Simple and Selective Determination of Free Chlorine in Aqueous Solutions by an Electrophilic Aromatic Substitution Reaction Followed by Liquid Chromatography Coupled with Mass Spectrometry
We developed a selective technique to rapidly measure free chlorine, which is the sum of elemental chlorine (Cl<sub>2</sub>), hypochlorous acid (HOCl), and hypochlorite (OCl<sup>−</sup>) in water samples via an electrophilic aromatic substitution reaction hyphenated with liqu...
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2024-12-01
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| author | Avital Shifrovitch Moran Madmon Tamar Shamai Yamin Avi Weissberg |
| author_facet | Avital Shifrovitch Moran Madmon Tamar Shamai Yamin Avi Weissberg |
| author_sort | Avital Shifrovitch |
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| description | We developed a selective technique to rapidly measure free chlorine, which is the sum of elemental chlorine (Cl<sub>2</sub>), hypochlorous acid (HOCl), and hypochlorite (OCl<sup>−</sup>) in water samples via an electrophilic aromatic substitution reaction hyphenated with liquid chromatography-electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS). Sample preparation involved derivatization at 25 °C for 15 min with 3,4,5-trimethoxyphenylacetic acid (TMPAA) in an aqueous solution prior to analysis. Several parameters were evaluated to determine the optimized reaction and for the production of informative MS/MS spectrum of the derivatization product, 2-chloro-3,4,5-trimethoxyphenylacetic acid (Cl-TMPAA). The resulting Cl-TMPAA derivative displayed an informative ESI-MS/MS spectrum characterized by product ions at <i>m</i>/<i>z</i> 232.0142, 200.0245, and 185.0009 from the precursor ion at <i>m</i>/<i>z</i> 259.0379. The linear dynamic range of the method (0.1–10 µg/mL) was fitted to concentration levels relevant to forensic toxicology issues. Compared with other analytical techniques, this newly established LC-MS-based method demonstrated specificity, simplicity, and rapidity. This method enables the detection of free chlorine for forensic investigations in criminal cases. |
| format | Article |
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| institution | OA Journals |
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| language | English |
| publishDate | 2024-12-01 |
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| spelling | doaj-art-e298fb2aac98403dbf7c0a2ca80711d12025-08-20T02:01:09ZengMDPI AGOrganics2673-401X2024-12-015461462210.3390/org5040032Simple and Selective Determination of Free Chlorine in Aqueous Solutions by an Electrophilic Aromatic Substitution Reaction Followed by Liquid Chromatography Coupled with Mass SpectrometryAvital Shifrovitch0Moran Madmon1Tamar Shamai Yamin2Avi Weissberg3Department of Analytical Chemistry, Israel Institute for Biological Research (IIBR), Ness Ziona 7410001, IsraelDepartment of Analytical Chemistry, Israel Institute for Biological Research (IIBR), Ness Ziona 7410001, IsraelDepartment of Analytical Chemistry, Israel Institute for Biological Research (IIBR), Ness Ziona 7410001, IsraelDepartment of Analytical Chemistry, Israel Institute for Biological Research (IIBR), Ness Ziona 7410001, IsraelWe developed a selective technique to rapidly measure free chlorine, which is the sum of elemental chlorine (Cl<sub>2</sub>), hypochlorous acid (HOCl), and hypochlorite (OCl<sup>−</sup>) in water samples via an electrophilic aromatic substitution reaction hyphenated with liquid chromatography-electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS). Sample preparation involved derivatization at 25 °C for 15 min with 3,4,5-trimethoxyphenylacetic acid (TMPAA) in an aqueous solution prior to analysis. Several parameters were evaluated to determine the optimized reaction and for the production of informative MS/MS spectrum of the derivatization product, 2-chloro-3,4,5-trimethoxyphenylacetic acid (Cl-TMPAA). The resulting Cl-TMPAA derivative displayed an informative ESI-MS/MS spectrum characterized by product ions at <i>m</i>/<i>z</i> 232.0142, 200.0245, and 185.0009 from the precursor ion at <i>m</i>/<i>z</i> 259.0379. The linear dynamic range of the method (0.1–10 µg/mL) was fitted to concentration levels relevant to forensic toxicology issues. Compared with other analytical techniques, this newly established LC-MS-based method demonstrated specificity, simplicity, and rapidity. This method enables the detection of free chlorine for forensic investigations in criminal cases.https://www.mdpi.com/2673-401X/5/4/32free chlorineaqueous mediaderivatizationelectrophilic aromatic substitutionLC-ESI-MS/MS |
| spellingShingle | Avital Shifrovitch Moran Madmon Tamar Shamai Yamin Avi Weissberg Simple and Selective Determination of Free Chlorine in Aqueous Solutions by an Electrophilic Aromatic Substitution Reaction Followed by Liquid Chromatography Coupled with Mass Spectrometry Organics free chlorine aqueous media derivatization electrophilic aromatic substitution LC-ESI-MS/MS |
| title | Simple and Selective Determination of Free Chlorine in Aqueous Solutions by an Electrophilic Aromatic Substitution Reaction Followed by Liquid Chromatography Coupled with Mass Spectrometry |
| title_full | Simple and Selective Determination of Free Chlorine in Aqueous Solutions by an Electrophilic Aromatic Substitution Reaction Followed by Liquid Chromatography Coupled with Mass Spectrometry |
| title_fullStr | Simple and Selective Determination of Free Chlorine in Aqueous Solutions by an Electrophilic Aromatic Substitution Reaction Followed by Liquid Chromatography Coupled with Mass Spectrometry |
| title_full_unstemmed | Simple and Selective Determination of Free Chlorine in Aqueous Solutions by an Electrophilic Aromatic Substitution Reaction Followed by Liquid Chromatography Coupled with Mass Spectrometry |
| title_short | Simple and Selective Determination of Free Chlorine in Aqueous Solutions by an Electrophilic Aromatic Substitution Reaction Followed by Liquid Chromatography Coupled with Mass Spectrometry |
| title_sort | simple and selective determination of free chlorine in aqueous solutions by an electrophilic aromatic substitution reaction followed by liquid chromatography coupled with mass spectrometry |
| topic | free chlorine aqueous media derivatization electrophilic aromatic substitution LC-ESI-MS/MS |
| url | https://www.mdpi.com/2673-401X/5/4/32 |
| work_keys_str_mv | AT avitalshifrovitch simpleandselectivedeterminationoffreechlorineinaqueoussolutionsbyanelectrophilicaromaticsubstitutionreactionfollowedbyliquidchromatographycoupledwithmassspectrometry AT moranmadmon simpleandselectivedeterminationoffreechlorineinaqueoussolutionsbyanelectrophilicaromaticsubstitutionreactionfollowedbyliquidchromatographycoupledwithmassspectrometry AT tamarshamaiyamin simpleandselectivedeterminationoffreechlorineinaqueoussolutionsbyanelectrophilicaromaticsubstitutionreactionfollowedbyliquidchromatographycoupledwithmassspectrometry AT aviweissberg simpleandselectivedeterminationoffreechlorineinaqueoussolutionsbyanelectrophilicaromaticsubstitutionreactionfollowedbyliquidchromatographycoupledwithmassspectrometry |