Dataset Information

Comparison of the equilibrium, kinetic and water exchange properties of some metal ion-DOTA and DOTA-bis(amide) complexes.

ABSTRACT: The 1,7-diacetate-4,10-diacetamide substituted 1,4,7,10-tetraazacyclododecane structural unit is common to several responsive Magnetic Resonance Imaging (MRI) contrast agents (CAs). While some of these complexes (agents capable of sensing fluctuations in Zn²⁺, Ca²⁺ etc. ions) have already been tested in vivo, the detailed physico-chemical characterization of such ligands have not been fully studied. To fill this gap, we synthesized a representative member of this ligand family possessing two acetate and two n-butylacetamide pendant side-arms (DO2A2M^nBu?=?1,4,7,10-tetraazacyclodoecane-1,7-di(acetic acid)-4,10-di(N-butylacetamide)), and studied its complexation properties with some essential metal and a few lanthanide(III) (Ln(III)) ions. Our studies revealed that the ligand basicity, the stability of metal ion complexes, the trend of stability constants along the Ln(III) series, the formation rates of the Ln(III) complexes and the exchange rate of the bound water molecule in the Gd(III) complex fell between those of Ln(DOTA)^- and Ln(DOTA-tetra(amide))³⁺ complexes (DOTA?=?1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid, DOTAM?=?1,4,7,10-tetrakis(carbamoylmethyl)-1,4,7,10-tetraazacyclododecane). The only exception is the stability of Cu(DO2A2M^nBu) which was found to be only slightly lower than that of Cu(DOTA)^2- (log K_CuL?=?19.85 vs. 21.98). This is likely reflects exclusive coordination of the negatively charged acetate donor atoms to the Cu²⁺ ion forming an octahedral complex with the amides remaining uncoordinated. The only anomaly observed during the study was the rates of acid assisted dissociation of the Ln(III) complexes, which occur at a rate similar to those observed for the Ln(DOTA)^- complexes. These data indicate that even though the Ln(DO2A2M^nBu)⁺ complexes have lower thermodynamic stabilities, their kinetic inertness should be sufficient for in vivo use.

SUBMITTER: Tircso G

PROVIDER: S-EPMC7937998 | biostudies-literature | 2020 May

REPOSITORIES: biostudies-literature

ACCESS DATA

Publications

Comparison of the equilibrium, kinetic and water exchange properties of some metal ion-DOTA and DOTA-bis(amide) complexes.

Tircsó Gyula G Tircsóné Benyó Enikő E Garda Zoltán Z Singh Jaspal J Trokowski Robert R Brücher Ernő E Sherry A Dean AD Tóth Éva É Kovács Zoltán Z

Journal of inorganic biochemistry 20200220

The 1,7-diacetate-4,10-diacetamide substituted 1,4,7,10-tetraazacyclododecane structural unit is common to several responsive Magnetic Resonance Imaging (MRI) contrast agents (CAs). While some of these complexes (agents capable of sensing fluctuations in Zn<sup>2+</sup>, Ca<sup>2+</sup> etc. ions) have already been tested in vivo, the detailed physico-chemical characterization of such ligands have not been fully studied. To fill this gap, we synthesized a representative member of this ligand fam ...[more]

PMID: 32146160

Similar Datasets

Project description:Highlights • We derive a model that provides an exact solution to the substrate-water exchange kinetics in a double-conformation system.• This model is used to interpret recently published data for Ca2+- and Sr2+-containing PSII in the S2 state, in which the g = 2.0 and g = 4.1 conformations coexist.• The component concentrations derived from the kinetic model provide an analytic description of the substrate-water exchange kinetics.• Contrary to previous reports, there is no significant effect of substituting Sr2+ for Ca2+ on any of the exchange rate constants.• The exchange rate of the slowly-exchanging water (Ws) in the S2 state g = 4.1 conformation is much faster than that in the g = 2.0 conformation, consistent with the assignment of Ws to W1 or W2 bound as terminal ligands to Mn4. We derive a model that provides an exact solution to the substrate-water exchange kinetics in a double-conformation system and use this model to interpret recently published data for Ca2+- and Sr2+-containing PSII in the S2 state, in which the g = 2.0 and g = 4.1 conformations coexist. The component concentrations derived from the kinetic model provide an analytic description of the substrate-water exchange kinetics, allowing us to more accurately interpret the results. Based on this model and the previously reported data on the S2 state g = 2.0 conformation, we obtain the substrate-water exchange rates of the g = 4.1 conformation and the conformational change rates. Two conclusions are made from the analyses. First, contrary to previous reports, there is no significant effect of substituting Sr2+ for Ca2+ on any of the exchange rate constants. Second, the exchange rate of the slowly-exchanging water (Ws) in the S2 state g = 4.1 conformation is much faster than that in the S2 state g = 2.0 conformation. The second conclusion is consistent with the assignment of Ws to W1 or W2 bound as terminal ligands to Mn4; Mn4 has been proposed to undergo an oxidation state change from Mn(IV) in the g = 2.0 conformation to Mn(III) in the g = 4.1 conformation.

Dataset Information

Comparison of the equilibrium, kinetic and water exchange properties of some metal ion-DOTA and DOTA-bis(amide) complexes.

Publications

Comparison of the equilibrium, kinetic and water exchange properties of some metal ion-DOTA and DOTA-bis(amide) complexes.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets