Complex formation between [(η6-p-cym)Ru(H2O)3]2+ and oligopeptides containing three histidyl moieties

Bihari, Zsolt; Ugone, Valeria; Garribba, Eugenio; Lihi, Norbert; Buglyó, Péter

doi:10.1016/j.jorganchem.2016.09.013

Cited by 8 publications

(6 citation statements)

References 49 publications

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“…The functional B3P86 is frequently used in the literature because of its high degree of accuracy for predicting the structures of transition metal complexes . b, [ ] On the basis of these results, it is possible to argue that the geometry optimization is reasonably accurate to simulate the electronic absorption spectra.…”

Section: Resultsmentioning

confidence: 99%

Accurate prediction of vertical electronic transitions of Ni(II) coordination compounds via time dependent density functional theory

Sciortino

Lihi

Czine

et al. 2018

Int J of Quantum Chemistry

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Time dependent density functional theory calculations are completed for five Ni(II) complexes formed by polydentate peptides to predict the electronic absorption spectrum. The ligands examined were glycyl-glycyl-glycine (GGG), glycyl-glycyl-glycyl-glycine (GGGG), glycyl-glycyl-histidine (GGH), glycyl-glycyl-cysteine (GGC), and triethylenetetramine (trien). Fifteen functionals and two basis sets were tested. On the basis of the mean absolute percent deviation (MAPD), the ranking among the functionals is:ing the basis sets, the triple-f def2-TZVP performs better than the double-f LANL2DZ. With the functional HSE06 and basis set def2-TZVP the MAPD with respect to the experimental k max is 1.65% with a standard deviation of 1.26%. The absorption electronic spectra were interpreted in terms of vertical excitations between occupied and virtual MOs based on Ni-d atomic orbitals. The electronic structure of the Ni(II) species is also discussed. K E Y W O R D S electronic structure, nickel, peptides, time dependent density functional theory, UV-Vis spectroscopy 1 | I N TR ODU C TI ONThe prediction of the structure, reactivity, and stability of a chemical compound has always been a big challenge not only in chemistry, but also in physics and biology. During the past decades, computational methods allowed the chemists to calculate the structure, molecular properties, and energetics of many chemical species. Among these methods, density functional theory (DFT) [1] has reached an enormous popularity and many reviews have been published. [2][3][4][5][6][7][8][9][10] The main advantage of DFT is that many packages are available, commercially or free of charge, which allow one calculations on large molecules in an user friendly manner; nowadays, molecules with more than one hundred atoms can be treated routinely. At the Int J Quantum Chem. 2018;e25655. https://doi.org/10.1002/qua.25655

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Section: Resultsmentioning

confidence: 99%

Accurate prediction of vertical electronic transitions of Ni(II) coordination compounds via time dependent density functional theory

Sciortino

Lihi

Czine

et al. 2018

Int J of Quantum Chemistry

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“…Reaction rates of coordinating ligands with RuCym are strongly affected by the type of the donor atoms. Complex formation with (O,O) or (O,O,O) donor ligands is a fast process at physiological pH, while (N) and (N,N,N) donor ligands chelate the RuCym rather slowly (hours to days) [59, 69, 76, 77]. Reaction rate with (O,N) donor bearing ligands mainly depends on the actual protonation state of the given donor atom, thus it also depends on the actual pH, and the interaction may take place from few minutes to several hours [57, 72].…”

Section: Resultsmentioning

confidence: 99%

Binding mechanisms of half-sandwich Rh(III) and Ru(II) arene complexes on human serum albumin: a comparative study

Dömötör

Enyedy

2019

J Biol Inorg Chem

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Various half-sandwich ruthenium(II) arene complexes and rhodium(III) arene complexes have been intensively investigated due to their prominent anticancer activity. The interaction of the organometallic complexes of Ru(η 6 - p -cymene) and Rh(η 5 -C 5 Me 5 ) with human serum albumin (HSA) was studied in detail by a combination of various methods such as ultrafiltration, capillary electrophoresis, 1 H NMR spectroscopy, fluorometry and UV–visible spectrophotometry in the presence of 100 mM chloride ions. Binding characteristics of the organometallic ions and their complexes with deferiprone, 2-picolinic acid, maltol, 6-methyl-2-picolinic acid and 2-quinaldic acid were evaluated. Kinetic aspects and reversibility of the albumin binding are also discussed. The effect of low-molecular-mass blood components on the protein binding was studied in addition to the interaction of organorhodium complexes with cell culture medium components. The organometallic ions were found to bind to HSA to a high extent via a coordination bond. Release of the bound metal ions was kinetically hindered and could not be induced by the denaturation of the protein. Binding of the Ru(η 6 - p -cymene) triaqua cation was much slower (ca. 24 h) compared to the rhodium congener (few min), while their complexes interacted with the protein relatively fast (1–2 h). The studied complexes were bound to HSA coordinatively. The highly stable and kinetically inert 2-picolinate Ru(η 6 - p -cymene) complex bound in an associative manner preserving its original entity, while lower stability complexes decomposed partly or completely upon binding to HSA. Fast, non-specific and high-affinity binding of the complexes on HSA highlights their coordinative interaction with various types of proteins possibly decreasing effective drug concentration. Graphic abstract Electronic supplementary material The online version of this article (10.1007/s00775-019-01683-0) contains supplementary material, which is available to authorized users.

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“…Complexes bearing the [(η 6 -p-cym)Ru] 2+ or [(η 5 -Cp*)Rh] 2+ (p-cym = 1-methyl-4isopropylbenzene; Cp* = pentamethyl-cyclopentadienyl anion) entities play an important role as promising candidates with-depending upon the coordinating ligands-proven anticancer potential. Regarding the organoruthenium and -rhodium solution equilibrium studies, complexation of these cations with ambidentate type aminohydroxamates [13,14], peptidehydroxamates [15], histidine-containing oligopeptides [16,17], an 1,10-phenanthroline conjugated SAHA (SAHA = suberoylanilide hydroxamic acid) [18], an 8-hydroxy-quinolineproline hybrid [19] and with 2,4-dipicolinic acid [20] was already explored, too.…”

Section: Introductionmentioning

confidence: 99%

Donor Atom Preference of Organoruthenium and Organorhodium Cations on the Interaction with Novel Ambidentate (N,N) and (O,O) Chelating Ligands in Aqueous Solution

et al. 2021

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Two novel, pyridinone-based chelating ligands containing separated (O,O) and (Namino,Nhet) chelating sets (Namino = secondary amine; Nhet = pyrrole N for H(L3) (1-(3-(((1H-pyrrole-2-yl)methyl)amino)propyl)-3-hydroxy-2-methylpyridin-4(1H)-one) or pyridine N for H(L5) (3-hydroxy-2-methyl-1-(3-((pyridin-2-ylmethyl)amino)propyl)pyridin-4(1H)-one)) were synthesized via reduction of the appropriate imines. Their proton dissociation processes were explored, and the molecular structures of two synthons were assessed by X-ray crystallography. These ambidentate chelating ligands are intended to develop Co(III)/PGM (PGM = platinum group metal) heterobimetallic multitargeted complexes with anticancer potential. To explore their metal ion binding ability, the interaction with Pd(II), [(η6-p-cym)Ru]2+ and [(η5-Cp*)Rh]2+ (p-cym = 1-methyl-4-isopropylbenzene, Cp* = pentamethyl-cyclopentadienyl anion) cations was studied in aqueous solution with the combined use of pH-potentiometry, NMR and HR ESI-MS. In general, organorhodium was found to form more labile complexes over ruthenium, while complexation of the (N,N) chelating set was slower than the processes of the pyridinone unit with (O,O) coordination. Formation of the organoruthenium complexes starts at lower pH (higher thermodynamic stabilities of the corresponding complexes) than for [(η5-Cp*)Rh]2+ but, due to the higher affinity of [η6-p-cym)Ru]2+ towards hydrolysis, the complexed ligands are capable of competing with hydroxide ion in a lesser extent than for the rhodium systems. As a result, under biologically relevant conditions, the rhodium binding effectivity of the ligands becomes comparable or even slightly higher than their effectivity towards ruthenium. Our results indicate that H(L3) is a less efficient (N,N) chelator for these metal ions than H(L5). Similarly, due to the relative effectivity of the (O,O) and (N,N) chelates at a 1:1 metal-ion-to-ligand ratio, H(L5) coordinates in a (N,N) manner to both cations in the whole pH range studied while, for H(L3), the complexation starts with (O,O) coordination. At a 2:1 metal-ion-to-ligand ratio, H(L3) cannot hinder the intensive hydrolysis of the second metal ion, although a small amount of 2:1 complex with [(η5-Cp*)Rh]2+ can also be detected.

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Complex formation between [(η6-p-cym)Ru(H2O)3]2+ and oligopeptides containing three histidyl moieties

Cited by 8 publications

References 49 publications

Accurate prediction of vertical electronic transitions of Ni(II) coordination compounds via time dependent density functional theory

Accurate prediction of vertical electronic transitions of Ni(II) coordination compounds via time dependent density functional theory

Binding mechanisms of half-sandwich Rh(III) and Ru(II) arene complexes on human serum albumin: a comparative study

Donor Atom Preference of Organoruthenium and Organorhodium Cations on the Interaction with Novel Ambidentate (N,N) and (O,O) Chelating Ligands in Aqueous Solution

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