{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,17]],"date-time":"2025-10-17T14:11:40Z","timestamp":1760710300649,"version":"build-2065373602"},"reference-count":36,"publisher":"MDPI AG","issue":"13","license":[{"start":{"date-parts":[[2020,7,2]],"date-time":"2020-07-02T00:00:00Z","timestamp":1593648000000},"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>Metal phthalocyanines are well-known sensing phases with applications in different scientific fields due to their interesting properties. Detailed characterization by Raman spectroscopy was performed in order to study the shifting of the vibrational bands related to the coordination sphere of each metal phthalocyanine. In this work, a study involving the use of screen-printed electrodes (SPEs) with various metal phthalocyanines to electrochemically detect and quantify chlorine (Cl2) gas is presented. The Cl2 gas was generated in-situ via oxidation of the chloride present in form of aqueous salt solutions. The developed method offers not only the possibility to quantify chlorine, but also to discriminate among several chlorinated species due to the changes observed in the voltammetric profiles associated with the interaction between the specie assayed and the phthalocyanine metallic center. Optimization of detecting parameters was also performed to apply this procedure for the quantification of chlorine generated from commercial chlorine tablets. The development of this proof of concept shows interesting possibilities and easy-to-use applications with novel on metal phthalocyanines based SPE sensors.<\/jats:p>","DOI":"10.3390\/s20133702","type":"journal-article","created":{"date-parts":[[2020,7,3]],"date-time":"2020-07-03T06:51:20Z","timestamp":1593759080000},"page":"3702","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":1,"title":["Screen-Printed Electrodes Modified with Metal Phthalocyanines: Characterization and Electrocatalysis in Chlorinated Media"],"prefix":"10.3390","volume":"20","author":[{"given":"Daniel","family":"Antu\u00f1a-Jim\u00e9nez","sequence":"first","affiliation":[{"name":"Metrohm DropSens S.L., Vivero Ciencias de la Salud, C\/Colegio Santo Domingo de Guzm\u00e1n s\/n, 33010 Oviedo (Asturias), Spain"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-8399-962X","authenticated-orcid":false,"given":"David","family":"Ib\u00e1\u00f1ez","sequence":"additional","affiliation":[{"name":"Metrohm DropSens S.L., Vivero Ciencias de la Salud, C\/Colegio Santo Domingo de Guzm\u00e1n s\/n, 33010 Oviedo (Asturias), Spain"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1402-6506","authenticated-orcid":false,"given":"Mar\u00eda Bego\u00f1a","family":"Gonz\u00e1lez-Garc\u00eda","sequence":"additional","affiliation":[{"name":"Metrohm DropSens S.L., Vivero Ciencias de la Salud, C\/Colegio Santo Domingo de Guzm\u00e1n s\/n, 33010 Oviedo (Asturias), Spain"}]},{"given":"David","family":"Hern\u00e1ndez-Santos","sequence":"additional","affiliation":[{"name":"Metrohm DropSens S.L., Vivero Ciencias de la Salud, C\/Colegio Santo Domingo de Guzm\u00e1n s\/n, 33010 Oviedo (Asturias), Spain"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9224-1666","authenticated-orcid":false,"given":"Pablo","family":"Fanjul-Bolado","sequence":"additional","affiliation":[{"name":"Metrohm DropSens S.L., Vivero Ciencias de la Salud, C\/Colegio Santo Domingo de Guzm\u00e1n s\/n, 33010 Oviedo (Asturias), Spain"}]}],"member":"1968","published-online":{"date-parts":[[2020,7,2]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"75","DOI":"10.1002\/tcr.20139","article-title":"Phthalocyanines: From outstanding electronic properties to emerging applications","volume":"8","author":"Claessens","year":"2008","journal-title":"Chem. Rec."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"991","DOI":"10.1142\/S1088424606000338","article-title":"Multi-layer preparation of phthalocyanine dye and diazonium resin using a self-assembly fabrication method","volume":"10","author":"Park","year":"2006","journal-title":"J. Porphyr. Phthalocyanines"},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"3759","DOI":"10.1002\/1099-0690(200110)2001:20<3759::AID-EJOC3759>3.0.CO;2-U","article-title":"Phthalocyanines as active materials for optical limiting","volume":"20","author":"Dini","year":"2001","journal-title":"Eur. J. Org. Chem."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"1","DOI":"10.1016\/j.ccr.2018.10.007","article-title":"Phthalocyanines for dye-sensitized solar cells","volume":"381","author":"Urbani","year":"2019","journal-title":"Coord. Chem. Rev."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"557","DOI":"10.1002\/(SICI)1099-0739(199610)10:8<557::AID-AOC521>3.0.CO;2-3","article-title":"Phthalocyanines as sensitive materials for chemical sensors","volume":"10","author":"Zhou","year":"1996","journal-title":"Appl. Organomet. Chem."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"2016","DOI":"10.1002\/anie.200502820","article-title":"Data storage media current developments in optical data storage with organic dyes","volume":"45","author":"Mustroph","year":"2016","journal-title":"Angew. Chem."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"81","DOI":"10.1016\/S0022-0728(02)00757-X","article-title":"Spectroelectrochemical studies of manganese phthalocyanine thin films for applications in electrochromic devices","volume":"524\u2013525","author":"Lin","year":"2002","journal-title":"J. Electroanal. Chem."},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"18891","DOI":"10.1016\/j.ijhydene.2019.02.052","article-title":"Copper(II) phthalocyanine\/metal organic framework electrocatalyst for hydrogen evolution reaction application","volume":"44","author":"Monama","year":"2019","journal-title":"Int. J. Hydrog. Energy"},{"doi-asserted-by":"crossref","unstructured":"Govan, J., Orellana, W., Zagal, J.H., and Tasca, F. (2020). Penta-coordinated transition metal macrocycles as electrocatalysts for the oxygen reduction reaction. J. Solid State Electrochem.","key":"ref_9","DOI":"10.1007\/s10008-019-04489-x"},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"69","DOI":"10.1016\/j.aca.2012.03.039","article-title":"Comparative study of different alcohol sensors based on screen-printed carbon electrodes","volume":"728","author":"Rama","year":"2012","journal-title":"Anal. Chim. Acta"},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"974","DOI":"10.1002\/cphc.200700081","article-title":"Spectroelectrochemistry of carbon nanostructures","volume":"8","author":"Kavan","year":"2007","journal-title":"ChemPhysChem"},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"14","DOI":"10.1016\/j.elecom.2015.02.012","article-title":"Monitoring charge transfer at polarisable liquid\/liquid interfaces employing time-resolved Raman spectroelectrochemistry","volume":"54","author":"Plana","year":"2015","journal-title":"Electrochem. Commun."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"107848","DOI":"10.1016\/j.dyepig.2019.107848","article-title":"Raman and fluorescence spectroelectrochemical monitoring of resazurin-resorufin fluorogenic system","volume":"172","year":"2020","journal-title":"Dye. Pigment."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"2112","DOI":"10.1016\/j.polymdegradstab.2011.09.017","article-title":"A UV-Visible\/Raman spectroelectrochemical study of the stability of poly(3,4-ethylendioxythiophene) films","volume":"96","author":"Zanfrognini","year":"2011","journal-title":"Polym. Degrad. Stab."},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"183","DOI":"10.1016\/j.electacta.2018.01.060","article-title":"Quantitative Raman spectroelectrochemistry using silver screen-printed electrodes","volume":"264","author":"Heras","year":"2018","journal-title":"Electrochim. Acta"},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"2639","DOI":"10.1039\/C5SC04486C","article-title":"The importance of nickel oxyhydroxide deprotonation on its activity towards electrochemical water oxidation","volume":"7","author":"Koper","year":"2016","journal-title":"Chem. Sci."},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"1419","DOI":"10.1039\/b007763l","article-title":"Phthalocyanines: Structure and vibrations","volume":"3","author":"Tackley","year":"2001","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_18","first-page":"481","article-title":"Raman spectroscopy of phthalocyanines and their sulfonated derivatives","volume":"747","author":"Szymczyk","year":"2005","journal-title":"J. Mol. Struct."},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"10757","DOI":"10.1063\/1.1370064","article-title":"Ground state electronic structures and spectra of zinc complexes of porphyrin, tetraazaporphyrin, tetrabenzoporphyrin, and phthalocyanine: A density functional theory study","volume":"114","author":"Nguyen","year":"2001","journal-title":"J. Chem. Phys."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"73","DOI":"10.1016\/j.molstruc.2019.04.032","article-title":"Effect of fluorosubstitution and central metals on the molecular structure and vibrational spectra of metal phthalocyanines","volume":"1189","author":"Klyamer","year":"2019","journal-title":"J. Mol. Struct."},{"doi-asserted-by":"crossref","unstructured":"Mukherjee, D., Manjunatha, R., Sampath, S., and Ray, A.K. (2017). Phthalocyanines as sensitive materials for chemical sensors. Materials for Chemical Sensing, Springer; Nature Switzerland AG.","key":"ref_21","DOI":"10.1007\/978-3-319-47835-7_8"},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"154","DOI":"10.1088\/0022-3727\/21\/1\/021","article-title":"Gas sensitivity of some metal phthalocyanines","volume":"21","author":"Collins","year":"1988","journal-title":"J. Phys. D Appl. Phys."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"87","DOI":"10.1016\/j.snb.2017.08.013","article-title":"Reversible and fast responding ppb level Cl2 sensor based on noncovalent modified carbon nanotubes with Hexadecafluorinated copper phthalocyanine","volume":"255","author":"Sharma","year":"2018","journal-title":"Sens. Actuators B Chem."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"814","DOI":"10.1016\/j.msec.2008.07.020","article-title":"Investigation of gas-sensing properties of copper phthalocyanine films","volume":"29","author":"Basova","year":"2009","journal-title":"Mater. Sci. Eng. C"},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"255","DOI":"10.1016\/S0040-6090(02)01129-X","article-title":"High sensitivity chlorine gas sensors using Cu-phthalocyanine thin films","volume":"425","author":"Miyata","year":"2003","journal-title":"Thin Solid Film."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"1485","DOI":"10.1016\/j.talanta.2010.07.026","article-title":"Room temperature ppb level Cl2 sensing using sulphonated copper phthalocyanine films","volume":"82","author":"Kumar","year":"2010","journal-title":"Talanta"},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"3949","DOI":"10.1039\/b005091l","article-title":"IR and Raman assignments for zinc phthalocyanine from DFT calculations","volume":"2","author":"Tackley","year":"2000","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"280","DOI":"10.1016\/j.dyepig.2015.05.017","article-title":"Gold(III) phthalocyanine chloride: Optical and structural characterization of thin films","volume":"122","author":"Basova","year":"2015","journal-title":"Dye. Pigment."},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"7265","DOI":"10.1021\/acsomega.8b03500","article-title":"Methodological survey of simplified TD-DFT methods for fast and accurate interpretation of UV-Vis-NIR spectra of phthalocyanines","volume":"4","author":"Martynov","year":"2019","journal-title":"ACS Omega"},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"23","DOI":"10.1016\/j.chemphys.2018.06.021","article-title":"Gas sensing behavior of metal-phthalocyanines: Effects of electronic structure on sensitivity","volume":"513","author":"Rana","year":"2018","journal-title":"Chem. Phys."},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"4135","DOI":"10.1039\/C6RA25185D","article-title":"Enhanced Cl2 sensitivity of cobalt-phthalocyanine film by utilizing a porous nanostructured surface fabricated on glass","volume":"7","author":"Kumar","year":"2017","journal-title":"RSC Adv."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"18508","DOI":"10.1021\/jacs.9b09016","article-title":"The myth of d8 copper(III)","volume":"141","author":"Dimucci","year":"2019","journal-title":"J. Am. Chem. Soc."},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"191","DOI":"10.1016\/j.aca.2004.03.005","article-title":"A sensor for acetaminophen in a blood medium using a Cu(II)-conducting polymer complex modified electrode","volume":"512","author":"Boopathi","year":"2004","journal-title":"Anal. Chim. Acta"},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"8627","DOI":"10.1021\/jp060322a","article-title":"Femtosecond transient absorption, Raman, and electrochemistry studies of tetrasulfonated copper phthalocyanine in water solutions","volume":"110","author":"Abramczyk","year":"2006","journal-title":"J. Phys. Chem. A"},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"23572","DOI":"10.1021\/acs.jpcc.5b07753","article-title":"Electrochemical behavior of chlorine on platinum microdisk and screen-printed electrodes in a room temperature ionic liquid","volume":"119","author":"Murugappan","year":"2015","journal-title":"J. Phys. Chem. C"},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"173","DOI":"10.1016\/j.ijheh.2005.11.004","article-title":"Sodium dichloroisocyanurate (NaDCC) tablets as an alternative to sodium hypochlorite for the routine treatment of drinking water at the household level","volume":"209","author":"Clasen","year":"2006","journal-title":"Int. J. Hyg. Environ. Health"}],"container-title":["Sensors"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1424-8220\/20\/13\/3702\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,11]],"date-time":"2025-10-11T09:46:19Z","timestamp":1760175979000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1424-8220\/20\/13\/3702"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2020,7,2]]},"references-count":36,"journal-issue":{"issue":"13","published-online":{"date-parts":[[2020,7]]}},"alternative-id":["s20133702"],"URL":"https:\/\/doi.org\/10.3390\/s20133702","relation":{},"ISSN":["1424-8220"],"issn-type":[{"type":"electronic","value":"1424-8220"}],"subject":[],"published":{"date-parts":[[2020,7,2]]}}}