{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,8,27]],"date-time":"2026-08-27T03:02:55Z","timestamp":1787799775647,"version":"build-2784847793"},"reference-count":25,"publisher":"MDPI AG","issue":"15","license":[{"start":{"date-parts":[[2020,8,4]],"date-time":"2020-08-04T00:00:00Z","timestamp":1596499200000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"name":"European Union and the European Regional Development Fund","award":["GINOP-2.3.2-15-2016-00041"],"award-info":[{"award-number":["GINOP-2.3.2-15-2016-00041"]}]},{"name":"National Research, Development and Innovation Office (NKFI)","award":["K-132685"],"award-info":[{"award-number":["K-132685"]}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["IJMS"],"abstract":"<jats:p>Aromatic isocyanides including isocyanonaphthalene derivatives have been proven to be very effective fluorescent sensors for the quantification of Hg(II) ions in water. Thus, the reaction of 1,5-isocyanoaminonaphthalene (1,5-ICAN), which is one of the most important members of this family, with water and HgCl2 as the oxidation agents, was studied by fluorescence spectroscopy and mass spectrometry in order to get deeper insight into the kinetics and mechanistic details of this complex reaction. The reactions of 1,5-ICAN with water and HgCl2 were performed in various water\/co-solvent mixtures of different compositions. The co-solvents used in this study were both aprotic solvents including tetrahydrofuran, acetonitrile and N,N-dimethylformamide and protic solvents, such as ethanol and 2-propanol. It was found that in aprotic solvents the conversion of the isocyano group to amino moiety takes place, while in protic solvents the corresponding carbamate (urethane) group is formed in addition to the amino moiety. The variation of the resulting fluorescence intensities versus time curves were described using an irreversible, consecutive reaction model, in which the formation of isocyanate and carbamic acid intermediates, as well as diamino and carbamate (in the case of protic solvents) products were assumed. The formation of these intermediates and products was unambiguously confirmed by mass spectrometric measurements. Furthermore, by fitting the model to the experimental fluorescence versus time curves, the corresponding rate coefficients were determined. It was observed that the overall rate of transformation of the isocyano group to amino moiety increased with the water concentration and the polarity of the co-solvent. It was also supported that formation of diamino and carbamate derivatives in protic solvents takes place simultaneously and that the ratio of the amino to the carbamate function increased with the increasing water concentration. In addition, with an extension, the model presented herein proved to be capable of describing the kinetics of the transformation of 1,5-diisocyanonaphthalene (1,5-DIN) into 1,5-diaminonaphthalene (1,5-DAN) in the mixtures of water\/aprotic solvents.<\/jats:p>","DOI":"10.3390\/ijms21155588","type":"journal-article","created":{"date-parts":[[2020,8,5]],"date-time":"2020-08-05T06:02:21Z","timestamp":1596607341000},"page":"5588","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":5,"title":["Conversion of Isocyanide to Amine in The Presence of Water and Hg(II) Ions: Kinetics and Mechanism as Detected by Fluorescence Spectroscopy and Mass Spectrometry"],"prefix":"10.3390","volume":"21","author":[{"given":"Anita","family":"Adamoczky","sequence":"first","affiliation":[{"name":"Department of Applied Chemistry, Faculty of Science and Technology, University of Debrecen, H-4032 Debrecen, Hungary"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Lajos","family":"Nagy","sequence":"additional","affiliation":[{"name":"Department of Applied Chemistry, Faculty of Science and Technology, University of Debrecen, H-4032 Debrecen, Hungary"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-3484-2244","authenticated-orcid":false,"given":"Mikl\u00f3s","family":"Nagy","sequence":"additional","affiliation":[{"name":"Department of Applied Chemistry, Faculty of Science and Technology, University of Debrecen, H-4032 Debrecen, Hungary"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Mikl\u00f3s","family":"Zsuga","sequence":"additional","affiliation":[{"name":"Department of Applied Chemistry, Faculty of Science and Technology, University of Debrecen, H-4032 Debrecen, Hungary"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5274-6117","authenticated-orcid":false,"given":"S\u00e1ndor","family":"K\u00e9ki","sequence":"additional","affiliation":[{"name":"Department of Applied Chemistry, Faculty of Science and Technology, University of Debrecen, H-4032 Debrecen, Hungary"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"1968","published-online":{"date-parts":[[2020,8,4]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"1585","DOI":"10.1351\/pac199870081585","article-title":"The determination of mercury species in environmental and biological samples (Technical report)","volume":"70","author":"Morita","year":"1998","journal-title":"Pure Appl. Chem."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"4967","DOI":"10.1021\/es305071v","article-title":"Mercury as a globalpollutant: Sources, pathways, and effects","volume":"47","author":"Driscoll","year":"2013","journal-title":"Environ. Sci. Technol."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"1157","DOI":"10.1007\/s00706-008-0867-7","article-title":"Titrimetric analysis of total mercury ions including mercury(I) ions","volume":"139","author":"Li","year":"2008","journal-title":"Monatsh. Chem."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"333","DOI":"10.1016\/S0003-2670(01)82463-6","article-title":"The fluorimetric determination of mercury","volume":"64","author":"Holzbecher","year":"1973","journal-title":"Anal. Chim. Acta."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"497","DOI":"10.1016\/S0003-2670(00)86826-9","article-title":"A spectropolarimetric titrimetric method for the determination of cadmium, mercury, lead and bismuth","volume":"49","author":"Palma","year":"1970","journal-title":"Anal. Chim. Acta."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"24","DOI":"10.1016\/j.aca.2019.09.075","article-title":"Determination of mercury at picogram level in natural waters with inductively coupled plasma mass spectrometry by using 3D printed metal scavengers","volume":"1092","author":"Kulomaki","year":"2019","journal-title":"Anal. Chim. Acta."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"83","DOI":"10.1016\/j.bios.2013.11.074","article-title":"Nitrogen-doped carbon quantum dots: Facile synthesis and application as a \u201cturn-off\u2019 fluorescent probe for detection of Hg2+ ions","volume":"55","author":"Zhang","year":"2014","journal-title":"Biosens. Bioelectron."},{"key":"ref_8","first-page":"96","article-title":"A modified fluorescein derivative with improved water-solubility for turn-on fluorescent determination of Hg2+ in aqueous and living cells","volume":"89\u2013170","author":"Guang","year":"2017","journal-title":"Talanta"},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"810","DOI":"10.1016\/j.snb.2018.01.222","article-title":"Ratiometric fluorescence sensor based on dithiothreitol modified carbon dots-gold nanoclusters for the sensitive detection of mercury ions in water samples","volume":"262","author":"Liu","year":"2018","journal-title":"Sens. Actuators. B Chem."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"377","DOI":"10.1016\/j.snb.2014.11.105","article-title":"A ratiometric fluorescence sensor for highly selective and sensitive detection of mercuric ion","volume":"209","author":"Ma","year":"2015","journal-title":"Sens. Actuators. B Chem."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"12168","DOI":"10.1039\/C9NJ01366K","article-title":"A highly selective and sensitive ESIPT-based coumarin\u2013triazole polymer for the ratiometric, detection of Hg2+","volume":"43","author":"Ngororabanga","year":"2019","journal-title":"New J. Chem."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"907","DOI":"10.1016\/j.snb.2015.11.018","article-title":"A colorimetric and ratiometric fluorescent probe for mercury (II) in lysosome","volume":"224","author":"Zhang","year":"2016","journal-title":"Sens. Actuators. B Chem."},{"key":"ref_13","doi-asserted-by":"crossref","unstructured":"Ngororabanga, J.M.V., Tshentu, Z.R., and Mama, N. (2020). A New Highly Selective Colorimetric and Fluorometric Coumarin-based Chemosensor for Hg2+. J. Fluoresc.","DOI":"10.1007\/s10895-020-02542-x"},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"165","DOI":"10.1016\/j.talanta.2019.04.007","article-title":"Isocyanonaphthalenes as extremely low molecular weight, selective, ratiometric fluorescent probes for Mercury(II)","volume":"201","author":"Nagy","year":"2019","journal-title":"Talanta"},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"3074","DOI":"10.1016\/j.snb.2017.09.132","article-title":"Isocyano-functionalized, 1,8-naphthalimide-based chromophore as efficient ratiometric fluorescence probe for Hg2+ in aqueous medium","volume":"255","author":"Zhang","year":"2018","journal-title":"Sens. Actuators. B Chem."},{"key":"ref_16","doi-asserted-by":"crossref","unstructured":"Tian, M., Wang, C., Ma, Q., Bai, Y., Sun, J., and Ding, C. (2020). A Highly Selective Fluorescent Probe for Hg2+ Based on a 1,8-Naphthalimide Derivative. ACS Omega.","DOI":"10.1021\/acsomega.0c01790"},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"19","DOI":"10.1016\/j.jphotochem.2013.07.007","article-title":"Solvatochromic properties of a new isocyanonaphthalene based fluorophore","volume":"270","author":"Nagy","year":"2013","journal-title":"J. Photochem. Photobiol. A Chem."},{"key":"ref_18","first-page":"431","article-title":"An algorithm for least-squares estimation of nonlinear parameters","volume":"11","author":"Marquardt","year":"1963","journal-title":"Appl. Math."},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"333","DOI":"10.1016\/S0022-328X(00)86941-7","article-title":"The reaction of isocyanide-mercuric chloride complexes, with amines. Preparation of guanidines","volume":"94","author":"Sawai","year":"1975","journal-title":"J. Organomet. Chem."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"4263","DOI":"10.1016\/S0040-4039(01)94290-X","article-title":"Oxidative D-addition of isonitrile by use of mercuric salts synthesis of urea and urethane","volume":"42","author":"Sawai","year":"1972","journal-title":"Tetrahedron Lett."},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"1906","DOI":"10.1246\/bcsj.49.1906","article-title":"Reaction of isocyanides with mercuric-chloride","volume":"49","author":"Sawai","year":"1976","journal-title":"Bull. Chem. Soc. Jpn."},{"key":"ref_22","unstructured":"Sonnenschein, M.F. (2015). Polyurethanes-Science. Technology, Markets, and Trends, John Wiley & Sons, Inc.. Available online: https:\/\/www.wiley.com\/en-hu\/Polyurethanes%3A+Science%2C+Technology%2C+Markets%2C+and+Trends-p-9781118737910."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"1435","DOI":"10.1016\/j.cjche.2017.03.012","article-title":"Kinetics of water-isocyanate reaction in N,N-dimethylformamide","volume":"25","author":"Chen","year":"2017","journal-title":"Chin. J. Chem. Eng."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"444","DOI":"10.3390\/surfaces2020032","article-title":"A simple method for the quantification of free isocyanates on the surface of cellulose nanocrystals upon carbamation using toluene diisocyanate","volume":"2","author":"Abushammala","year":"2019","journal-title":"Surfaces"},{"key":"ref_25","unstructured":"Smallwood, I.M. (1996). Handbook of Organic Solvent Properties, Elsevier. Available online: https:\/\/www.directtextbook.com\/isbn\/9780340645789."}],"container-title":["International Journal of Molecular Sciences"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1422-0067\/21\/15\/5588\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,11]],"date-time":"2025-10-11T09:54:21Z","timestamp":1760176461000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1422-0067\/21\/15\/5588"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2020,8,4]]},"references-count":25,"journal-issue":{"issue":"15","published-online":{"date-parts":[[2020,8]]}},"alternative-id":["ijms21155588"],"URL":"https:\/\/doi.org\/10.3390\/ijms21155588","relation":{},"ISSN":["1422-0067"],"issn-type":[{"value":"1422-0067","type":"electronic"}],"subject":[],"published":{"date-parts":[[2020,8,4]]}}}