Electronic structure contributions to function in bioinorganic chemistry

Solomon, Edward I.; Lowery, Michael D.

doi:10.1126/science.8384374

Cited by 406 publications

(244 citation statements)

References 63 publications

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“…1 This prominent role has led to a considerable research effort to study the structure and dynamics of these systems with the aim of understanding their function. [2][3][4][5][6][7][8][9] Spectroscopic methods have played an important role in this work. A variety of spectroscopic techniques have been applied to study these proteins, predominantly by Solomon and co-workers.…”

Section: Introductionmentioning

confidence: 99%

Modelling the spectroscopy and dynamics of plastocyanin

Robinson

Besley

2010

Phys. Chem. Chem. Phys.

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The electronic absorption, electronic circular dichroism and X-ray absorption spectroscopy of the blue copper protein plastocyanin is studied with density functional theory, time-dependent density functional theory and multireference configuration interaction in conjunction with classical molecular dynamics simulations. A strong correlation is observed between the excitation energy of the intense ligand to metal charge transfer band and the copper-cysteine sulfur bond length. The results suggest that the copper-cysteine sulfur bond length in the crystal structure of plastocyanin is too short and should be closer to the corresponding bond lengths in related blue copper proteins. Averaging over many structural conformations is required to reproduce the major features of the experimental circular dichroism spectra. A correlation between the rotational strength of the ligand to metal charge transfer band and the distortion of the copper atom from the plane of the cysteine sulfur and histidine nitrogen atoms is found. X-ray absorption calculations show a smaller sulfur p orbital character in the singly occupied molecular orbital of cucumber basic protein compared to plastocyanin.

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Section: Introductionmentioning

confidence: 99%

Modelling the spectroscopy and dynamics of plastocyanin

Robinson

Besley

2010

Phys. Chem. Chem. Phys.

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“…Because of favorable combinations of covalency and oxidation/reduction potentials, the activation of molecular oxygen by its coordination to one or two supported ͑i.e., ligated͒ Cu͑I͒ ions is common to a number of biological and inorganic catalytic processes. [26][27][28][29][30][31][32][33][34][35][36][37][38][39] In the case of monocopper species LCuO 2 , where L is a general ligand or ligands, one possible oxidation state that may be assigned to the complex is LCu͑II͒O 2 ͑−͒; thus, the copper atom has been oxidized by one electron and the O 2 fragment is formally a superoxide radical anion. Similarly, in the case of dicopper species ͑LCu͒ 2 O 2 , one possible oxidation state of the complex is formally ͓LCu͑II͔͒ 2 ͓͑O 2 ͒͑2−͔͒; in this instance, each copper atom has been oxidized by one electron and the O 2 fragment is formally a peroxide dianion.…”

Section: Application To Supported Cuo 2 and Cu 2 O 2 Systemsmentioning

confidence: 99%

The restricted active space followed by second-order perturbation theory method: Theory and application to the study of CuO2 and Cu2O2 systems

Malmqvist

Pierloot

Shahi

et al. 2008

The Journal of Chemical Physics

479

532

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A multireference second-order perturbation theory using a restricted active space self-consistent field wave function as reference ͑RASPT2/RASSCF͒ is described. This model is particularly effective for cases where a chemical system requires a balanced orbital active space that is too large to be addressed by the complete active space self-consistent field model with or without second-order perturbation theory ͑CASPT2 or CASSCF, respectively͒. Rather than permitting all possible electronic configurations of the electrons in the active space to appear in the reference wave function, certain orbitals are sequestered into two subspaces that permit a maximum number of occupations or holes, respectively, in any given configuration, thereby reducing the total number of possible configurations. Subsequent second-order perturbation theory captures additional dynamical correlation effects. Applications of the theory to the electronic structure of complexes involved in the activation of molecular oxygen by mono-and binuclear copper complexes are presented. In the mononuclear case, RASPT2 and CASPT2 provide very similar results. In the binuclear cases, however, only RASPT2 proves quantitatively useful, owing to the very large size of the necessary active space.

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“…In this homogeneous chemistry, the bis(µ-oxo)dicopper core is capable of isomerizing to the (µ-η 2 :η 2 -peroxo)dicopper core, i.e., [Cu 2 (µ-η 2 :η 2 -O 2 )] 2+ (Structure B) [51,52]. The latter peroxo-dicopper core is also present in the enzyme hemocyanin, found in arthropods and mollusks, where it performs the reversible binding of O 2 [53,54]. Therefore, we suggested that the bis(µ-oxo)dicopper core in Cu-ZSM-5 fulfills the key role of the continuous O 2 release and in this way guarantees the sustained high activity of Cu-ZSM-5 [49].…”

Section: Introductionmentioning

confidence: 99%

An operando optical fiber UV–vis spectroscopic study of the catalytic decomposition of NO and N2O over Cu-ZSM-5

Groothaert

Lievens

Leeman

et al. 2003

Journal of Catalysis

137

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The role of the bis(µ-oxo)dicopper core, i.e., [Cu 2 (µ-O) 2 ] 2+ , in the decomposition of NO and N 2 O by the Cu-ZSM-5 zeolite has been studied with combined operando UV-vis monitoring of the catalyst and on-line GC analysis. An optical fiber was mounted on the outer surface of the quartz wall of the plug-flow reactor and collected the UV-vis diffuse reflectance spectra under true catalytic conditions.

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Electronic structure contributions to function in bioinorganic chemistry

Cited by 406 publications

References 63 publications

Modelling the spectroscopy and dynamics of plastocyanin

Modelling the spectroscopy and dynamics of plastocyanin

The restricted active space followed by second-order perturbation theory method: Theory and application to the study of CuO2 and Cu2O2 systems

An operando optical fiber UV–vis spectroscopic study of the catalytic decomposition of NO and N2O over Cu-ZSM-5

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