Complexes of the Mycotoxins Citrinin and Ochratoxin A with Aluminum Ions and their Spectroscopic Properties

The sensitive detection of the mycotoxin citrinin (CIT) utilizing its fluorescence requires approaches to enhance the emission. In this respect, we studied the complexation of CIT and ochratoxin A (OTA) with Al<sup>3+</sup> in methanol using absorption and fluorescence spectroscopy. In t...

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Main Authors: Julia Keller, Daniel Moldenhauer, Liam Byrne, Hajo Haase, Ute Resch-Genger, Matthias Koch
Format: Article
Language:English
Published: MDPI AG 2018-12-01
Series:Toxins
Subjects:
Online Access:https://www.mdpi.com/2072-6651/10/12/538
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author Julia Keller
Daniel Moldenhauer
Liam Byrne
Hajo Haase
Ute Resch-Genger
Matthias Koch
author_facet Julia Keller
Daniel Moldenhauer
Liam Byrne
Hajo Haase
Ute Resch-Genger
Matthias Koch
author_sort Julia Keller
collection DOAJ
description The sensitive detection of the mycotoxin citrinin (CIT) utilizing its fluorescence requires approaches to enhance the emission. In this respect, we studied the complexation of CIT and ochratoxin A (OTA) with Al<sup>3+</sup> in methanol using absorption and fluorescence spectroscopy. In this context, an isocratic high performance liquid chromatography (HPLC) method using a polymer column and a fluorescence detector was also developed that enables the separation of the metal ion complexes from the free ligands and non-complexed Al<sup>3+</sup>. CIT and OTA showed distinct changes in their absorption and fluorescence properties upon Al<sup>3+</sup>-coordination, and the fluorescence of CIT was considerably enhanced. Analysis of the photometrically assessed titration of CIT and OTA with Al<sup>3+</sup> using the Job plot method revealed 1:2 and 1:1 stoichiometries for the Al<sup>3+</sup> complexes of CIT (Al:CIT) and OTA (Al:OTA), respectively. In the case of CIT, only one &#946;-diketone moiety participates in Al<sup>3+</sup> coordination. These findings can be elegantly exploited for signal amplification and provide the base to reduce the limit of detection for CIT quantification by about an order of magnitude, as revealed by HPLC measurements using a fluorescence detector.
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spelling doaj.art-52434f8fdd0949ce956aae738a3c5d322022-12-22T02:55:03ZengMDPI AGToxins2072-66512018-12-01101253810.3390/toxins10120538toxins10120538Complexes of the Mycotoxins Citrinin and Ochratoxin A with Aluminum Ions and their Spectroscopic PropertiesJulia Keller0Daniel Moldenhauer1Liam Byrne2Hajo Haase3Ute Resch-Genger4Matthias Koch5Division of Organic Trace and Food Analysis, Department of Analytical Chemistry, Reference Materials, Bundesanstalt für Materialforschung und-prüfung (BAM), Richard-Willstätter-Str. 11, D-12489 Berlin, GermanyDivision of Organic Trace and Food Analysis, Department of Analytical Chemistry, Reference Materials, Bundesanstalt für Materialforschung und-prüfung (BAM), Richard-Willstätter-Str. 11, D-12489 Berlin, GermanyDivision of Organic Trace and Food Analysis, Department of Analytical Chemistry, Reference Materials, Bundesanstalt für Materialforschung und-prüfung (BAM), Richard-Willstätter-Str. 11, D-12489 Berlin, GermanyDivision of Organic Trace and Food Analysis, Department of Analytical Chemistry, Reference Materials, Bundesanstalt für Materialforschung und-prüfung (BAM), Richard-Willstätter-Str. 11, D-12489 Berlin, GermanyDivision of Organic Trace and Food Analysis, Department of Analytical Chemistry, Reference Materials, Bundesanstalt für Materialforschung und-prüfung (BAM), Richard-Willstätter-Str. 11, D-12489 Berlin, GermanyDivision of Organic Trace and Food Analysis, Department of Analytical Chemistry, Reference Materials, Bundesanstalt für Materialforschung und-prüfung (BAM), Richard-Willstätter-Str. 11, D-12489 Berlin, GermanyThe sensitive detection of the mycotoxin citrinin (CIT) utilizing its fluorescence requires approaches to enhance the emission. In this respect, we studied the complexation of CIT and ochratoxin A (OTA) with Al<sup>3+</sup> in methanol using absorption and fluorescence spectroscopy. In this context, an isocratic high performance liquid chromatography (HPLC) method using a polymer column and a fluorescence detector was also developed that enables the separation of the metal ion complexes from the free ligands and non-complexed Al<sup>3+</sup>. CIT and OTA showed distinct changes in their absorption and fluorescence properties upon Al<sup>3+</sup>-coordination, and the fluorescence of CIT was considerably enhanced. Analysis of the photometrically assessed titration of CIT and OTA with Al<sup>3+</sup> using the Job plot method revealed 1:2 and 1:1 stoichiometries for the Al<sup>3+</sup> complexes of CIT (Al:CIT) and OTA (Al:OTA), respectively. In the case of CIT, only one &#946;-diketone moiety participates in Al<sup>3+</sup> coordination. These findings can be elegantly exploited for signal amplification and provide the base to reduce the limit of detection for CIT quantification by about an order of magnitude, as revealed by HPLC measurements using a fluorescence detector.https://www.mdpi.com/2072-6651/10/12/538complexationaluminumfluorescenceJob plotHPLC-DAD/FLD
spellingShingle Julia Keller
Daniel Moldenhauer
Liam Byrne
Hajo Haase
Ute Resch-Genger
Matthias Koch
Complexes of the Mycotoxins Citrinin and Ochratoxin A with Aluminum Ions and their Spectroscopic Properties
Toxins
complexation
aluminum
fluorescence
Job plot
HPLC-DAD/FLD
title Complexes of the Mycotoxins Citrinin and Ochratoxin A with Aluminum Ions and their Spectroscopic Properties
title_full Complexes of the Mycotoxins Citrinin and Ochratoxin A with Aluminum Ions and their Spectroscopic Properties
title_fullStr Complexes of the Mycotoxins Citrinin and Ochratoxin A with Aluminum Ions and their Spectroscopic Properties
title_full_unstemmed Complexes of the Mycotoxins Citrinin and Ochratoxin A with Aluminum Ions and their Spectroscopic Properties
title_short Complexes of the Mycotoxins Citrinin and Ochratoxin A with Aluminum Ions and their Spectroscopic Properties
title_sort complexes of the mycotoxins citrinin and ochratoxin a with aluminum ions and their spectroscopic properties
topic complexation
aluminum
fluorescence
Job plot
HPLC-DAD/FLD
url https://www.mdpi.com/2072-6651/10/12/538
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