Preparation, Spectrochemical, and Computational Analysis of L-Carnosine (2-[(3-Aminopropanoyl)amino]-3-(1H-imidazol-5-yl)propanoic Acid) and Its Ruthenium (II) Coordination Complexes in Aqueous Solution

Molecules

Michael Lee Branham¹  Parvesh Singh¹  Krishna Bisetty¹  Myalo Sabela¹ 

[1] ¹School of Pharmacy and Pharmacology, University of KwaZulu-Natal, Durban, 4001, South Africa ²Department of Chemistry, Durban University of Technology, Durban, 4001, South Africa

关键词: carnosine;    ¹³C-NMR;    ¹H-NMR;    ¹⁵N-NMR;    metallopeptides;    ruthenium complexation;   

DOI  :  10.3390/molecules161210269

来源: mdpi

【 摘 要 】

This study reports the synthesis and characterization of novel ruthenium (II) complexes with the polydentate dipeptide, L-carnosine (2-[(3-aminopropanoyl)amino]-3-(1H-imidazol-5-yl)propanoic acid). Mixed-ligand complexes with the general composition [ML_p(Cl)_q(H₂O)_r]·xH₂O (M = Ru(II); L = L-carnosine; p = 3 − q; r = 0–1; and x = 1–3) were prepared by refluxing aqueous solutions of the ligand with equimolar amounts of ruthenium chloride (black-alpha form) at 60 °C for 36 h. Physical properties of the complexes were characterized by elemental analysis, DSC/TGA, and cyclic voltammetry. The molecular structures of the complexes were elucidated using UV-Vis, ATR-IR, and heteronuclear NMR spectroscopy, then confirmed by density function theory (DFT) calculations at the B3LYP/LANL2DZ level. Two-dimensional NMR experiments (¹H COSY, ¹³C gHMBC, and ¹⁵N gHMBC) were also conducted for the assignment of chemical shifts and calculation of relative coordination-induced shifts (RCIS) by the complex formed. According to our results, the most probable coordination geometries of ruthenium in these compounds involve nitrogen (N1) from the imidazole ring and an oxygen atom from the carboxylic acid group of the ligand as donor atoms. Additional thermogravimetric and electrochemical data suggest that while the tetrahedral-monomer or octahedral-dimer are both possible structures of the formed complexes, the metal in either structure occurs in the (2+) oxidation state. Resulting RCIS values indicate that the amide-carbonyl, and the amino-terminus of the dipeptide are not involved in chelation and these observations correlate well with theoretical shift predictions by DFT.

【 授权许可】

CC BY   
This is an open access article distributed under the Creative Commons Attribution License (CC BY) which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.