume":"118","author":"Oliveira","year":"2006","journal-title":"Catal. Today"},{"key":"ref_44","first-page":"1","article-title":"Gas Chromatography-Mass Spectrometry Analysis of Photosensitive Characteristics in Citrus and Herb Essential Oils","volume":"6","author":"Ying","year":"2014","journal-title":"J. Chromatogr. Sep. Tech."},{"key":"ref_45","doi-asserted-by":"crossref","first-page":"132497","DOI":"10.1016\/j.snb.2022.132497","article-title":"SO2 Sensing Mechanism of Nanostructured SiC-SiOxC Core Shell: An Operando DRIFT Investigation","volume":"371","author":"Valt","year":"2022","journal-title":"Sens. Actuators B Chem."}],"container-title":["Sensors"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1424-8220\/23\/14\/6291\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,10]],"date-time":"2025-10-10T20:10:23Z","timestamp":1760127023000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1424-8220\/23\/14\/6291"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2023,7,11]]},"references-count":45,"journal-issue":{"issue":"14","published-online":{"date-parts":[[2023,7]]}},"alternative-id":["s23146291"],"URL":"https:\/\/doi.org\/10.3390\/s23146291","relation":{},"ISSN":["1424-8220"],"issn-type":[{"value":"1424-8220","type":"electronic"}],"subject":[],"published":{"date-parts":[[2023,7,11]]}}}