Dioxygen Activation by Mononuclear Copper Enzymes: Insights from a Tripodal Ligand Mimicking Their Cu<sub>M</sub> Coordination Sphere

Lande, Aurélien de la; Salahub, Dennis R.; Moliner, Vicent; Gérard, Hélène; Piquemal, Jean‐Philip; Parisel, Olivier

doi:10.1021/ic900567z

Cited by 12 publications

(12 citation statements)

References 25 publications

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“…The SF-TDDFT strategy has already been applied to several problems in chemistry, such as the study of the diradical character and singlet-triplet splittings of organic systems [25][26][27][28] and the study of organic triradicals, 21 bioinorganic chemistry, [29][30][31][32] conical intersections, 33,34 and electron transfer couplings. [35][36][37] Multiplicity-changing excitation energies are of special interest for transition metals, which have many spin states with very small energy differences.…”

Section: Introductionmentioning

confidence: 99%

Density functional study of multiplicity-changing valence and Rydberg excitations of p-block elements: Delta self-consistent field, collinear spin-flip time-dependent density functional theory (DFT), and conventional time-dependent DFT

Yang

Peverati

Truhlar

et al. 2011

The Journal of Chemical Physics

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A database containing 17 multiplicity-changing valence and Rydberg excitation energies of p-block elements is used to test the performance of density functional theory (DFT) with approximate density functionals for calculating relative energies of spin states. We consider only systems where both the low-spin and high-spin state are well described by a single Slater determinant, thereby avoiding complications due to broken-symmetry solutions. Because the excitations studied involve a spin change, they require a balanced treatment of exchange and correlation, thus providing a hard test for approximate density functionals. We test three formalisms for predicting the multiplicity-changing transition energies. First is the ΔSCF method; we also test time-dependent density functional theory (TDDFT), both in its conventional form starting from the low-spin state and in its collinear spin-flip form starting from the high-spin state. Very diffuse basis functions are needed to give a qualitatively correct description of the Rydberg excitations. The scalar relativistic effect needs to be considered when quantitative results are desired, and we include it in the comparisons. With the ΔSCF method, most of the tested functionals give mean unsigned errors (MUEs) larger than 6 kcal/mol for valence excitations and MUEs larger than 3 kcal/mol for Rydberg excitations, but the performance for the Rydberg states is much better than can be obtained with time-dependent DFT. It is surprising to see that the long-range corrected functionals, which have 100% Hartree-Fock exchange at large inter-electronic distance, do not improve the performance for Rydberg excitations. Among all tested density functionals, ΔSCF calculations with the O3LYP, M08-HX, and OLYP functionals give the best overall performance for both valence and Rydberg excitations, with MUEs of 2.1, 2.6, and 2.7 kcal/mol, respectively. This is very encouraging since the MUE of the CCSD(T) coupled cluster method with quintuple zeta basis sets is 2.0 kcal/mol; however, caution is advised since many popular density functionals give poor results, and there can be very significant differences between the ΔSCF predictions and those from TDDFT.

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Section: Introductionmentioning

confidence: 99%

Density functional study of multiplicity-changing valence and Rydberg excitations of p-block elements: Delta self-consistent field, collinear spin-flip time-dependent density functional theory (DFT), and conventional time-dependent DFT

Yang

Peverati

Truhlar

et al. 2011

The Journal of Chemical Physics

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“…To go a step further towards accuracy we have also considered the recent Spin-Flip Time-Dependent DFT formalism (SF-DFT) as an alternative to the BS-DFT techniques (de la Lande et al , 2007; de la Lande et al , 2008a; de la Lande et al , 2008b; de la Lande et al , 2009). This approach was shown to bevery promising for the treatment of mononuclear Cu/O 2 adducts found in non-coupled copper monooxygenases.…”

Section: Choice Of the Model And Methodologiesmentioning

confidence: 99%

Study of the docking of competitive inhibitors at a model of tyrosinase active site: Insights from joint broken-symmetry/spin-flip DFT computations and ELF topological analysis

Lande¹,

Maddaluno²,

Parisel³

et al. 2010

Interdiscip Sci Comput Life Sci

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Following our previous study (Piquemal et al., New J. Chem., 2003, 27, 909), we present here a DFT study of the inhibition of the Tyrosinase enzyme. Broken-symmetry DFT computations are supplemented with Spin-Flip TD-DFT calculations, which, for the first time, are applied to such a dicopper enzyme. The chosen biomimetic model encompasses a dioxygen molecule, two Cu(II) cations, and six imidazole rings. The docking energy of a natural substrate, namely phenolate, together with those of several inhibitor and non-inhibitor compounds, are reported and show the ability of the model to rank the most potent inhibitors in agreement with experimental data. With respect to broken-symmetry calculations, the Spin-Flip TD-DFT approach reinforces the possibility for theory to point out potent inhibitors: the need for the deprotonation of the substrates, natural or inhibitors, is now clearly established. Moreover, Electron Localization Function (ELF) topological analysis computations are used to deeply track the particular electronic distribution of the Cu-O-Cu three-center bonds involved in the enzymatic Cu 2 O 2 metallic core (Piquemal and Pilmé, J. Mol. Struct.: Theochem, 2006, 77, 764). It is shown that such bonds exhibit very resilient out-of-plane density expansions that play a key role in docking interactions: their 3D-orientation could be the topological electronic signature of oxygen activation within such systems.

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“…It contains a Cu 2 /(μ − η 2 : η 2 − O 2 ) core with an unusual organization consisting of a three‐center CuOCu bond 21. The second adduct, [(Mim N2S )Cu(O 2 )] + , is a biomimicking model of the Cu M active site found in the noncoupled dicopper enzymes PHM, DβM, and TβM 22. These systems have been studied in their singlet and triplet spin states through extensive use of MOs, see, for example, ref 23.…”

Section: Positions and Characteristics (Volume/population) Of The Valmentioning

confidence: 99%

“…The singlet–triplet gaps (in kcal/mol), extracted from refs. 22 and 24, were computed with a spin‐flip TD‐DFT (details can be found in Supporting Information).…”

Section: Positions and Characteristics (Volume/population) Of The Valmentioning

confidence: 99%

Spin‐driven activation of dioxygen in various metalloenzymes and their inspired models

Lande¹,

Salahub²,

Maddaluno³

et al. 2010

J Comput Chem

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Although potentially powerful, molecular oxygen is an inert oxidant due to the triplet nature of its ground state. Therefore, many enzymesse various metal cations (M) to produce singlet active species M(n) O(2) . In this communication we investigate the topology of the Electron Localization Function (ELF) within five biomimetic complexes which are representative of the strategies followed by metalloenzymes to activate O(2) . Thanks to its coupling to the constrained DFT methods the ELF analysis reveals the tight connection between the spin state of the adduct and the spatial organization of the oxygen lone pairs. We suggest that enzymes could resort to spin state control to tune the regioselectivity of substrate oxidations.

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Dioxygen Activation by Mononuclear Copper Enzymes: Insights from a Tripodal Ligand Mimicking Their Cu_M Coordination Sphere

Cited by 12 publications

References 25 publications

Density functional study of multiplicity-changing valence and Rydberg excitations of p-block elements: Delta self-consistent field, collinear spin-flip time-dependent density functional theory (DFT), and conventional time-dependent DFT

Density functional study of multiplicity-changing valence and Rydberg excitations of p-block elements: Delta self-consistent field, collinear spin-flip time-dependent density functional theory (DFT), and conventional time-dependent DFT

Study of the docking of competitive inhibitors at a model of tyrosinase active site: Insights from joint broken-symmetry/spin-flip DFT computations and ELF topological analysis

Spin‐driven activation of dioxygen in various metalloenzymes and their inspired models

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Dioxygen Activation by Mononuclear Copper Enzymes: Insights from a Tripodal Ligand Mimicking Their CuM Coordination Sphere

Cited by 12 publications

References 25 publications

Density functional study of multiplicity-changing valence and Rydberg excitations of p-block elements: Delta self-consistent field, collinear spin-flip time-dependent density functional theory (DFT), and conventional time-dependent DFT

Density functional study of multiplicity-changing valence and Rydberg excitations of p-block elements: Delta self-consistent field, collinear spin-flip time-dependent density functional theory (DFT), and conventional time-dependent DFT

Study of the docking of competitive inhibitors at a model of tyrosinase active site: Insights from joint broken-symmetry/spin-flip DFT computations and ELF topological analysis

Spin‐driven activation of dioxygen in various metalloenzymes and their inspired models

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Dioxygen Activation by Mononuclear Copper Enzymes: Insights from a Tripodal Ligand Mimicking Their Cu_M Coordination Sphere