{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,27]],"date-time":"2026-09-27T14:51:46Z","timestamp":1790520706530,"version":"4.1.0"},"reference-count":59,"publisher":"Wiley","issue":"12","license":[{"start":{"date-parts":[[2012,5,4]],"date-time":"2012-05-04T00:00:00Z","timestamp":1336089600000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Rapid Comm Mass Spectrometry"],"published-print":{"date-parts":[[2012,6,30]]},"abstract":"<jats:sec>\n                    <jats:title>RATIONALE<\/jats:title>\n                    <jats:p>\n                      Although\n                      <jats:italic>para<\/jats:italic>\n                      \u2010phenylenediamine (PPD) is known to cause severe allergic contact dermatitis in consequence of autoxidation and\/or skin metabolism pathways, it is commonly utilized as an ingredient in permanent hair dyes. The aim of this work was to simultaneously accelerate the autoxidation process and to simulate the metabolic activation of PPD using a purely instrumental system.\n                    <\/jats:p>\n                  <\/jats:sec>\n                  <jats:sec>\n                    <jats:title>METHODS<\/jats:title>\n                    <jats:p>Electrochemistry (EC) in combination with electrospray ionization mass spectrometry (ESI\u2010MS) was used in this study to assess the skin\u2010sensitizing potential of PPD. Online and offline coupled EC\/ESI\u2010MS experiments were carried out and the emerging oxidation products were investigated. In a second approach, these primary species were allowed to react with the nucleophiles glutathione (GSH), cysteine (Cys), potassium cyanide (KCN) and lysine (Lys) in order to evaluate their reactivity.<\/jats:p>\n                  <\/jats:sec>\n                  <jats:sec>\n                    <jats:title>RESULTS<\/jats:title>\n                    <jats:p>\n                      The reactive\n                      <jats:italic>p<\/jats:italic>\n                      \u2010phenylene quinone diimine (PPQD), which can form upon autoxidation and\/or skin metabolism of PPD, was effectively generated in a simple EC cell next to further oxidation products, including the trimeric product Bandrowski's Base (BB). Conjugation with GSH and Cys was successfully proven, but no adducts with KCN or Lys were observed. Furthermore, the application of different concentration ratios between PPD and nucleophile was shown to play a crucial role concerning the type of oxidation products and adducts being formed.\n                    <\/jats:p>\n                  <\/jats:sec>\n                  <jats:sec>\n                    <jats:title>CONCLUSIONS<\/jats:title>\n                    <jats:p>\n                      It was found that EC\/MS is a well\u2010suited approach for the targeted generation of reactive haptens such as PPQD while avoiding detection problems due to the complexity of matrices encountered when conducting conventional\n                      <jats:italic>in vitro<\/jats:italic>\n                      or\n                      <jats:italic>in vivo<\/jats:italic>\n                      experiments. Copyright \u00a9 2012 John Wiley &amp; Sons, Ltd.\n                    <\/jats:p>\n                  <\/jats:sec>","DOI":"10.1002\/rcm.6249","type":"journal-article","created":{"date-parts":[[2012,5,7]],"date-time":"2012-05-07T00:57:22Z","timestamp":1336352242000},"page":"1453-1464","source":"Crossref","is-referenced-by-count":24,"title":["Electrochemistry\/mass spectrometry as a tool in the investigation of the potent skin sensitizer\n                    <i>p<\/i>\n                    \u2010phenylenediamine and its reactivity toward nucleophiles"],"prefix":"10.1002","volume":"26","author":[{"given":"Sandra","family":"Jahn","sequence":"first","affiliation":[{"name":"University of M\u00fcnster Institute of Inorganic and Analytical Chemistry and NRW Graduate School of Chemistry  Corrensstr. 30 48149 M\u00fcnster Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Helene","family":"Faber","sequence":"additional","affiliation":[{"name":"University of M\u00fcnster Institute of Inorganic and Analytical Chemistry and NRW Graduate School of Chemistry  Corrensstr. 30 48149 M\u00fcnster Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Raniero","family":"Zazzeroni","sequence":"additional","affiliation":[{"name":"Unilever UK SEAC  Colworth Science Park Sharnbrook MK44 1LQ UK"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Uwe","family":"Karst","sequence":"additional","affiliation":[{"name":"University of M\u00fcnster Institute of Inorganic and Analytical Chemistry and NRW Graduate School of Chemistry  Corrensstr. 30 48149 M\u00fcnster Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2012,5,4]]},"reference":[{"key":"e_1_2_6_2_1","doi-asserted-by":"publisher","DOI":"10.1016\/0021-8707(59)90053-X"},{"key":"e_1_2_6_3_1","doi-asserted-by":"crossref","first-page":"7","DOI":"10.1038\/jid.1965.2","article-title":"Cellular passive transfer of contact hypersensitivity to paraphenylenediamine and to 2,4\u2010dinitrochlorobenzene in guinea pigs","volume":"44","author":"Kind P. 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