{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,12]],"date-time":"2025-10-12T04:04:37Z","timestamp":1760241877844,"version":"build-2065373602"},"reference-count":57,"publisher":"MDPI AG","issue":"11","license":[{"start":{"date-parts":[[2018,10,23]],"date-time":"2018-10-23T00:00:00Z","timestamp":1540252800000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Sensors"],"abstract":"<jats:p>It was already demonstrated by our research group that a direct catalytic methanol (or ethanol) fuel cell (DMFC) device can be used also for analytical purposes, such as the determination of ethanol content in beverages. In the present research we extended the application to the analysis of several ethanol-based pharmaceutical products, i.e., pharmaceutical tinctures (dyes) and disinfectants. In recent work we have also shown that the use of alcohol dehydrogenase enzyme as a component of the anodic section of a direct catalytic methanol (or ethanol) fuel cell significantly improves the performance of a simple DMFC device, making it more suitable to measure ethanol (or methanol) in real samples by this cell. At the same time, we have also shown that DMFC can respond to certain organic compounds that are more complex than methanol and ethanol and having R(R\u2019)CH-OH group in the molecule. Firstly, pharmaceutical dyes were analyzed for their ethanol content using the simple catalytic DMFC device, with good accuracy and precision. The results are illustrated in the present paper. Additionally, a detailed investigation carried out on commercial denatured alcoholic samples evidenced several interferences due to the contained additives. Secondly, we hypothesized that by using the enzymatic fuel cell it would be possible to improve the determination, for instance, of certain antibiotics, such as imipenem, or else carry out determinations of ethanol content in saliva and serum (simulating forensic tests, correlated to drivers \u201cbreath test\u201d); even if this has already been hypothesized in previous papers, the present study is the first to perform them experimentally, obtaining satisfactory results. In practice, all of the goals which we proposed were reached, confirming the remarkable opportunities of the enzymatic (or non-enzymatic) DMFC device.<\/jats:p>","DOI":"10.3390\/s18113596","type":"journal-article","created":{"date-parts":[[2018,10,24]],"date-time":"2018-10-24T02:59:40Z","timestamp":1540349980000},"page":"3596","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":13,"title":["Direct Methanol (or Ethanol) Fuel Cell as Enzymatic or Non-Enzymatic Device, Used to Check Ethanol in Several Pharmaceutical and Forensic Samples"],"prefix":"10.3390","volume":"18","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-3292-1053","authenticated-orcid":false,"given":"Mauro","family":"Tomassetti","sequence":"first","affiliation":[{"name":"Department of Chemistry, \u201cLa Sapienza\u201d University of Rome, 00185 Rome, Italy"}]},{"given":"Riccardo","family":"Angeloni","sequence":"additional","affiliation":[{"name":"Department of Chemistry, \u201cLa Sapienza\u201d University of Rome, 00185 Rome, Italy"}]},{"given":"Sergio","family":"Marchiandi","sequence":"additional","affiliation":[{"name":"Department of Chemistry, \u201cLa Sapienza\u201d University of Rome, 00185 Rome, Italy"}]},{"given":"Mauro","family":"Castrucci","sequence":"additional","affiliation":[{"name":"Department of Chemistry, \u201cLa Sapienza\u201d University of Rome, 00185 Rome, Italy"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5780-4400","authenticated-orcid":false,"given":"Maria Pia","family":"Sammartino","sequence":"additional","affiliation":[{"name":"Department of Chemistry, \u201cLa Sapienza\u201d University of Rome, 00185 Rome, Italy"}]},{"given":"Luigi","family":"Campanella","sequence":"additional","affiliation":[{"name":"Department of Chemistry, \u201cLa Sapienza\u201d University of Rome, 00185 Rome, Italy"}]}],"member":"1968","published-online":{"date-parts":[[2018,10,23]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"383","DOI":"10.1016\/0141-0229(83)90013-3","article-title":"Bioelectrochemical fuel cell and sensor based on a quino protein, alcohol dehydrogenase","volume":"5","author":"Davis","year":"1983","journal-title":"Enzyme Microb. Technol."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"3783","DOI":"10.1149\/1.1838873","article-title":"A methanol sensor for portable direct methanol fuel cells","volume":"145","author":"Barton","year":"1998","journal-title":"J. Electrochem. Soc."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"117","DOI":"10.1149\/1.1390975","article-title":"Design and operation of an electrochemical methanol concentration sensor for direct methanol fuel cell systems","volume":"3","author":"Narayanan","year":"2000","journal-title":"Electrochem. Solid State Lett."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"A88","DOI":"10.1149\/1.1563874","article-title":"Reliable and fast-responding methanol concentration sensor with novel design","volume":"6","author":"Qi","year":"2003","journal-title":"Electrochem. Solid State Lett."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"1115","DOI":"10.1016\/j.jpowsour.2006.07.033","article-title":"A methanol concentration sensor using twin membrane electrode assemblies operated in pulsed mode for DMFC","volume":"162","author":"Sun","year":"2006","journal-title":"J. Power Sources"},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"626","DOI":"10.1016\/j.jpowsour.2005.09.067","article-title":"Liquid methanol concentration sensors for direct methanol fuel cells","volume":"159","author":"Zhao","year":"2006","journal-title":"J. Power Sources"},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"160","DOI":"10.1016\/S1452-3981(23)17146-X","article-title":"A methanol concentration sensor using twin membrane electrode assemblies for direct methanol fuel cells","volume":"1","author":"Sun","year":"2006","journal-title":"Int. J. Electrochem. Sci."},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"95","DOI":"10.1016\/j.jpowsour.2006.01.030","article-title":"A review of anode catalysis in the direct methanol fuel cell","volume":"155","author":"Liu","year":"2006","journal-title":"J. Power Sources"},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"14","DOI":"10.1016\/S0022-0728(98)00197-1","article-title":"Methanol oxidation and direct methanol fuel cells: A selective review","volume":"461","author":"Wasmus","year":"1999","journal-title":"J. Electroanal. Chem."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"445","DOI":"10.1016\/S0920-5861(97)00054-0","article-title":"Mechanism and electrocatalysis in the direct methanol fuel cell","volume":"38","author":"Hamnett","year":"1997","journal-title":"Catal. Today"},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"272","DOI":"10.1016\/j.jpowsour.2005.05.049","article-title":"The power performance curve for engineering analysis of fuel cells","volume":"155","author":"Benziger","year":"2006","journal-title":"J. Power Sources"},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"2134","DOI":"10.3844\/ajassp.2006.2134.2135","article-title":"Characteristic curve of a fuel cell","volume":"3","author":"Isa","year":"2006","journal-title":"Am. J. Appl. Sci."},{"key":"ref_13","unstructured":"Sparks, D., Laroche, C., Tran, N., Goetzinger, D., Najafi, N., and Kawaguchi, K. (2005, January 23\u201325). A new methanol concentration microsensor for improved DMFC performance. Proceedings of the 2005 Fuel Cell Summit, Uncasville, CT, USA."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"51","DOI":"10.1016\/j.rser.2015.11.039","article-title":"Vapor feed direct methanol fuel cells (DMFCs): A review","volume":"56","author":"Mallick","year":"2016","journal-title":"Renew. Sustain. Energy Rev."},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"117","DOI":"10.1007\/s100080050075","article-title":"Direct methanol fuel cells for vehicular applications","volume":"2","author":"Shukla","year":"1998","journal-title":"J. Solid State Electrochem."},{"key":"ref_16","unstructured":"(2016). Report on Fuel Cell Development in India, Appendix\u2014VI."},{"key":"ref_17","unstructured":"Youngseung, N. (2017). Characterization of Autonomous Direct Methanol Fuel Cell Systems with Various Designs for Portable Applications. [Ph.D. Thesis, Technische Universit\u00e4t Braunschweig]."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"10409","DOI":"10.3390\/en80910409","article-title":"Increasing Fuel Efficiency of Direct Methanol Fuel Cell Systems with Feedforward Control of the Operating Concentration","volume":"8","author":"Na","year":"2015","journal-title":"Energies"},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"1847","DOI":"10.1002\/ep.12633","article-title":"Environmental Aspects of Direct Methanol Fuel Cell: Experimental Detection of Methanol Electro-Oxidation Products","volume":"36","author":"Bayramoglu","year":"2017","journal-title":"Environ. Prog. Sustain. Energy"},{"key":"ref_20","unstructured":"Patrabansh, S., El-Sharkh, M.Y., Alam, M., and Yasser, R. (2014, January 7\u20139). DMFC Models and Applications\u2014A Literature Survey, Part I. Proceedings of the 2014 International Conference on Industrial Engineering and Operations Management, Bali, Indonesia."},{"key":"ref_21","doi-asserted-by":"crossref","unstructured":"Tafaoli-Masoule, M., Bahrami, A., and Mohammadrezaei, D. (2013). Optimum Conditions for Maximum Power of a Direct Methanol Fuel Cell. ISRN Mech. Eng.","DOI":"10.1155\/2013\/872873"},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"71","DOI":"10.1016\/S1452-3981(23)17137-9","article-title":"Electrochemical Analysis of Direct Methanol Fuel Cells for Low Temperature Operation","volume":"1","author":"Baglio","year":"2006","journal-title":"Int. J. Electrochem. Sci."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"5408","DOI":"10.1016\/j.ijhydene.2015.01.034","article-title":"Development and performance analysis of a metallic passive micro-direct methanol fuel cell for portable applications","volume":"40","author":"Falcao","year":"2015","journal-title":"Int. J. Hydrog. Energy"},{"key":"ref_24","unstructured":"Zhang, X.W. (2005). Membranes for direct methanol fuel cell applications: Analysis based on characterization, experimentation and modeling. Advances in Fuel Cells, Research Signpost."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"1001","DOI":"10.1016\/j.electacta.2015.12.171","article-title":"Catalytic fuel cell used as an analytical tool for methanol and ethanol determination. Application to ethanol determination in alcoholic beverages","volume":"191","author":"Tomassetti","year":"2016","journal-title":"Electrochim. Acta"},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"91","DOI":"10.21014\/acta_imeko.v7i2.444","article-title":"Ethanol content determination in hard liquor drinks, beers, and wines, using a catalytic fuel cell. Comparison with other two conventional enzymatic biosensors: Correlation and statistical data","volume":"7","author":"Tomassetti","year":"2018","journal-title":"Acta Imeko"},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"7311","DOI":"10.1007\/s00216-016-9795-2","article-title":"Further development on DMFC device used for analytical purpose: Real applications in the pharmaceutical field and possible in biological fluids","volume":"408","author":"Tomassetti","year":"2016","journal-title":"Anal. Bioanal. Chem."},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"91","DOI":"10.1016\/j.bios.2015.06.029","article-title":"Enzymatic biofuel cells: 30 years of critical advancements","volume":"76","author":"Rasmussen","year":"2016","journal-title":"Biosens. Bioelectron."},{"key":"ref_29","unstructured":"(2018, August 03). University of Canterbury Christchurch New Zealand: Determination of Ethanol by Redox Titration with Potassium Dichromate. Available online: http:\/\/www.chemteach.ac.nz\/investigations\/ethanol.shtml."},{"key":"ref_30","first-page":"133","article-title":"A rapid method for determination of ethanol in alcoholic beverages using capillary gas chromatography","volume":"11","author":"Wang","year":"2003","journal-title":"J. Food Drug Anal."},{"key":"ref_31","first-page":"113","article-title":"Rapid determination of ethanol content in spirits and in beer by high resolution gas chromatography","volume":"30","author":"Naviglio","year":"2001","journal-title":"Industrie delle Bevande"},{"key":"ref_32","first-page":"6","article-title":"Alcohol determination in beverages using polar capillary gas chromatography-mass spectroscopy and an acetonitrile internal standard","volume":"3","author":"Brill","year":"2012","journal-title":"Concordia Coll. J. Anal. Chem."},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"387","DOI":"10.1016\/S0021-9673(02)00942-1","article-title":"Determination of ethanol in alcoholic beverages by high-performance liquid chromatography-flame ionization detection using pure water as mobile phase","volume":"976","author":"Yaritaa","year":"2002","journal-title":"J. Chromatogr. A"},{"key":"ref_34","first-page":"375","article-title":"Determination of sugar, glycerol and ethanol in ratafee with high performance liquid chromatography","volume":"24","author":"Huang","year":"2002","journal-title":"Yunnan Daxue Xuebao Ziran Kexueban"},{"key":"ref_35","first-page":"1","article-title":"Colorimetric method for the estimation of ethanol in alcoholic drinks","volume":"1","author":"Sumbhate","year":"2012","journal-title":"J. Anal. Tech."},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"745","DOI":"10.1016\/j.talanta.2011.01.078","article-title":"Flow injection colorimetric method using acidic ceric nitrate as reagent for determination of ethanol","volume":"84","author":"Pinyoua","year":"2011","journal-title":"Talanta"},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"1199","DOI":"10.1016\/S0039-9140(00)00610-X","article-title":"Determination of ethanol in liquor by near-infrared spectrophotometry with flow injection","volume":"53","author":"Tipparat","year":"2001","journal-title":"Talanta"},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"1","DOI":"10.1186\/1752-153X-4-5","article-title":"Rapid and mobile determination of alcoholic strength in wine, beer and spirits using a flow-through infrared sensor","volume":"4","author":"Lachenmeier","year":"2010","journal-title":"Chem. Cent. J."},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"825","DOI":"10.1016\/j.foodchem.2005.12.032","article-title":"Rapid quality control of spirit drinks and beer using multivariate data analysis of Fourier transform infrared spectra","volume":"101","author":"Lachenmeier","year":"2007","journal-title":"Food Chem."},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"277","DOI":"10.1016\/j.proche.2009.07.069","article-title":"Application of amperometric enzyme biosensors for wine and must analysis","volume":"1","author":"Goriushkina","year":"2009","journal-title":"Procedia Chem."},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"151","DOI":"10.1016\/S0022-0728(99)00271-5","article-title":"An electrochemical alcohol sensor based on a co-electrodeposited Pt-WO3 electrode","volume":"471","author":"Chen","year":"1999","journal-title":"J. Electroanal. Chem."},{"key":"ref_42","doi-asserted-by":"crossref","first-page":"428","DOI":"10.2174\/157341112803216852","article-title":"Electrochemical biosensors for the determination of the antioxidant capacity in foods and beverages based on reactive oxygen species","volume":"8","author":"Barthelmebs","year":"2012","journal-title":"Curr. Anal. Chem."},{"key":"ref_43","unstructured":"Pingarron Carrazon, J.M., Reviejo Garcia, A.J., Rodriguez Gorostiza, F.J., Hernandez Fernandez, J., Munoz Pascual, F.J., Ibanez Lopez, J.D., and Martin Garzo, L.A. (2006). Device for Ethanol Content Determination in Blood. (WO2006070027), Patent."},{"key":"ref_44","doi-asserted-by":"crossref","first-page":"1","DOI":"10.1016\/j.aca.2013.09.020","article-title":"A novel non invasive electrochemical biosensing device for in situ determination of the alcohol content in blood by monitoring ethanol in sweat","volume":"806","author":"Gamella","year":"2014","journal-title":"Anal. Chim. Acta"},{"key":"ref_45","doi-asserted-by":"crossref","first-page":"86","DOI":"10.2174\/157340808785107565","article-title":"Study of the catalytic mechanism of the enzyme catalase on organic hydroperoxides in non-polar organic solvent","volume":"4","author":"Campanella","year":"2008","journal-title":"Curr. Enzym. Inhib."},{"key":"ref_46","doi-asserted-by":"crossref","first-page":"56","DOI":"10.2174\/1573411010666140612004417","article-title":"Ethanol determination in alcholic beverages using two different amperometric enzyme sensor","volume":"11","author":"Angeloni","year":"2015","journal-title":"Curr. Anal. Chem."},{"key":"ref_47","doi-asserted-by":"crossref","first-page":"78","DOI":"10.1016\/j.snb.2010.03.040","article-title":"An innovative organic phase enzyme electrode (OPEE) for the determination of ethanol in leadless petrols","volume":"147","author":"Campanella","year":"2010","journal-title":"Sens. Actuators B"},{"key":"ref_48","unstructured":"(1993). Commission Regulation No 3199\/93 on Mutual Recognition of the Processes for the Full Denaturing of Alcohol for the Purpose of Exemption from Excise Duty, The Commission of the European Communities. Modified by G.U. European (374\/42 of 22 December 2004)."},{"key":"ref_49","doi-asserted-by":"crossref","first-page":"3668","DOI":"10.1002\/ange.200454199","article-title":"Cyclometalated ruthenium (II) complexes as highly active transfer hydrogenation catalysts","volume":"116","author":"Baratta","year":"2004","journal-title":"Angew. Chem."},{"key":"ref_50","doi-asserted-by":"crossref","first-page":"1394","DOI":"10.1093\/clinchem\/25.8.1394","article-title":"Inter-& intra-individual variations in saliva\/blood alcohol ratio during ethanol metabolism in man","volume":"25","author":"Jones","year":"1979","journal-title":"Clin. Chem."},{"key":"ref_51","doi-asserted-by":"crossref","first-page":"283","DOI":"10.1042\/cs0560283","article-title":"Correlation of ethanol concentrations in blood and saliva","volume":"56","author":"McColl","year":"1979","journal-title":"Clin. Sci."},{"key":"ref_52","doi-asserted-by":"crossref","first-page":"199","DOI":"10.3109\/00365517909106094","article-title":"Assessment of an automated enzymatic method for ethanol determination in microsamples of saliva","volume":"39","author":"Jones","year":"1979","journal-title":"Scand. J. Clin. Lab. Investig."},{"key":"ref_53","doi-asserted-by":"crossref","first-page":"53","DOI":"10.1111\/j.1440-1681.1979.tb00007.x","article-title":"Distribution of ethanol between saliva and blood in man","volume":"6","author":"Jones","year":"1979","journal-title":"Clin. Exp. Pharmacol. Physiol."},{"key":"ref_54","doi-asserted-by":"crossref","first-page":"252","DOI":"10.1016\/j.jpowsour.2016.05.133","article-title":"Recent advances on enzymatic glucose\/oxygen and hydrogen\/oxygen biofuel cells: Achievements and limitations","volume":"325","author":"Cosnier","year":"2016","journal-title":"J. Power Sources"},{"key":"ref_55","doi-asserted-by":"crossref","first-page":"27","DOI":"10.1007\/BF02918975","article-title":"Microbial fuel-cells Electricity production from carbohydrates","volume":"39","author":"Allen","year":"1993","journal-title":"Appl. Biochem. Biotechnol."},{"key":"ref_56","doi-asserted-by":"crossref","first-page":"2521","DOI":"10.1016\/j.electacta.2004.10.080","article-title":"Development of alcohol\/O2 biofuel cells using salt-extracted tetrabutylammonium bromide\/Nafion membranes to immobilize dehydrogenase enzymes","volume":"50","author":"Akers","year":"2005","journal-title":"Electrochim. Acta"},{"key":"ref_57","doi-asserted-by":"crossref","first-page":"228","DOI":"10.1016\/j.copbio.2007.03.007","article-title":"Enzyme-based biofuel cells","volume":"18","author":"Minteer","year":"2007","journal-title":"Curr. Opin. Biotechnol."}],"container-title":["Sensors"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1424-8220\/18\/11\/3596\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,11]],"date-time":"2025-10-11T15:25:36Z","timestamp":1760196336000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1424-8220\/18\/11\/3596"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2018,10,23]]},"references-count":57,"journal-issue":{"issue":"11","published-online":{"date-parts":[[2018,11]]}},"alternative-id":["s18113596"],"URL":"https:\/\/doi.org\/10.3390\/s18113596","relation":{},"ISSN":["1424-8220"],"issn-type":[{"type":"electronic","value":"1424-8220"}],"subject":[],"published":{"date-parts":[[2018,10,23]]}}}