authors |
Alexandre Hautier, Tiago Carvalho, Daniela Valensin, A. Jalila Simaan, Bruno Faure, Pedro Mateus, Rita Delgado, Olga Iranzo |
nationality |
International |
journal |
Dalton Transactions |
abstract |
Cite this: DOI: 10.1039/c8dt05037f
Received 21st December 2018, Accepted 24th December 2018 DOI: 10.1039/c8dt05037f rsc.li/dalton
The role of methylation in the copper(II) coordination properties of a His-containing decapeptide† Alexandre Hautier,a Tiago Carvalho,
a Daniela Valensin, b A. Jalila Simaan,a Bruno Faure, a Pedro Mateus, c Rita Delgado c and Olga Iranzo *a
N-Methylation of the peptide amide bond has proven to be a powerful strategy to fine-tune the confor- mation and properties of peptides. In this context and for the first time, we show that N-methylation can also be used to control the copper(II) coordination properties of peptides and stabilize at high pH values the copper(II) species lacking amidate coordination. Namely, we have prepared a derivative of the O-Asp peptide where the copper(II) coordinating amino acids, i.e. Asp and His residues, were N-methylated (ONMe-Asp). A combined study using potentiometric and spectroscopic (UV-Vis, CD, EPR and NMR) tech- niques indicates the formation of the wanted major species, [CuH(ONMe-Asp)]2+, where copper(II)is bound to His4(Nε), His7(Nε), His9(Nε) and Asp2(COO−). With respect to the parent non-methylated O-Asp peptide, [CuH(ONMe-Asp)]2+ is stable at higher pH values but has lower affinity for copper(II). Additionally, electrochemical studies reveal a Cu(II) ⇌ Cu(I) redox process with a larger cathodic and anodic peak separ- ation. Species containing copper(II) coordinating amidates were not observed for this ONMe-Asp peptide. |
publisher |
Royal Society of Chemistry |
year published |
2019 |
volume |
48 |
issue |
5 |
beginning page |
1859 |
ending page |
1870 |
digital object identifier (doi) |
10.1039/C8DT05037F |
ciceco authors
impact metrics
journal analysis (jcr 2019):
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journal impact factor |
4.174 |
5 year journal impact factor |
3.812 |
category normalized journal impact factor percentile |
90 |
dimensions (citation analysis):
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altmetrics (social interaction):
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