Use of Fluorescence Spectroscopy and Chemometrics to Visualise Fluoroquinolones Photodegradation Major Trends: A Confirmation Study with Mass Spectrometry
In this work, we employed EEM-PARAFAC (fluorescence excitation-emission matrices-parallel factor analysis) as a low-cost tool to study the oxidation pathways of (fluoro)quinolones. Amounts of 12.5 μM of enrofloxacin (ENR), ciprofloxacin (CIP), ofloxacin (OFL), oxolinic acid (OA), and flumequine (FLU...
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| Format: | Article |
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MDPI AG
2023-01-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/28/2/777 |
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| author | Iván Sciscenko Paula García-Negueroles Ana María Amat Isabel Oller Carlos Escudero-Oñate Laura Ferrando-Climent Antonio Arques |
| author_facet | Iván Sciscenko Paula García-Negueroles Ana María Amat Isabel Oller Carlos Escudero-Oñate Laura Ferrando-Climent Antonio Arques |
| author_sort | Iván Sciscenko |
| collection | DOAJ |
| description | In this work, we employed EEM-PARAFAC (fluorescence excitation-emission matrices-parallel factor analysis) as a low-cost tool to study the oxidation pathways of (fluoro)quinolones. Amounts of 12.5 μM of enrofloxacin (ENR), ciprofloxacin (CIP), ofloxacin (OFL), oxolinic acid (OA), and flumequine (FLU), as individual solutions, were irradiated under UVA light. A 5-component PARAFAC model was obtained, four of them related to the parent pollutants, named as ENR-like (including CIP), OFL-like, OA-like, and FLU-like, and an additional one related to photoproducts, called ENRox-like (with an emission red-shift with respect to the ENR-like component). Mass spectrometry was employed to correlate the five PARAFAC components with their plausible molecular structures. Results indicated that photoproducts presenting: (i) hydroxylation or alkyl cleavages exhibited fingerprints analogous to those of the parent pollutants; (ii) defluorination and hydroxylation emitted within the ENRox-like region; (iii) the aforementioned changes plus piperazine ring cleavage emitted within the OA-like region. Afterwards, the five antibiotics were mixed in a single solution (each at a concentration of 0.25 μM) in seawater, PARAFAC being also able to deconvolute the fingerprint of humic-like substances. This approach could be a potential game changer in the analysis of (fluorescent) contaminants of emerging concern removals in complex matrices, giving rapid visual insights into the degradation pathways. |
| first_indexed | 2024-03-09T11:35:23Z |
| format | Article |
| id | doaj.art-dbd90c6e53254157a7c125917ee11c54 |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-09T11:35:23Z |
| publishDate | 2023-01-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-dbd90c6e53254157a7c125917ee11c542023-11-30T23:44:44ZengMDPI AGMolecules1420-30492023-01-0128277710.3390/molecules28020777Use of Fluorescence Spectroscopy and Chemometrics to Visualise Fluoroquinolones Photodegradation Major Trends: A Confirmation Study with Mass SpectrometryIván Sciscenko0Paula García-Negueroles1Ana María Amat2Isabel Oller3Carlos Escudero-Oñate4Laura Ferrando-Climent5Antonio Arques6Departamento de Ingeniería Textil y Papelera, Universitat Politècnica de València (UPV), Plaza Ferrándiz y Carbonell s/n, 03801 Alcoy, SpainDepartamento de Ingeniería Textil y Papelera, Universitat Politècnica de València (UPV), Plaza Ferrándiz y Carbonell s/n, 03801 Alcoy, SpainDepartamento de Ingeniería Textil y Papelera, Universitat Politècnica de València (UPV), Plaza Ferrándiz y Carbonell s/n, 03801 Alcoy, SpainCIEMAT-Plataforma Solar de Almería, Carretera de Senés km 4, 04200 Tabernas, SpainInstitute for Energy Technology (IFE), Instituttveien 18, 2007 Kjeller, NorwayInstitute for Energy Technology (IFE), Instituttveien 18, 2007 Kjeller, NorwayDepartamento de Ingeniería Textil y Papelera, Universitat Politècnica de València (UPV), Plaza Ferrándiz y Carbonell s/n, 03801 Alcoy, SpainIn this work, we employed EEM-PARAFAC (fluorescence excitation-emission matrices-parallel factor analysis) as a low-cost tool to study the oxidation pathways of (fluoro)quinolones. Amounts of 12.5 μM of enrofloxacin (ENR), ciprofloxacin (CIP), ofloxacin (OFL), oxolinic acid (OA), and flumequine (FLU), as individual solutions, were irradiated under UVA light. A 5-component PARAFAC model was obtained, four of them related to the parent pollutants, named as ENR-like (including CIP), OFL-like, OA-like, and FLU-like, and an additional one related to photoproducts, called ENRox-like (with an emission red-shift with respect to the ENR-like component). Mass spectrometry was employed to correlate the five PARAFAC components with their plausible molecular structures. Results indicated that photoproducts presenting: (i) hydroxylation or alkyl cleavages exhibited fingerprints analogous to those of the parent pollutants; (ii) defluorination and hydroxylation emitted within the ENRox-like region; (iii) the aforementioned changes plus piperazine ring cleavage emitted within the OA-like region. Afterwards, the five antibiotics were mixed in a single solution (each at a concentration of 0.25 μM) in seawater, PARAFAC being also able to deconvolute the fingerprint of humic-like substances. This approach could be a potential game changer in the analysis of (fluorescent) contaminants of emerging concern removals in complex matrices, giving rapid visual insights into the degradation pathways.https://www.mdpi.com/1420-3049/28/2/777antibioticslow-cost analysispharmaceuticalsphotolysisseawatertransformation products |
| spellingShingle | Iván Sciscenko Paula García-Negueroles Ana María Amat Isabel Oller Carlos Escudero-Oñate Laura Ferrando-Climent Antonio Arques Use of Fluorescence Spectroscopy and Chemometrics to Visualise Fluoroquinolones Photodegradation Major Trends: A Confirmation Study with Mass Spectrometry Molecules antibiotics low-cost analysis pharmaceuticals photolysis seawater transformation products |
| title | Use of Fluorescence Spectroscopy and Chemometrics to Visualise Fluoroquinolones Photodegradation Major Trends: A Confirmation Study with Mass Spectrometry |
| title_full | Use of Fluorescence Spectroscopy and Chemometrics to Visualise Fluoroquinolones Photodegradation Major Trends: A Confirmation Study with Mass Spectrometry |
| title_fullStr | Use of Fluorescence Spectroscopy and Chemometrics to Visualise Fluoroquinolones Photodegradation Major Trends: A Confirmation Study with Mass Spectrometry |
| title_full_unstemmed | Use of Fluorescence Spectroscopy and Chemometrics to Visualise Fluoroquinolones Photodegradation Major Trends: A Confirmation Study with Mass Spectrometry |
| title_short | Use of Fluorescence Spectroscopy and Chemometrics to Visualise Fluoroquinolones Photodegradation Major Trends: A Confirmation Study with Mass Spectrometry |
| title_sort | use of fluorescence spectroscopy and chemometrics to visualise fluoroquinolones photodegradation major trends a confirmation study with mass spectrometry |
| topic | antibiotics low-cost analysis pharmaceuticals photolysis seawater transformation products |
| url | https://www.mdpi.com/1420-3049/28/2/777 |
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