Interaction of Redox-Active Copper(II) with Catecholamines: A Combined Spectroscopic and Theoretical Study
In this work, attention is focused on the non-essential amino acid L-Tyrosine (TYR) hydroxylated to L-DOPA, which is the precursor to the neurotransmitters dopamine, noradrenaline (norepinephrine; NE) and adrenaline (epinephrine; EP) known as catecholamines and their interactions with redox-active C...
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MDPI AG
2023-05-01
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| Online Access: | https://www.mdpi.com/2304-6740/11/5/208 |
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| author | Miriama Šimunková Zuzana Barbieriková Milan Mazúr Marian Valko Suliman Y. Alomar Saleh H. Alwasel Michal Malček |
| author_facet | Miriama Šimunková Zuzana Barbieriková Milan Mazúr Marian Valko Suliman Y. Alomar Saleh H. Alwasel Michal Malček |
| author_sort | Miriama Šimunková |
| collection | DOAJ |
| description | In this work, attention is focused on the non-essential amino acid L-Tyrosine (TYR) hydroxylated to L-DOPA, which is the precursor to the neurotransmitters dopamine, noradrenaline (norepinephrine; NE) and adrenaline (epinephrine; EP) known as catecholamines and their interactions with redox-active Cu(II). Catecholamines have multiple functions in biological systems, including the regulation of the central nervous system, and free (unbound) redox metal ions are present in many diseases with disturbed metal homeostasis. The interaction between catecholamines and Cu(II) has been studied by means of Electron Paramagnetic Resonance spectroscopy (EPR), EPR spin trapping and UV-vis spectroscopy. The obtained spectroscopic results are supported by Density Functional Theory calculations. Only minor qualitative and quantitative changes in the UV-vis spectra of all the studied compounds have been observed following their interactions with Cu(II) ions. The low-temperature EPR spectra were more convincing and confirmed the interaction between Cu(II) ions and all the studied compounds, involving hydroxyl groups and amino nitrogens. The use of an ABTS assay revealed that the compounds under study possessed radical-scavenging activities against ABTS<sup>•+</sup> in the order TYR < EP < DA < NE~L-DOPA. The neurotransmitters DA, NE and EP, following their interaction with Cu(II), exhibit the ability to (partially) reduce Cu(II) to Cu(I) species which was confirmed using the Cu(I) specific chelator neocuproine. EPR spin-trapping experiments revealed the suppressed formation of hydroxyl radicals (<sup>•</sup>OH) in a copper(II) catalyzed Fenton-like system in the presence of catecholamines. Only in the case of EP was autooxidation in a stock solution observed. Furthermore, the oxidation of EP is enhanced in the presence of Cu(II) ions. In conclusion, it has been confirmed that the oxidation of catecholamines in the presence of copper promotes the redox cycling process, resulting in the formation of ROS, which may, in turn, cause damage to neuronal systems. |
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| language | English |
| last_indexed | 2024-03-11T03:38:59Z |
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| spelling | doaj.art-d638d0dfc3584aacbfbc38671ed3c0662023-11-18T01:49:08ZengMDPI AGInorganics2304-67402023-05-0111520810.3390/inorganics11050208Interaction of Redox-Active Copper(II) with Catecholamines: A Combined Spectroscopic and Theoretical StudyMiriama Šimunková0Zuzana Barbieriková1Milan Mazúr2Marian Valko3Suliman Y. Alomar4Saleh H. Alwasel5Michal Malček6Department of Physical Chemistry, Institute of Physical Chemistry and Chemical Physics, Faculty of Chemical and Food Technology, Slovak University of Technology, Radlinského 9, 812 37 Bratislava, SlovakiaDepartment of Physical Chemistry, Institute of Physical Chemistry and Chemical Physics, Faculty of Chemical and Food Technology, Slovak University of Technology, Radlinského 9, 812 37 Bratislava, SlovakiaDepartment of Physical Chemistry, Institute of Physical Chemistry and Chemical Physics, Faculty of Chemical and Food Technology, Slovak University of Technology, Radlinského 9, 812 37 Bratislava, SlovakiaDepartment of Physical Chemistry, Institute of Physical Chemistry and Chemical Physics, Faculty of Chemical and Food Technology, Slovak University of Technology, Radlinského 9, 812 37 Bratislava, SlovakiaZoology Department, College of Science, King Saud University, Riyadh 11451, Saudi ArabiaZoology Department, College of Science, King Saud University, Riyadh 11451, Saudi ArabiaDepartment of Physical Chemistry, Institute of Physical Chemistry and Chemical Physics, Faculty of Chemical and Food Technology, Slovak University of Technology, Radlinského 9, 812 37 Bratislava, SlovakiaIn this work, attention is focused on the non-essential amino acid L-Tyrosine (TYR) hydroxylated to L-DOPA, which is the precursor to the neurotransmitters dopamine, noradrenaline (norepinephrine; NE) and adrenaline (epinephrine; EP) known as catecholamines and their interactions with redox-active Cu(II). Catecholamines have multiple functions in biological systems, including the regulation of the central nervous system, and free (unbound) redox metal ions are present in many diseases with disturbed metal homeostasis. The interaction between catecholamines and Cu(II) has been studied by means of Electron Paramagnetic Resonance spectroscopy (EPR), EPR spin trapping and UV-vis spectroscopy. The obtained spectroscopic results are supported by Density Functional Theory calculations. Only minor qualitative and quantitative changes in the UV-vis spectra of all the studied compounds have been observed following their interactions with Cu(II) ions. The low-temperature EPR spectra were more convincing and confirmed the interaction between Cu(II) ions and all the studied compounds, involving hydroxyl groups and amino nitrogens. The use of an ABTS assay revealed that the compounds under study possessed radical-scavenging activities against ABTS<sup>•+</sup> in the order TYR < EP < DA < NE~L-DOPA. The neurotransmitters DA, NE and EP, following their interaction with Cu(II), exhibit the ability to (partially) reduce Cu(II) to Cu(I) species which was confirmed using the Cu(I) specific chelator neocuproine. EPR spin-trapping experiments revealed the suppressed formation of hydroxyl radicals (<sup>•</sup>OH) in a copper(II) catalyzed Fenton-like system in the presence of catecholamines. Only in the case of EP was autooxidation in a stock solution observed. Furthermore, the oxidation of EP is enhanced in the presence of Cu(II) ions. In conclusion, it has been confirmed that the oxidation of catecholamines in the presence of copper promotes the redox cycling process, resulting in the formation of ROS, which may, in turn, cause damage to neuronal systems.https://www.mdpi.com/2304-6740/11/5/208catecholaminescopper(II)neurotransmittersradical-scavenging activityEPR spectroscopyspin-trapping |
| spellingShingle | Miriama Šimunková Zuzana Barbieriková Milan Mazúr Marian Valko Suliman Y. Alomar Saleh H. Alwasel Michal Malček Interaction of Redox-Active Copper(II) with Catecholamines: A Combined Spectroscopic and Theoretical Study Inorganics catecholamines copper(II) neurotransmitters radical-scavenging activity EPR spectroscopy spin-trapping |
| title | Interaction of Redox-Active Copper(II) with Catecholamines: A Combined Spectroscopic and Theoretical Study |
| title_full | Interaction of Redox-Active Copper(II) with Catecholamines: A Combined Spectroscopic and Theoretical Study |
| title_fullStr | Interaction of Redox-Active Copper(II) with Catecholamines: A Combined Spectroscopic and Theoretical Study |
| title_full_unstemmed | Interaction of Redox-Active Copper(II) with Catecholamines: A Combined Spectroscopic and Theoretical Study |
| title_short | Interaction of Redox-Active Copper(II) with Catecholamines: A Combined Spectroscopic and Theoretical Study |
| title_sort | interaction of redox active copper ii with catecholamines a combined spectroscopic and theoretical study |
| topic | catecholamines copper(II) neurotransmitters radical-scavenging activity EPR spectroscopy spin-trapping |
| url | https://www.mdpi.com/2304-6740/11/5/208 |
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