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Interaction of the Fungal Metabolite Harzianic Acid with Rare-Earth Cations (Pr(3+), Eu(3+), Ho(3+), Tm(3+))
Rare-earth elements (REEs) are in all respect a class of new contaminants that may have toxic effects on organisms and microorganisms and information on their interactions with natural ligands should be of value to predict and control their diffusion in natural environments. In the current study, we...
Autores principales: | , , , , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
MDPI
2022
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9571137/ https://www.ncbi.nlm.nih.gov/pubmed/36235005 http://dx.doi.org/10.3390/molecules27196468 |
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author | Salvatore, Maria Michela Siciliano, Antonietta Staropoli, Alessia Vinale, Francesco Nicoletti, Rosario DellaGreca, Marina Guida, Marco Salvatore, Francesco Iuliano, Mauro Andolfi, Anna De Tommaso, Gaetano |
author_facet | Salvatore, Maria Michela Siciliano, Antonietta Staropoli, Alessia Vinale, Francesco Nicoletti, Rosario DellaGreca, Marina Guida, Marco Salvatore, Francesco Iuliano, Mauro Andolfi, Anna De Tommaso, Gaetano |
author_sort | Salvatore, Maria Michela |
collection | PubMed |
description | Rare-earth elements (REEs) are in all respect a class of new contaminants that may have toxic effects on organisms and microorganisms and information on their interactions with natural ligands should be of value to predict and control their diffusion in natural environments. In the current study, we investigate interactions of tripositive cations of praseodymium, europium, holmium, and thulium with harzianic acid (H(2)L), a secondary metabolite produced by selected strains of fungi belonging to the Trichoderma genus. We applied the same techniques and workflow previously employed in an analogous study concerning lanthanum, neodymium, samarium, and gadolinium tripositive cations. Therefore, in the current study, HPLC-ESI-HRMS experiments, circular dichroism (CD), and UV-Vis spectrophotometric absorption data, as well as accurate pH measurements, were applied to characterize bonding interactions between harzianic acid and Pr(3+), Eu(3+), Ho(3+), and Tm(3+) cations. Problems connected to the low solubility of harzianic acid in water were overcome by employing a 0.1 M NaClO(4)/(CH(3)OH + H(2)O 50/50 w/w) mixed solvent. For Pr(3+), Ho(3+), and Tm(3+), only the mono complexes PrL(+), HoL(+), and TmL(+) were detected and their formation constant determined. Eu(3+) forms almost exclusively the bis complex [Formula: see text] for which the corresponding formation constant is reported; under our experimental conditions, the mono complex EuL(+) is irrelevant. Combining the results of the present and previous studies, a picture of interactions of harzianic acid with rare-earth cations extending over 8 of the 17 REEs can be composed. In order to complement chemical information with toxicological information, a battery of bioassays was applied to evaluate the effects of praseodymium, europium, holmium, and thulium tripositive cations on a suite of bioindicators including Aliivibrio fischeri (Gram-negative bacterium), Raphidocelis subcapitata (green alga), and Daphnia magna (microcrustacean), and median effective concentration (EC50) values of Pr(3+), Eu(3+), Ho(3+), and Tm(3+) for the tested species were assessed. |
format | Online Article Text |
id | pubmed-9571137 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2022 |
publisher | MDPI |
record_format | MEDLINE/PubMed |
spelling | pubmed-95711372022-10-17 Interaction of the Fungal Metabolite Harzianic Acid with Rare-Earth Cations (Pr(3+), Eu(3+), Ho(3+), Tm(3+)) Salvatore, Maria Michela Siciliano, Antonietta Staropoli, Alessia Vinale, Francesco Nicoletti, Rosario DellaGreca, Marina Guida, Marco Salvatore, Francesco Iuliano, Mauro Andolfi, Anna De Tommaso, Gaetano Molecules Article Rare-earth elements (REEs) are in all respect a class of new contaminants that may have toxic effects on organisms and microorganisms and information on their interactions with natural ligands should be of value to predict and control their diffusion in natural environments. In the current study, we investigate interactions of tripositive cations of praseodymium, europium, holmium, and thulium with harzianic acid (H(2)L), a secondary metabolite produced by selected strains of fungi belonging to the Trichoderma genus. We applied the same techniques and workflow previously employed in an analogous study concerning lanthanum, neodymium, samarium, and gadolinium tripositive cations. Therefore, in the current study, HPLC-ESI-HRMS experiments, circular dichroism (CD), and UV-Vis spectrophotometric absorption data, as well as accurate pH measurements, were applied to characterize bonding interactions between harzianic acid and Pr(3+), Eu(3+), Ho(3+), and Tm(3+) cations. Problems connected to the low solubility of harzianic acid in water were overcome by employing a 0.1 M NaClO(4)/(CH(3)OH + H(2)O 50/50 w/w) mixed solvent. For Pr(3+), Ho(3+), and Tm(3+), only the mono complexes PrL(+), HoL(+), and TmL(+) were detected and their formation constant determined. Eu(3+) forms almost exclusively the bis complex [Formula: see text] for which the corresponding formation constant is reported; under our experimental conditions, the mono complex EuL(+) is irrelevant. Combining the results of the present and previous studies, a picture of interactions of harzianic acid with rare-earth cations extending over 8 of the 17 REEs can be composed. In order to complement chemical information with toxicological information, a battery of bioassays was applied to evaluate the effects of praseodymium, europium, holmium, and thulium tripositive cations on a suite of bioindicators including Aliivibrio fischeri (Gram-negative bacterium), Raphidocelis subcapitata (green alga), and Daphnia magna (microcrustacean), and median effective concentration (EC50) values of Pr(3+), Eu(3+), Ho(3+), and Tm(3+) for the tested species were assessed. MDPI 2022-10-01 /pmc/articles/PMC9571137/ /pubmed/36235005 http://dx.doi.org/10.3390/molecules27196468 Text en © 2022 by the authors. https://creativecommons.org/licenses/by/4.0/Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/). |
spellingShingle | Article Salvatore, Maria Michela Siciliano, Antonietta Staropoli, Alessia Vinale, Francesco Nicoletti, Rosario DellaGreca, Marina Guida, Marco Salvatore, Francesco Iuliano, Mauro Andolfi, Anna De Tommaso, Gaetano Interaction of the Fungal Metabolite Harzianic Acid with Rare-Earth Cations (Pr(3+), Eu(3+), Ho(3+), Tm(3+)) |
title | Interaction of the Fungal Metabolite Harzianic Acid with Rare-Earth Cations (Pr(3+), Eu(3+), Ho(3+), Tm(3+)) |
title_full | Interaction of the Fungal Metabolite Harzianic Acid with Rare-Earth Cations (Pr(3+), Eu(3+), Ho(3+), Tm(3+)) |
title_fullStr | Interaction of the Fungal Metabolite Harzianic Acid with Rare-Earth Cations (Pr(3+), Eu(3+), Ho(3+), Tm(3+)) |
title_full_unstemmed | Interaction of the Fungal Metabolite Harzianic Acid with Rare-Earth Cations (Pr(3+), Eu(3+), Ho(3+), Tm(3+)) |
title_short | Interaction of the Fungal Metabolite Harzianic Acid with Rare-Earth Cations (Pr(3+), Eu(3+), Ho(3+), Tm(3+)) |
title_sort | interaction of the fungal metabolite harzianic acid with rare-earth cations (pr(3+), eu(3+), ho(3+), tm(3+)) |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9571137/ https://www.ncbi.nlm.nih.gov/pubmed/36235005 http://dx.doi.org/10.3390/molecules27196468 |
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