Nickel Complexes of Carboxylate-Containing Polydentate Ligands as Models for the Active Site of Urease

Carlsson, Håkan; Haukka, Matti; Bousseksou, Azzedine; Latour, Jean‐Marc; Nordlander, Ebbe

doi:10.1021/ic049048u

Cited by 94 publications

(57 citation statements)

References 69 publications

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“…31-33 and Carlsson, et al . 34-37 are developed from the AOM and the ligand field (LF) effects are handled through explicit diagonalization of a perturbed d-orbital matrix due to the presence of ligands. These methods have demonstrated satisfactory agreements with experiments and ab initio calculations when used to study a range of TM systems with different coordination geometries and ligation states.…”

Section: Introductionmentioning

confidence: 99%

An Angular Overlap Model for Cu(II) Ion in the AMOEBA Polarizable Force Field

Xiang

Ponder

2013

J. Chem. Theory Comput.

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An extensible polarizable force field for transition metal ion was developed based on AMOEBA and the angular overlap model (AOM) with consistent treatment of electrostatics for all atoms. Parameters were obtained by fitting molecular mechanics (MM) energies to various ab initio gas-phase calculations. The results of parameterization were presented for copper (II) ion ligated to water and model fragments of amino acid residues involved in the copper binding sites of type 1 copper proteins. Molecular dynamics (MD) simulations were performed on aqueous copper (II) ion at various temperatures, as well as plastocyanin (1AG6) and azurin (1DYZ). Results demonstrated that the AMOEBA-AOM significantly improves the accuracy of classical MM in a number of test cases when compared to ab initio calculations. The Jahn-Teller distortion for hexa-aqua copper (II) complex was handled automatically without specifically designating axial and in-plane ligands. Analyses of MD trajectories resulted in a 6-coordination first solvation shell for aqueous copper (II) ion and a 1.8ns average residence time of water molecules. The ensemble average geometries of 1AG6 and 1DYZ copper binding sites were in general agreement with X-ray and previous computational studies.

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Section: Introductionmentioning

confidence: 99%

An Angular Overlap Model for Cu(II) Ion in the AMOEBA Polarizable Force Field

Xiang

Ponder

2013

J. Chem. Theory Comput.

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“…1) have been shown to stabilize dinuclear species [20][21][22] [23] could be grown and their structures were determined by X-ray diffraction (Fig. 2) [24].…”

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confidence: 99%

Systematic synthesis of functional unsymmetric FeZn model complexes for plant purple acid phosphatases

Jarenmark

Carlsson

Трухан

et al. 2010

Inorganic Chemistry Communications

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a b s t r a c tThe heterodinuclear complexes [FeZn(L)(CH 3 CO 2 ) 2 ] + (L = ICIMP or IPCPMP) are structural models for the dinuclear active sites of plant purple acid phosphatases. They can be systematically synthesized from mononuclear iron complexes and enhance the rate of transesterification of 2-hydroxypropyl p-nitrophenyl phosphate, an assay for the catalytic hydrolysis performed by purple acid phosphatases.Ó 2009 Elsevier B.V. All rights reserved.The purple acid phosphatases catalyze the hydrolysis of phosphoesters at acidic pH. This class of enzymes contain active sites with dinuclear Fe(III)M(II) (M = Fe, Zn, Mn) cores [1], a number of which have been crystallographically characterized [2][3][4][5][6][7][8]. The structures of the active sites of the purple acid phosphatases isolated from plants are closely related and contain one iron and one zinc ion about 3.0-3.4 Å apart. The metals are ligated by histidines, tyrosines and carboxylate-containing amino acid residues and bridged by one of the carboxylate oxygens of an aspartate and a water or hydroxide molecule.The publication of the crystal structure of kidney bean purple acid phosphatase (kbPAP) [2] has provided impetus for the preparation of model complexes that may aid in the elucidation of the catalytic mechanism of this and related enzymes. Thus, FeZn complexes based on dinucleating ligands that contain a central bridging phenolate moiety have been published [9][10][11][12][13][14][15][16][17][18][19]. These model complexes have been prepared by simultaneous or stepwise addition of one equivalent of each metal salt. Here, we wish to present the controlled stepwise assembly of model complexes for kbPAP that not only contain an unsymmetric coordination environment, but also provide a vacant coordination site on one metal.The unsymmetric ligands H 2 ICIMP and H 2 IPCPMP (Fig. 1) have been shown to stabilize dinuclear species [20-22]. Addition of Fe (ClO 4 ) 3 (1-2 equivalents) to H 2 ICIMP in methanol, or FeCl 3 to an acetonitrile solution of H 4 IPCPMP(PF 6 ) 2 , yields purple solutions. The purple color indicates coordination of the phenolate moieties of the unsymmetric ligands; the color arises from the phenolate? Fe(III) LMCT electronic transition. Deep purple single crystals of the products [Fe(H 2 ICIMP)(H 2 O)Cl][Fe(H 2 ICIMP)(MeOH)Cl] [ClO 4 ] 4 (1) and [Fe(H 2 IPCPMP)Cl 2 ][PF 6 ] (2) [23] could be grown and their structures were determined by X-ray diffraction (Fig. 2) [24]. The structure of 1 contains two separate octahedrally coordinated Fe(ICIMP) molecules, which only differ in the bound solvent molecules (water or methanol). The iron(III) ion is in both cases located in the tetradentate pocket of the ligand, in keeping with the chelate effect. Another reason for the site preference may be the preference of the hard iron(III) ion for the hard carboxylate oxygen donor [25]. It is likely that the chloride ion originates from the ligand, which was isolated as a hydrochloride salt [26]. The crystal structure of 2 (Fig. 2, bottom) reveals an e...

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“…Ligand H 3 L 3 [16], N-(6-(((pyridin-2-ylmethyl)amino)methyl)pyridin-2-yl)pivalamide (1) [24,27,28], 3-(chloromethyl)-2-hydroxy-5-methylbenzaldehyde (2) [29,30], 2-(aminomethyl)phenol (4) [31], N-(6-(bromomethyl)pyridin-2-yl)pivalamide (6) [27,[32][33][34], BDNPP [35], and DNPP [36] were prepared as described previously 4.1.1.1. Compound 3.…”

Section: Ligand Synthesesmentioning

confidence: 99%

Asymmetric mono- and dinuclear Ga III and Zn II complexes as models for purple acid phosphatases

Bosch

Comba

Gahan

et al. 2016

Journal of Inorganic Biochemistry

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Derivatives of the known dinucleating ligands HL (2,6-bis{[bis(pyridin-2-ylmethyl)amino]methyl}-4-methylphenol) and HL (2-{[bis(pyridin-2-ylmethyl)amino]methyl}-6-{[(2-hydroxybenzyl)(pyridine-2-ylmethyl)amino]methyl}-4-methylphenol) with two pivaloylamido hydrogen bond donor substituents, HL and HL, have been prepared. The mono-, homo- and heterodinuclear Zn and Ga complexes of these ligands have been prepared and characterized. The solution equilibria are discussed on the basis of extensive NMR spectroscopic, mass spectrometric and pH-dependent UV-vis spectroscopic titrations. The phosphoester hydrolysis activity of the complexes has been studied as a function of pH and substrate concentration and analyzed using Michaelis-Menten kinetics. It emerges that the mixed metal (mixed valent) complex of the ligand with an asymmetric disposition of the hydrogen bonding substituents (HL) is a functional model for the mixed valent, dinuclear metallohydrolase purple acid phosphatase. This complex combines the essential structural features of the active site of PAP and is the first heterodinuclear model complex mimicking the essential function of PAPs, i.e. the hydrolysis of phosphomonoesters.

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Nickel Complexes of Carboxylate-Containing Polydentate Ligands as Models for the Active Site of Urease

Cited by 94 publications

References 69 publications

An Angular Overlap Model for Cu(II) Ion in the AMOEBA Polarizable Force Field

An Angular Overlap Model for Cu(II) Ion in the AMOEBA Polarizable Force Field

Systematic synthesis of functional unsymmetric FeZn model complexes for plant purple acid phosphatases

Asymmetric mono- and dinuclear Ga III and Zn II complexes as models for purple acid phosphatases

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